阅读说明：本技术 聚四氟乙烯和拉伸体 (Polytetrafluoroethylene and stretched body ) 是由 加藤丈人 藤本阳平 市川贤治 佐藤洋之 宇佐美亮太 难波义典 吉田裕俊 伊藤剑吾 奥 于 2019-07-23 设计创作，主要内容包括：本发明提供一种拉伸性优异的聚四氟乙烯。本发明涉及一种聚四氟乙烯,其特征在于,标准比重为2.175以下,热不稳定指数(TII)为20以上。(The invention provides polytetrafluoroethylene with excellent stretchability. The present invention relates to polytetrafluoroethylene characterized by having a standard specific gravity of 2.175 or less and a Thermal Instability Index (TII) of 20 or more.)

1. A polytetrafluoroethylene, characterized in that,

the standard specific gravity is below 2.175,

the thermal instability index TII is 20 or more.

2. A polytetrafluoroethylene, characterized in that,

the standard specific gravity is below 2.175,

the 0.1% weight loss temperature is below 400 ℃.

3. A polytetrafluoroethylene, characterized in that,

the standard specific gravity is below 2.175,

the 1.0% weight loss temperature is below 492 ℃.

4. A polytetrafluoroethylene, characterized in that,

the breaking strength is more than 10.0N,

the thermal instability index TII is 20 or more.

5. A polytetrafluoroethylene, characterized in that,

the breaking strength is more than 10.0N,

the 0.1% weight loss temperature is below 400 ℃.

6. A polytetrafluoroethylene, characterized in that,

the breaking strength is more than 10.0N,

the 1.0% weight loss temperature is below 492 ℃.

7. The polytetrafluoroethylene according to any of claims 1-6,

the stress relaxation time is 50 seconds or more.

8. The polytetrafluoroethylene according to any of claims 1-7,

the extrusion pressure is 30.0MPa or less.

9. The polytetrafluoroethylene according to any of claims 1-8,

the polytetrafluoroethylene is molded, heat-treated at 100 ℃ for 2 hours, at 200 ℃ for 4 hours, and at 370 ℃ for 5 hours, and the brightness L of a sheet cut from the thus-obtained fired body is 90.0 or less.

10. The polytetrafluoroethylene according to any of claims 1-9,

the heat shrinkage of the fired body obtained by molding polytetrafluoroethylene, heat-treating at 100 ℃ for 2 hours, at 200 ℃ for 4 hours, and at 370 ℃ for 5 hours is 7.0% or more.

11. The polytetrafluoroethylene according to any of claims 1-10,

the polytetrafluoroethylene is molded, heat-treated at 100 ℃ for 2 hours, at 200 ℃ for 4 hours, and at 370 ℃ for 5 hours, and the contact angle of the surface of the sheet cut out from the fired body obtained by the molding is 107 DEG or more, the surface corresponding to the inside of the fired body.

12. The polytetrafluoroethylene according to any of claims 1-11 as a powder.

13. A stretched body comprising the polytetrafluoroethylene according to any one of claims 1-12.

Technical Field

The present invention relates to polytetrafluoroethylene and an elongated body.

Background

When polytetrafluoroethylene is molded and highly stretched in an unfired state, a porous polytetrafluoroethylene film can be obtained. The porous membrane is permeable to gas such as water vapor, but water droplets cannot pass through the porous membrane because of the high water resistance of polytetrafluoroethylene. The unique property is utilized to be applied to clothes, separation membranes and the like.

Patent document 1 describes a method for polymerizing a fluorine-containing monomer in a polymerization reactor to form a dispersion of fluorine-containing polymer particles in an aqueous medium, the method including an initial period and a stabilization period following the initial period, the initial period including a step of preparing an initial dispersion of fluorine-containing polymer particles in the aqueous medium in the polymerization reactor, the stabilization period including a step of polymerizing a fluorine-containing monomer in the polymerization reactor and a step of adding a hydrocarbon-containing surfactant to the polymerization reactor, and the fluorine-containing surfactant is not added during the stabilization period.

Patent document 2 describes a method for polymerizing a fluorine-containing monomer in a polymerization reactor to form a dispersion of fluorine-containing polymer particles in an aqueous medium, the method including an initial period including a step of adding (a) an aqueous medium, (b) a water-soluble hydrocarbon-containing compound, (c) a decomposing agent, (d) a fluorine-containing monomer, and (e) a polymerization initiator to the polymerization reactor, and the decomposing agent is added before the polymerization initiator without adding a fluorine-based surfactant to the initial period.

Patent document 3 describes a method for polymerizing a fluorine-containing monomer in a polymerization reactor to form a dispersion of fluorine-containing polymer particles in an aqueous medium, which comprises: a step of charging an aqueous medium, a polymerization initiator, a fluorine-containing monomer and a hydrocarbon-containing surfactant into the polymerization reactor; and a step of deactivating the hydrocarbon-containing surfactant.

Patent document 4 describes a method for reducing thermochromism of a fluorinated polymer resin produced by the following steps: a step of polymerizing a fluorine-containing monomer in an aqueous dispersion medium to form an aqueous fluorinated polymer dispersion; separating the fluorinated polymer resin in a wet form from the aqueous medium to separate the fluorinated polymer from the aqueous medium; and drying to produce a fluorinated polymer resin in dry form, said method comprising the step of exposing said fluorinated polymer resin in wet or dry form to an oxidizing agent.

Documents of the prior art

Patent document

Patent document 1: japanese Kohyo publication No. 2013-542308

Patent document 2: japanese Kohyo publication No. 2013-542309

Patent document 3: japanese Kohyo publication No. 2013-542310

Patent document 4: international publication No. 2013/169581

Disclosure of Invention

Problems to be solved by the invention

The invention provides polytetrafluoroethylene with excellent stretchability and a stretched body containing the polytetrafluoroethylene. The present invention preferably provides a stretched body excellent in breaking strength and stress relaxation time.

Means for solving the problems

The present invention relates to polytetrafluoroethylene characterized by having a standard specific gravity of 2.175 or less and a Thermal Instability Index (TII) of 20 or more.

The present invention also relates to a polytetrafluoroethylene having a standard specific gravity of 2.175 or less and a 0.1% weight loss temperature of 400 ℃ or less.

The present invention also relates to polytetrafluoroethylene having a standard specific gravity of 2.175 or less and a 1.0% weight loss temperature of 492 ℃ or less.

The present invention also relates to a polytetrafluoroethylene having a breaking strength of 10.0N or more and a Thermal Instability Index (TII) of 20 or more.

The present invention also relates to a polytetrafluoroethylene having a breaking strength of 10.0N or more and a 0.1% weight loss temperature of 400 ℃ or less.

The present invention also relates to polytetrafluoroethylene having a breaking strength of 10.0N or more and a 1.0% weight loss temperature of 492 ℃ or less.

The polytetrafluoroethylene of the invention preferably has a stress relaxation time of 50 seconds or more.

The polytetrafluoroethylene of the invention is preferably extruded at a pressure of 30.0MPa or less.

The polytetrafluoroethylene of the present invention is molded, heat-treated at 100 ℃ for 2 hours, heat-treated at 200 ℃ for 4 hours, and heat-treated at 370 ℃ for 5 hours, and the brightness L of a sheet cut out from the thus-obtained fired body is preferably 90.0 or less.

The polytetrafluoroethylene of the present invention is molded, heat-treated at 100 ℃ for 2 hours, heat-treated at 200 ℃ for 4 hours, and heat-treated at 370 ℃ for 5 hours, and the heat shrinkage of the resulting fired body is preferably 7.0% or more.

In the polytetrafluoroethylene of the present invention, the contact angle of the surface corresponding to the inside of the fired body of the sheet cut out from the fired body thus obtained is preferably 107 ° or more by molding the polytetrafluoroethylene, heat-treating at 100 ℃ for 2 hours, heat-treating at 200 ℃ for 4 hours, and heat-treating at 370 ℃ for 5 hours.

The polytetrafluoroethylene of the invention is preferably a powder.

The present invention also relates to a stretched body comprising the polytetrafluoroethylene.

ADVANTAGEOUS EFFECTS OF INVENTION

The polytetrafluoroethylene of the present invention has the above-described structure, and therefore has excellent stretchability. The drawn body of the present invention has the above-described structure, and therefore, is excellent in breaking strength and stress relaxation time.

Detailed Description

In the present specification, unless otherwise specified, "organic group" means a group containing 1 or more carbon atoms or a group formed by removing 1 hydrogen atom from an organic compound.

Examples of the "organic group" include:

an alkyl group which may have 1 or more substituents,

An alkenyl group which may have 1 or more substituents,

An alkynyl group which may have 1 or more substituents,

Cycloalkyl which may have 1 or more substituents,

Cycloalkenyl group which may have 1 or more substituents,

A cycloalkadienyl group which may have 1 or more substituents,

An aryl group which may have 1 or more substituents,

An aralkyl group which may have 1 or more substituents,

A non-aromatic heterocyclic group which may have 1 or more substituents,

A heteroaryl group which may have 1 or more substituents,

A cyano group,

Formyl, methyl,

RaO-、

RaCO-、

RaSO₂-、

RaCOO-、

RaNRaCO-、

RaCONRa-、

RaOCO-、

RaOSO₂-, and,

RaNRbSO₂-

(in the formulae, Ra is independently

An alkyl group which may have 1 or more substituents,

An alkenyl group which may have 1 or more substituents,

An alkynyl group which may have 1 or more substituents,

Cycloalkyl which may have 1 or more substituents,

Cycloalkenyl group which may have 1 or more substituents,

A cycloalkadienyl group which may have 1 or more substituents,

An aryl group which may have 1 or more substituents,

An aralkyl group which may have 1 or more substituents,

A non-aromatic heterocyclic group which may have 1 or more substituents, or

A heteroaryl group which may have 1 or more substituents,

rb is independently H or an alkyl group which may have 1 or more substituents).

The organic group is preferably an alkyl group which may have 1 or more substituents.

In the present specification, the term "substituent" refers to a group that can be substituted. Examples of the "substituent" include: aliphatic group, aromatic group, heterocyclic group, acyl group, acyloxy group, acylamino group, aliphatic oxy group, aromatic oxy group, heterocyclic oxy group, aliphatic oxycarbonyl group, aromatic oxycarbonyl group, heterocyclic oxycarbonyl group, carbamoyl group, aliphatic sulfonyl group, aromatic sulfonyl group, heterocyclic sulfonyl group, aliphatic sulfonyloxy group, aromatic sulfonyloxy group, heterocyclic sulfonyloxy group, sulfamoyl group, aliphatic sulfonamide group, aromatic sulfonamide group, heterocyclic sulfonamide group, amino group, aliphatic amino group, aromatic amino group, heterocyclic amino group, aliphatic oxycarbonylamino group, aromatic oxycarbonylamino group, heterocyclic oxycarbonylamino group, aliphatic sulfinyl group, aromatic sulfinyl group, aliphatic thio group, aromatic thio group, hydroxyl group, cyano group, sulfo group, carboxyl group, aliphatic oxyamino group, aromatic oxyamino group, carbamoyl aminocarbonyl group, amino group, heterocyclic oxycarbonyl amino group, heterocyclic oxycarbonylamino group, aliphatic sulfinyl group, aromatic, Sulfamoylamino, halogen atom, sulfamoylcarbamoyl, carbamoylsulfamoyl, dialiphatic oxyphosphinyl and diaryloxyphosphinyl.

The aliphatic group may be saturated or unsaturated, and may have a hydroxyl group, an aliphatic oxy group, a carbamoyl group, an aliphatic oxycarbonyl group, an aliphatic thio group, an amino group, an aliphatic amino group, an amido group, a carbamoylamino group, or the like. Examples of the aliphatic group include alkyl groups having 1 to 8, preferably 1 to 4, total carbon atoms, such as methyl, ethyl, vinyl, cyclohexyl, and carbamoylmethyl.

The aromatic group may have, for example, a nitro group, a halogen atom, an aliphatic oxy group, a carbamoyl group, an aliphatic oxycarbonyl group, an aliphatic thio group, an amino group, an aliphatic amino group, an acylamino group, a carbamoylamino group, or the like. Examples of the aromatic group include aryl groups having 6 to 12 carbon atoms, preferably 6 to 10 carbon atoms in total, such as phenyl, 4-nitrophenyl, 4-acetylaminophenyl, 4-methylsulfonylphenyl and the like.

The heterocyclic group may have a halogen atom, a hydroxyl group, an aliphatic oxy group, a carbamoyl group, an aliphatic oxycarbonyl group, an aliphatic thio group, an amino group, an aliphatic amino group, an acylamino group, a carbamoylamino group or the like. Examples of the heterocyclic group include 5-to 6-membered heterocyclic rings having 2 to 12, preferably 2 to 10, total carbon atoms, for example, 2-tetrahydrofuranyl group, 2-pyrimidinyl group and the like.

The acyl group may have an aliphatic carbonyl group, an arylcarbonyl group, a heterocyclic carbonyl group, a hydroxyl group, a halogen atom, an aromatic group, an aliphatic oxy group, a carbamoyl group, an aliphatic oxycarbonyl group, an aliphatic thio group, an amino group, an aliphatic amino group, an acylamino group, a carbamoylamino group, or the like. Examples of the acyl group include acyl groups having 2 to 8, preferably 2 to 4, total carbon atoms, such as acetyl, propionyl, benzoyl, and 3-pyridinecarbonyl.

The acylamino group may have an aliphatic group, an aromatic group, a heterocyclic group, etc., and may have, for example, an acetylamino group, a benzoylamino group, a 2-pyridinecarbonylamino group, a propionylamino group, etc. Examples of the acylamino group include acylamino groups having 2 to 12, preferably 2 to 8, total carbon atoms, alkylcarbonylamino groups having 2 to 8 total carbon atoms, for example, acetylamino group, benzoylamino group, 2-pyridinecarbonylamino group, propionylamino group and the like.

The aliphatic oxycarbonyl group may be saturated or unsaturated, and may have a hydroxyl group, an aliphatic oxy group, a carbamoyl group, an aliphatic oxycarbonyl group, an aliphatic thio group, an amino group, an aliphatic amino group, an amido group, a carbamoylamino group, or the like. Examples of the aliphatic oxycarbonyl group include an alkoxycarbonyl group having 2 to 8, preferably 2 to 4, total carbon atoms, such as a methoxycarbonyl group, an ethoxycarbonyl group, and a tert-butoxycarbonyl group.

The carbamoyl group may have an aliphatic group, an aromatic group, a heterocyclic group, or the like. Examples of the carbamoyl group include an unsubstituted carbamoyl group and an alkylcarbamoyl group having 2 to 9 total carbon atoms, preferably an unsubstituted carbamoyl group and an alkylcarbamoyl group having 2 to 5 total carbon atoms, for example, an N-methylcarbamoyl group, an N, N-dimethylcarbamoyl group, an N-phenylcarbamoyl group and the like.

The aliphatic sulfonyl group may be saturated or unsaturated, and may have a hydroxyl group, an aromatic group, an aliphatic oxy group, a carbamoyl group, an aliphatic oxycarbonyl group, an aliphatic thio group, an amino group, an aliphatic amino group, an acylamino group, a carbamoylamino group, or the like. Examples of the aliphatic sulfonyl group include alkylsulfonyl groups having 1 to 6, preferably 1 to 4, total carbon atoms, for example, methylsulfonyl group.

The aromatic sulfonyl group may have a hydroxyl group, an aliphatic oxy group, a carbamoyl group, an aliphatic oxycarbonyl group, an aliphatic thio group, an amino group, an aliphatic amino group, an acylamino group, a carbamoylamino group or the like. Examples of the aromatic sulfonyl group include arylsulfonyl groups having 6 to 10 total carbon atoms, for example, benzenesulfonyl groups.

The amino group may have an aliphatic group, an aromatic group, a heterocyclic group, or the like.

The acylamino group may have, for example, acetylamino, benzoylamino, 2-pyridinecarbonylamino, propionylamino and the like. Examples of the acylamino group include acylamino groups having 2 to 12 total carbon atoms, preferably 2 to 8 total carbon atoms, more preferably alkylcarbonylamino groups having 2 to 8 total carbon atoms, for example acetylamino group, benzoylamino group, 2-pyridinecarbonylamino group, propionylamino group and the like.

The aliphatic sulfonamide group, the aromatic sulfonamide group and the heterocyclic sulfonamide group may be, for example, a methylsulfonamide group, a benzenesulfonamide group, a 2-pyridinesulfonamide group or the like.

The sulfamoyl group may have an aliphatic group, an aromatic group, a heterocyclic group, or the like. Examples of the sulfamoyl group include a sulfamoyl group, an alkylsulfamoyl group having 1 to 9 total carbon atoms, a dialkylsulfamoyl group having 2 to 10 total carbon atoms, an arylsulfamoyl group having 7 to 13 total carbon atoms, and a heterocyclic sulfamoyl group having 2 to 12 total carbon atoms, and more preferably include a sulfamoyl group, an alkylsulfamoyl group having 1 to 7 total carbon atoms, a dialkylsulfamoyl group having 3 to 6 total carbon atoms, an arylsulfamoyl group having 6 to 11 total carbon atoms, and a heterocyclic sulfamoyl group having 2 to 10 total carbon atoms, such as a sulfamoyl group, a methylsulfamoyl group, an N, N-dimethylsulfamoyl group, a phenylsulfamoyl group, and a 4-pyridinesulfamoyl group.

The aliphatic oxy group may be saturated or unsaturated, and may have methoxy, ethoxy, isopropoxy, cyclohexyloxy, methoxyethoxy, or the like. Examples of the aliphatic oxy group include alkoxy groups having 1 to 8, preferably 1 to 6, total carbon atoms, for example, methoxy, ethoxy, isopropoxy, cyclohexyloxy, methoxyethoxy, and the like.

The aromatic amino group and the heterocyclic amino group may have an aliphatic group, an aliphatic oxy group, a halogen atom, a carbamoyl group, a heterocyclic group fused to the aryl group, or an aliphatic oxycarbonyl group, and preferably may have an aliphatic group having 1 to 4 total carbon atoms, an aliphatic oxy group having 1 to 4 total carbon atoms, a halogen atom, a carbamoyl group having 1 to 4 total carbon atoms, a nitro group, or an aliphatic oxycarbonyl group having 2 to 4 total carbon atoms.

The aliphatic thio group may be saturated or unsaturated, and examples thereof include alkylthio groups having 1 to 8 total carbon atoms, more preferably 1 to 6 total carbon atoms, such as methylthio, ethylthio, carbamoylmethylthio, and tert-butylthio.

The carbamoylamino group may have an aliphatic group, an aryl group, a heterocyclic group or the like. Examples of the carbamoylamino group include a carbamoylamino group, an alkylcarbamoylamino group having 2 to 9 total carbon atoms, a dialkylcarbamoylamino group having 3 to 10 total carbon atoms, an arylcarbamoylamino group having 7 to 13 total carbon atoms, a heterocyclic carbamoylamino group having 3 to 12 total carbon atoms, preferably a carbamoylamino group, an alkylcarbamoylamino group having 2 to 7 total carbon atoms, a dialkylcarbamoylamino group having 3 to 6 total carbon atoms, arylcarbamoylamino group having 7 to 11 total carbon atoms, heterocyclic carbamoylamino group having 3 to 10 total carbon atoms, for example, carbamoylamino group, methylcarbamoylamino group, N-dimethylcarbamoylamino group, phenylcarbamoylamino group, 4-pyridinecarbamoylamino group and the like.

In the present specification, the range represented by the endpoints includes all the numerical values included in the range (for example, 1 to 10 includes 1.4, 1.9, 2.33, 5.75, 9.98, and the like).

In the present specification, the expression "at least 1" includes all numerical values of 1 or more (for example, at least 2, at least 4, at least 6, at least 8, at least 10, at least 25, at least 50, at least 100, etc.).

Next, the polytetrafluoroethylene of the invention will be specifically described.

The polytetrafluoroethylene (hereinafter sometimes referred to as "PTFE") of the present invention has a standard specific gravity of 2.175 or less and a Thermal Instability Index (TII) of 20 or more. (hereinafter sometimes referred to as the first PTFE of the present invention.)

The first PTFE of the present invention preferably has a breaking strength of 10.0N or more. The 0.1% weight loss temperature of the first PTFE of the present invention may be 400 ℃ or less. The 1.0% weight loss temperature of the first PTFE of the present invention may be 492 ℃ or less.

The PTFE of the present invention has a standard specific gravity of 2.175 or less and a 0.1% weight loss temperature of 400 ℃. (hereinafter sometimes referred to as the second PTFE of the present invention.)

The second PTFE of the present invention preferably has a breaking strength of 10.0N or more. The second PTFE of the present invention preferably has a Thermal Instability Index (TII) of 20 or more. The 1.0% weight loss temperature of the second PTFE of the present invention may be 492 ℃ or less.

The PTFE of the present invention has a standard specific gravity of 2.175 or less and a 1.0% weight loss temperature of 492 ℃ or less. (hereinafter sometimes referred to as the third PTFE of the present invention.)

The third PTFE of the present invention preferably has a breaking strength of 10.0N or more. The third PTFE of the present invention preferably has a Thermal Instability Index (TII) of 20 or more. The 0.1% weight loss temperature of the third PTFE of the present invention may be 400 ℃ or less.

The first to third PTFE of the present invention are suitable for stretch molding by setting the Standard Specific Gravity (SSG) to 2.175 or less. In addition, a stretched body excellent in breaking strength and stress relaxation time can be obtained.

The PTFE of the present invention has a breaking strength of 10.0N or more and a Thermal Instability Index (TII) of 20 or more. (hereinafter sometimes referred to as the fourth PTFE of the present invention.)

The fourth PTFE of the present invention preferably has a standard specific gravity of 2.175 or less. The 0.1% weight loss temperature of the fourth PTFE of the present invention may be 400 ℃ or less. The 1.0% weight loss temperature of the fourth PTFE of the present invention may be 492 ℃ or less.

The fracture strength of the PTFE of the present invention is 10.0N or more, and the 0.1% weight loss temperature is 400 ℃. (hereinafter sometimes referred to as the fifth PTFE of the present invention.)

The fifth PTFE of the present invention preferably has a standard specific gravity of 2.175 or less. The fifth PTFE of the present invention preferably has a Thermal Instability Index (TII) of 20 or more. The 1.0% weight loss temperature of the fifth PTFE of the present invention may be 492 ℃ or less.

The fracture strength of the PTFE of the present invention is 10.0N or more, and the 1.0% weight loss temperature is 492 ℃ or less. (hereinafter sometimes referred to as the sixth PTFE of the present invention.)

The sixth PTFE of the present invention preferably has a standard specific gravity of 2.175 or less. The sixth PTFE of the present invention preferably has a Thermal Instability Index (TII) of 20 or more. The 0.1% weight loss temperature of the sixth PTFE of the present invention may be 400 ℃ or lower.

The fourth to sixth PTFE of the present invention are suitable for stretch molding by setting the breaking strength to 10.0N or more. In addition, a stretched body excellent in breaking strength and stress relaxation time can be obtained.

The PTFE of the present invention has a breaking strength of 10.0N or more and contains substantially no fluorosurfactant. (hereinafter sometimes referred to as the seventh PTFE of the present invention.)

The seventh PTFE of the present invention preferably has a standard specific gravity of 2.175 or less. The seventh PTFE of the present invention preferably has a Thermal Instability Index (TII) of 20 or more. The 0.1% weight loss temperature of the seventh PTFE of the present invention may be 400 ℃ or less. The 1.0% weight loss temperature of the seventh PTFE of the present invention may be 492 ℃ or less.

The PTFE of the present invention has a standard specific gravity of 2.175 or less and contains substantially no fluorosurfactant. (hereinafter sometimes referred to as the eighth PTFE of the present invention.)

The eighth PTFE of the present invention preferably has a breaking strength of 10.0N or more. The eighth PTFE of the present invention preferably has a Thermal Instability Index (TII) of 20 or more. The 0.1% weight loss temperature of the eighth PTFE of the present invention may be 400 ℃ or lower. The 1.0% weight loss temperature of the eighth PTFE of the present invention may be 492 ℃ or lower.

The seventh to eighth PTFE of the present invention are suitable for stretch molding by containing substantially no fluorosurfactant. In addition, a stretched body excellent in breaking strength and stress relaxation time can be obtained.

In the present specification, unless otherwise specified, "PTFE of the present invention" means the first to eighth PTFE of the present invention.

The PTFE of the present invention has a Standard Specific Gravity (SSG) of 2.175 or less, preferably 2.170 or less, more preferably 2.165 or less, further preferably 2.160 or less, and may be 2.155 or less. The SSG was measured by the underwater substitution method according to ASTM D-792 using a sample molded according to ASTM D4895-89.

PTFE having a Thermal Instability Index (TII) of 20 or more is obtained by using a hydrocarbon surfactant. The TII is preferably 25 or more, more preferably 30 or more, and still more preferably 35 or more. Particularly preferably 40 or more. The TII is measured according to ASTM D4895-89.

The PTFE having a weight loss temperature of 0.1% of 400 ℃ or lower is obtained by using a hydrocarbon surfactant. The 0.1% weight loss temperature is a value measured by the following method.

About 10mg of PTFE powder which had not been heated to a temperature of 300 ℃ or higher was precisely weighed, stored in a dedicated aluminum pan, and TG. DTA (differential thermal/thermogravimetric simultaneous measurement apparatus) was measured. With respect to the 0.1% weight loss temperature, the aluminum plate was heated at 10 ℃/min in a temperature range of 25 ℃ to 600 ℃ under an atmospheric atmosphere, and the temperature corresponding to the point at which the weight was reduced by 0.1 mass% was defined as the 0.1% weight loss temperature.

PTFE having a weight loss temperature of 1.0% or less of 492 ℃ is obtained by using a hydrocarbon surfactant. The 1.0% weight loss temperature is a value measured by the following method.

About 10mg of PTFE powder which had not been heated to a temperature of 300 ℃ or higher was precisely weighed, stored in a dedicated aluminum pan, and TG. DTA (differential thermal/thermogravimetric simultaneous measurement apparatus) was measured. With respect to the 1.0% weight loss temperature, the aluminum plate was heated at 10 ℃/min in the temperature range of 25 ℃ to 600 ℃ under the atmospheric atmosphere, and the temperature corresponding to the point at which the weight was reduced by 0.1 mass% was defined as the 0.1% weight loss temperature.

The average primary particle diameter of the PTFE of the present invention is preferably 150nm or more, and more preferably 180nm or more. The larger the average primary particle size of PTFE is, the more the increase in paste extrusion pressure can be suppressed in paste extrusion molding using the powder, and the film-forming property is also excellent. The upper limit is not particularly limited, and may be 500 nm. The upper limit is preferably 350nm from the viewpoint of productivity in the polymerization step. The above average primary particle diameter is determined as follows: the PTFE aqueous dispersion was diluted with water until the solid content reached 0.15 mass%, the transmittance per unit length of the resulting diluted emulsion was measured for a projection light of 550nm, and the number-based length-average particle diameter determined by measuring the orientation diameter using a transmission electron micrograph were measured to prepare a calibration curve, and the average primary particle diameter was determined from the measured transmittance of the projection light of 550nm for each sample using the calibration curve.

The extrusion pressure of the PTFE of the present invention is preferably 30.0MPa or less, more preferably 29.0MPa or less, still more preferably 28.0MPa or less, yet more preferably 25.0MPa or less, preferably 5.0MPa or more, and more preferably 10.0MPa or more. The extrusion pressure is a value obtained by the following method according to the method described in Japanese patent laid-open No. 2002-201217.

21.7g of a lubricant (trade name: Isopar H (registered trademark), manufactured by Exxon corporation) was added to 100g of PTFE powder, and the mixture was mixed in a glass bottle at room temperature for 3 minutes. Next, the glass bottle was left at room temperature (25 ℃ C.) for at least 1 hour before extrusion to obtain a lubricating resin. Lubricating resin was passed through a hole (diameter 2.5mm, land length 11mm, lead-in angle 30 °) at room temperature at a rate of 100: a uniform bead (extrusion molded article) was obtained by paste extrusion at a reduction ratio of 1. The extrusion speed, i.e., the ram speed, was set to 20 inches/minute (51 cm/minute). The extrusion pressure was determined by dividing the load at which the extrusion load reached a balanced state in the paste extrusion by the cross-sectional area of the cylinder used in the paste extrusion, and the obtained value was used as the extrusion pressure.

The PTFE of the present invention is preferably stretchable. In the present specification, "stretchable" means that the determination is made according to the following criteria.

The beads obtained by the paste extrusion were heated at 230 ℃ for 30 minutes, whereby the lubricant was removed from the beads. Next, the beads (extrusion molded articles) were cut into appropriate lengths, each end was fixed to a chuck at a chuck interval of 1.5 inches (38mm), and heated to 300 ℃ in an air circulating furnace. Next, the chucks are separated at a desired speed (elongation speed) to a separation distance corresponding to a desired elongation (total elongation), and an elongation test (tensile test) is performed. The elongation process is essentially as disclosed in U.S. Pat. No. 4,576,869, except that the extrusion rate (51 cm/min, not 84 cm/min) is different. "elongation" refers to an increase in length caused by stretching, and is usually expressed in relation to the original length. In the above production method, the elongation rate is 1000%/second, and the total elongation is 2400%. This means that the stretched beads having a uniform appearance were obtained without cutting in the tensile test.

The fracture strength of the PTFE of the present invention is more preferably 13.0N or more, further preferably 16.0N or more, further preferably 19.0N or more, further preferably 22.0N or more, further preferably 23.0N or more, further preferably 25.0N or more, further preferably 28.0N or more, further preferably 29.0N or more, further preferably 30.0N or more, further preferably 32.0N or more, further preferably 35.0N or more, further preferably 37.0N or more, further preferably 40.0N or more. The higher the breaking strength, the better, the breaking strength may be 100.0N or less, may be 80.0N or less, and may be 50.0N or less. The breaking strength is a value obtained by the following method.

The tensile beads (prepared by elongating beads) obtained in the above tensile test were held and fixed by a movable jaw having a gauge length of 5.0cm, and a tensile test was performed at a speed of 300 mm/min at 25 ℃ with the strength at break being taken as the breaking strength.

The PTFE of the present invention has a stress relaxation time of preferably 50 seconds or more, more preferably 80 seconds or more, further preferably 100 seconds or more, may be 120 seconds or more, may be 150 seconds or more, may be 190 seconds or more, may be 200 seconds or more, may be 220 seconds or more, may be 240 seconds or more, and may be 300 seconds or more. The stress relaxation time is a value measured by the following method.

Both ends of the stretched beads obtained in the above-described tensile test were attached to a fixing tool to prepare a bead sample of a total length of 8 inches (20cm) which was pulled tight. The oven was held at 390 ℃ and the fixture was inserted into the oven through a slit located in the side of the oven (covered). The time required from the moment of insertion into the oven until the bead sample broke was taken as the stress relaxation time.

The PTFE of the present invention may be molded, heat-treated at 100 ℃ for 2 hours, heat-treated at 200 ℃ for 4 hours, and heat-treated at 370 ℃ for 5 hours, and the brightness L of a sheet cut out from the fired body obtained thereby may be 90.0 or less, 80 or less, 70 or less, 60 or less, or 50 or less. The brightness L is a value measured by the following method.

210g of the powder was filled into a mold having an inner diameter of 50mm, and it took about 30 seconds to apply pressure until the final pressure reached about 200kg/cm²Then, the pressure was maintained for 5 minutes to prepare a preform. The preform was taken out from the mold, heat-treated in a hot air circulating electric furnace at 100 ℃ for 2 hours, 200 ℃ for 4 hours, and 370 ℃ for 5 hours, and then cooled to room temperature at a rate of 50 ℃/hour to obtain a cylindrical fired body. The fired body was cut along the side surfaces to produce a tape-shaped sheet having a thickness of 0.5 mm. The test piece was cut into a size of 100mm × 50mm from the strip, and the luminance (L;) of the strip was measured by a color difference meter (CR-400, manufactured by konica minolta optical corporation).

The heat shrinkage of the PTFE of the present invention in the sintered body obtained by molding PTFE, heat-treating at 100 ℃ for 2 hours, at 200 ℃ for 4 hours, and at 370 ℃ for 5 hours may be 7.0% or more, or 6.5% or more. The thermal shrinkage is a value measured by the following method.

210g of the powder was filled into a mold having an inner diameter of 50mm, and it took about 30 seconds to apply pressure until the final pressure reached about 200kg/cm ²Then, the pressure was maintained for 5 minutes to prepare a preform. The preform was taken out of the mold, and the diameter (a) of the preform was measured. Thereafter, the preform was heat-treated in a hot air circulating electric furnace at 100 ℃ for 2 hours, 200 ℃ for 4 hours, and 370 ℃ for 5 hours, and then cooled to room temperature at a rate of 50 ℃/hour to obtain a cylindrical fired body. The diameter (B) of the obtained fired body was measured, and the thermal shrinkage was calculated from the following equation.

Heat shrinkage ratio ((a) - (B))/(a) × 100

In the PTFE of the present invention, the PTFE is molded, heat-treated at 100 ℃ for 2 hours, heat-treated at 200 ℃ for 4 hours, and heat-treated at 370 ℃ for 5 hours, and the contact angle of the surface of the sheet cut out from the fired body obtained therefrom, which corresponds to the inside of the fired body, is preferably 107 ° or more, more preferably 108 ° or more, further preferably 109 ° or more, and particularly preferably 110 ° or more. The contact angle is a value measured by the following method.

210g of the powder was filled into a mold having an inner diameter of 50mm, and it took about 30 seconds to apply pressure until the final pressure reached about 200kg/cm²Then, the pressure was maintained for 5 minutes to prepare a preform. The preform was taken out from the mold, heat-treated in a hot air circulating electric furnace at 100 ℃ for 2 hours, 200 ℃ for 4 hours, and 370 ℃ for 5 hours, and then cooled to room temperature at a rate of 50 ℃/hour to obtain a cylindrical fired body. The fired body was cut along the side surfaces to produce a tape-shaped sheet having a thickness of 0.5 mm. The test piece was cut into a size of 50mm × 50mm from the strip, and the contact angle of the surface corresponding to the inner side of the strip was measured by a portable contact goniometer (PCA-1, manufactured by Kyowa interface chemical Co., Ltd.). The contact angle was calculated as follows: a water droplet is dropped onto a test piece, the shape of the droplet is introduced in a pattern by a CCD camera, the radius (r) and the height (h) of the droplet image are obtained by image processing, and the contact angle is calculated by substituting the following equation. (theta/2 method)

θ＝2arctan(h/r)

The peak temperature of the PTFE of the present invention is preferably 348 ℃ or lower, more preferably 346 ℃ or lower, and still more preferably 344 ℃ or lower. The peak temperature is a value measured by the following method.

About 10mg of PTFE powder which had not been heated to a temperature of 300 ℃ or higher was precisely weighed, stored in a dedicated aluminum pan, and TG. DTA (differential thermal/thermogravimetric simultaneous measurement apparatus) was measured. As for the peak temperature, the temperature of the aluminum plate was raised in the temperature range of 25 ℃ to 600 ℃ at 10 ℃/min under the atmospheric atmosphere, and the temperature corresponding to the minimum value of the Differential Thermal (DTA) curve was taken as the peak temperature.

The melting point of the PTFE of the present invention is preferably 348 ℃ or lower, more preferably 346 ℃ or lower, and still more preferably 344 ℃ or lower. The melting point is a value measured by the following method.

About 10mg of PTFE powder which had not been heated to a temperature of 300 ℃ or higher was precisely weighed, stored in a dedicated aluminum pan, and TG. DTA (differential thermal/thermogravimetric simultaneous measurement apparatus) was measured. The melting point was determined by raising the temperature of the aluminum plate at 10 ℃/min in the temperature range of 25 ℃ to 600 ℃ in the atmospheric atmosphere and setting the temperature corresponding to the minimum value of the differential thermal energy (DTA) curve as the melting point.

The PTFE of the present invention preferably contains substantially no fluorosurfactant. In the PTFE of the present invention, "the fluorosurfactant is not substantially contained" means that the fluorosurfactant is 10ppm or less with respect to the PTFE. The content of the fluorinated surfactant is preferably 1ppm or less, more preferably 100ppb or less, still more preferably 10ppb or less, still more preferably 1ppb or less, and particularly preferably the detection limit or less of the fluorinated surfactant obtained by measurement by liquid chromatography-mass spectrometry (LC/MS).

The amount of the above-mentioned fluorosurfactant can be determined by a known method. For example, quantification can be performed by LC/MS/MS analysis. First, the obtained PTFE powder was extracted into an organic solvent of methanol, and molecular weight information was extracted from the extract by LC/MS spectroscopy to confirm that the PTFE powder had a structural formula identical to that of a candidate surfactant.

Then, an aqueous solution having a concentration of 5 levels or more was prepared for the confirmed surfactant, and LC/MS analysis was performed for each concentration to prepare a calibration curve with respect to the area of the region.

The obtained PTFE powder was subjected to soxhlet extraction with methanol, and the extract was analyzed by LC/MS, whereby quantitative measurement was possible.

The fluorinated surfactant is the same as that exemplified in the production method described later. For example, the surfactant may contain a fluorine atom having a total carbon number of a portion other than the anionic group of 20 or less, may contain a fluorine atom having a molecular weight of 800 or less in the anionic portion, or may contain a fluorine-containing surfactant having a LogPOW of 3.5 or less.

The "anionic moiety" refers to a moiety of the above-mentioned fluorosurfactant other than cations. For example, F (CF) represented by the following formula (I) ₂)_n1COOM is "F (CF)₂)_n1COO'.

Examples of the anionic fluorosurfactant include those represented by the general formula (N)⁰) Specific examples of the compound include compounds represented by the general formula (N)¹) A compound represented by the general formula (N)²) A compound represented by the general formula (N)³) A compound represented by the general formula (N)⁴) A compound represented by the formula (N)⁵) The compounds shown. More specifically, there may be mentioned perfluorocarboxylic acid (I) represented by general formula (I), ω -H perfluorocarboxylic acid (II) represented by general formula (II), perfluoropolyether carboxylic acid (III) represented by general formula (III), perfluoroalkylalkylalkylene carboxylic acid (IV) represented by general formula (IV), perfluoroalkoxy fluorocarboxylic acid (V) represented by general formula (V), perfluoroalkylsulfonic acid (VI) represented by general formula (VI), ω -H perfluorosulfonic acid (VII) represented by general formula (VII), perfluoroalkylalkylalkylene sulfonic acid (VIII) represented by general formula (VIII), alkylalkylalkylene carboxylic acid (IX) represented by general formula (IX), fluorocarboxylic acid (X) represented by general formula (X), alkoxyfluorosulfonic acid (XI) represented by general formula (XI), and compound (XII) represented by general formula (XII).

The PTFE of the present invention preferably has a breaking strength of 29.0N or more as measured under the following condition (X) of stretched beads produced by heat treatment at a temperature of 240 ℃ and the following condition (a), and does not substantially contain a fluorosurfactant.

Condition (a):

to 100g of PTFE powder, 21.7g of a lubricant was added, and the mixture was mixed in a glass bottle at room temperature for 3 minutes. Next, the glass bottle was left at room temperature (25 ℃ C.) for at least 1 hour before extrusion to obtain a lubricating resin. Lubricating resin was passed through a hole (diameter 2.5mm, land length 11mm, lead-in angle 30 °) at room temperature at a rate of 100: a uniform bead (extrusion molded article) was obtained by paste extrusion at a reduction ratio of 1. The extrusion speed, i.e., the ram speed, was set to 20 inches/minute (51 cm/minute).

The lubricant-containing PTFE extruded beads obtained by the above paste extrusion were dried at 230 ℃ for 30 minutes, and the lubricant was removed from the beads, thereby obtaining dried PTFE extruded beads. Next, the dried PTFE extruded beads were cut to appropriate lengths, secured at each end to a collet at 1.5 inch (38mm) spacing, and heated to 300 ℃ in an air circulating oven. Next, the chucks were separated at 1000%/second to a separation distance equivalent to 2400%, and an elongation test was performed to obtain stretched beads. The elongation process is essentially as disclosed in U.S. Pat. No. 4,576,869, except that the extrusion rate (51 cm/min, not 84 cm/min) is different. "elongation" refers to an increase in length caused by stretching, and is usually expressed in relation to the original length. In the above production method, the elongation rate is 1000%/second, and the total elongation is 2400%.

Condition (X):

the above-mentioned stretched beads (prepared by stretching beads) were held and fixed by a movable jaw having a gauge length of 5.0cm, and a tensile test was conducted at 25 ℃ and a speed of 300 mm/min, and the strength at break was defined as the breaking strength.

As the lubricant, a lubricant composed of 100% isoparaffin, having an initial boiling point of 180 ℃, a dry point of 188 ℃, a flash point of 54 ℃ and a density (15 ℃) of 0.758g/cm³KB (Coomassie value) 26, aniline point 85 ℃ and aromatic content<As such a lubricant, Isopar H (registered trademark) manufactured by exxon corporation can be specifically used at 0.01 mass%.

The PTFE of the present invention is preferably a stretched product produced under the condition (a) by heat-treating at 240 ℃ and having a breaking strength of 29.0N or more and a Thermal Instability Index (TII) of 20 or more as measured under the condition (X).

The PTFE of the present invention preferably has a breaking strength of 29.0N or more as measured under the condition (X) in the stretched product produced under the condition (a). The breaking strength is more preferably 30.0N or more, further preferably 32.0N or more, and further preferably 35.0N or more. The higher the breaking strength, the better, the upper limit of the breaking strength is not limited, and may be 80.0N or less, or 50.0N or less, for example. The breaking strength is a value obtained by the following method.

After the above heat treatment, the drawn body produced under the condition (A) was held and fixed by a movable jaw having a gauge length of 5.0cm, and a tensile test was conducted at 25 ℃ and a speed of 300 mm/min, and the strength at break was defined as the breaking strength.

The PTFE of the present invention preferably has a breaking strength of 22.0N or more measured under the condition (X) of the stretched beads produced by heat treatment at a temperature of 240 ℃ under the following condition (B), and does not substantially contain a fluorosurfactant.

Condition (B):

to 100g of PTFE powder, 21.7g of a lubricant was added, and the mixture was mixed in a glass bottle at room temperature for 3 minutes. Next, the glass bottle was left at room temperature (25 ℃ C.) for at least 1 hour before extrusion to obtain a lubricating resin. Lubricating resin was passed through a hole (diameter 2.5mm, land length 11mm, lead-in angle 30 °) at room temperature at a rate of 100: a uniform bead (extrusion molded article) was obtained by paste extrusion at a reduction ratio of 1. The extrusion speed, i.e., the ram speed, was set to 20 inches/minute (51 cm/minute).

The lubricant-containing PTFE extruded beads obtained by the above paste extrusion were dried at 230 ℃ for 30 minutes, and the lubricant was removed from the beads, thereby obtaining dried PTFE extruded beads. Next, the dried PTFE extruded beads were cut to appropriate lengths, secured at each end to a collet at 2.0 inch (51mm) intervals, and heated to 300 ℃ in an air circulating oven. Next, the chucks were separated at 100%/second to a separation distance corresponding to 2400% of the desired elongation (total elongation), and an elongation test was performed to obtain a stretched bead. The elongation process is essentially as disclosed in U.S. Pat. No. 4,576,869, except that the extrusion rate (51 cm/min, not 84 cm/min) is different. "elongation" refers to an increase in length caused by stretching, and is usually expressed in relation to the original length.

Condition (X):

the above-mentioned stretched beads (prepared by stretching beads) were held and fixed by a movable jaw having a gauge length of 5.0cm, and a tensile test was conducted at 25 ℃ and a speed of 300 mm/min, and the strength at break was defined as the breaking strength.

As the lubricant, a lubricant composed of 100% isoparaffin, having an initial boiling point of 180 ℃, a dry point of 188 ℃, a flash point of 54 ℃ and a density (15 ℃) of 0.758g/cm³KB (combretastatin)Alcohol number) 26, aniline point 85 ℃, aromatic content<As such a lubricant, Isopar H (registered trademark) manufactured by exxon corporation can be specifically used at 0.01 mass%.

The PTFE of the present invention is preferably a stretched product produced under the condition (B) by heat-treating at 240 ℃ and having a breaking strength of 22.0N or more and a Thermal Instability Index (TII) of 20 or more.

The PTFE of the present invention preferably has a breaking strength of 22.0N or more as measured under the condition (X) in the stretched product produced under the condition (B). The breaking strength is more preferably 23.0N or more, further preferably 25.0N or more, further preferably 28.0N or more, and particularly preferably 30.0N or more. The higher the breaking strength, the better, the upper limit of the breaking strength is not limited, and may be 80.0N or less, or 50.0N or less, for example. The breaking strength is a value obtained by the following method.

The PTFE of the present invention is preferably 99.0 mass% or more of PTFE and 1.0 mass% or less of components other than PTFE, more preferably 99.5 mass% or more of PTFE and 0.5 mass% or less of components other than PTFE, still more preferably 99.9 mass% or more of PTFE and 0.1 mass% or less of components other than PTFE, and particularly preferably substantially 100.0 mass% of PTFE, based on the total mass of the solid content.

The PTFE of the present invention may be a wet powder, or may contain 0.0001 to 50 mass% of an aqueous medium. The amount of the aqueous medium may be 0.0001 to 1.0% by mass, or 0.0001 to 0.01% by mass.

The amount of the aqueous medium can be determined by the weight loss at the time of drying at 150 ℃ for 60 minutes.

In the PTFE of the present invention, the heat treatment is carried out at 240 ℃. More specifically, the reaction was carried out at 240 ℃ for 18 hours.

The heat treatment may be drying of the PTFE of the present invention. For example, when the PTFE of the present invention is a wet powder of PTFE, the moisture contained in the wet powder may be dried.

In the PTFE of the present invention, the stretched product is preferably produced under the above-mentioned condition (a) or condition (B).

The PTFE of the present invention preferably has an extrusion pressure of 50.0MPa or less, and a breaking strength of 29.0N or more measured under the condition (X) of the stretched product produced under the condition (a), and substantially contains no fluorosurfactant. The extrusion pressure is more preferably 40.0MPa or less, preferably 8.0MPa or more, and more preferably 10.0MPa or more.

The PTFE of the present invention preferably has an extrusion pressure of 50.0MPa or less, a breaking strength of 29.0N or more measured under the condition (X) of the stretched product produced under the condition (a), and a Thermal Instability Index (TII) of 20 or more. The extrusion pressure is more preferably 40.0MPa or less, preferably 8.0MPa or more, and more preferably 10.0MPa or more.

The PTFE of the present invention preferably has a breaking strength of 34.0N or more as measured under the condition (X) of the stretched product produced under the condition (a), and contains substantially no fluorosurfactant. The breaking strength is more preferably 35.0N or more, still more preferably 37.0N or more, and still more preferably 40.0N or more. The higher the breaking strength, the better, and the upper limit of the breaking strength is, for example, 100.0N.

The PTFE of the present invention preferably has a breaking strength of 34.0N or more and a Thermal Instability Index (TII) of 20 or more as measured under the condition (X) in the stretched product produced under the condition (a). The breaking strength is more preferably 35.0N or more, still more preferably 37.0N or more, and still more preferably 40.0N or more. The higher the breaking strength, the better, and the upper limit of the breaking strength is, for example, 100.0N.

The PTFE of the present invention preferably has a breaking strength of 29.0N or more as measured under the condition (X) of the stretched product produced under the condition (B), and contains substantially no fluorosurfactant. The breaking strength is more preferably 30.0N or more, further preferably 32.0N or more, and further preferably 35.0N or more. The higher the breaking strength, the better, the upper limit of the breaking strength is not limited, and may be, for example, 100.0N or less, or 80.0N or less.

The PTFE of the present invention preferably has a breaking strength of 29.0N or more and a Thermal Instability Index (TII) of 20 or more as measured under the condition (X) in the stretched product produced under the condition (B). The breaking strength is more preferably 30.0N or more, further preferably 32.0N or more, and further preferably 35.0N or more. The higher the breaking strength, the better, the upper limit of the breaking strength is not limited, and may be, for example, 100.0N or less, or 80.0N or less.

The PTFE of the present invention is preferably stretchable. In the present specification, "stretchable" means that the determination is made according to the following criteria.

21.7g of a lubricant (trade name: Isopar H (registered trademark), manufactured by Exxon corporation) was added to 100g of PTFE powder, and the mixture was mixed in a glass bottle at room temperature for 3 minutes. Next, the glass bottle was left at room temperature (25 ℃ C.) for at least 1 hour before extrusion to obtain a lubricating resin. Lubricating resin was passed through a hole (diameter 2.5mm, land length 11mm, lead-in angle 30 °) at room temperature at a rate of 100: paste extrusion was carried out at a reduction ratio of 1 to obtain uniform beads. The extrusion speed, i.e., the ram speed, was set to 20 inches/minute (51 cm/minute). The beads obtained by paste extrusion were heated at 230 ℃ for 30 minutes, whereby the lubricant was removed from the beads. Next, the beads (extrusion molded articles) were cut into appropriate lengths, each end was fixed to a chuck at a chuck interval of 1.5 inches (38mm), and heated to 300 ℃ in an air circulating furnace. Next, the chucks are separated at a desired speed (elongation speed) to a separation distance corresponding to a desired elongation (total elongation), and an elongation test is performed. The elongation process is essentially as disclosed in U.S. Pat. No. 4,576,869, except that the extrusion rate (51 cm/min, not 84 cm/min) is different. "elongation" refers to an increase in length caused by stretching, and is usually expressed in relation to the original length. In the above production method, the elongation rate is 1000%/second, and the total elongation is 2400%. This means that the stretched beads having a uniform appearance were obtained without cutting in the tensile test.

The average particle diameter (average secondary particle diameter) of PTFE of the present invention is preferably 100 to 2000. mu.m. The lower limit of the average secondary particle size is more preferably 200 μm or more, and still more preferably 300 μm or more. The upper limit of the average secondary particle size is preferably 1000 μm or less, more preferably 800 μm or less, and particularly preferably 700 μm or less. The average particle diameter is a value measured in accordance with JIS K6891.

PTFE of the present invention generally has stretchability, fibrillating properties, and non-melt secondary processability.

The above non-melt secondary processability means a property that the melt flow rate cannot be measured at a temperature higher than the peak temperature according to ASTM D-1238 and D-2116, that is, a property that it does not flow easily in the melting temperature region.

The PTFE of the present invention may be a Tetrafluoroethylene (TFE) homopolymer or a modified PTFE obtained by copolymerizing TFE with a modifying monomer.

The PTFE of the present invention can be stretched even in the case of TFE homopolymer. The present invention provides PTFE which is a TFE homopolymer and is stretchable.

In the case of modified PTFE, the PTFE of the present invention has higher fracture strength. The present invention provides a PTFE which is a modified PTFE and has a breaking strength of 10.0N or more.

The PTFE can be appropriately formed in various manners as described in the first to eighth PTFE of the present invention.

The above-mentioned modifying monomer is not particularly limited as long as it is copolymerizable with TFE, and examples thereof include perfluoroolefins such as hexafluoropropylene [ HFP ]; hydrogen-containing fluoroolefins such as trifluoroethylene and vinylidene fluoride [ VDF ]; a perfluorovinyl ether; (perfluoroalkyl) ethylene, and the like. The number of the modifying monomers used may be 1, or 2 or more.

The perfluorovinyl ether is not particularly limited, and examples thereof include those represented by the following general formula (a):

CF₂＝CF-ORf (A)

and (wherein Rf represents a perfluoroorganic group). In the present specification, the "perfluoro organic group" refers to an organic group in which all hydrogen atoms bonded to carbon atoms are replaced with fluorine atoms. The aforementioned perfluoroorganic group may have an ether oxygen.

Examples of the perfluorovinyl ether include perfluoro (alkyl vinyl ether) [ PAVE ] in which Rf in the general formula (a) is a perfluoroalkyl group having 1 to 10 carbon atoms. The perfluoroalkyl group preferably has 1 to 5 carbon atoms.

Examples of the perfluoroalkyl group in PAVE include a perfluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluorobutyl group, a perfluoropentyl group, and a perfluorohexyl group.

The perfluorovinyl ether may further include a monomer represented by the general formula (A) wherein Rf is a C4-9 perfluoro (alkoxyalkyl) group, and Rf is represented by the following formula:

[ solution 1]

(wherein m represents 0 or an integer of 1 to 4), and Rf is represented by the following formula:

[ solution 2]

(wherein n represents an integer of 1 to 4) or the like.

The (perfluoroalkyl) ethylene (PFAE) is not particularly limited, and examples thereof include (perfluorobutyl) ethylene (PFBE), and (perfluorohexyl) ethylene.

The above-mentioned modified monomer is also preferably exemplified by a comonomer (3) having a monomer reactivity ratio of 0.1 to 8. By the presence of the comonomer (3), PTFE particles having a small particle diameter can be obtained, and an aqueous dispersion having high dispersion stability can be obtained.

Here, the monomer reactivity ratio in copolymerization with TFE is a value obtained as follows: when the growth radical is smaller than the repeating unit based on TFE, the rate constant at the time when the growth radical reacts with TFE is divided by the rate constant at the time when the growth radical reacts with the comonomer, and the obtained value is the monomer reactivity ratio. The lower the value, the higher the reactivity of the comonomer with TFE. The monomer reactivity ratio can be calculated as follows: the composition of the resulting polymer immediately after the initiation of copolymerization of TFE and a comonomer was determined and calculated from Fineman-Ross formula.

The copolymerization was carried out in a stainless steel autoclave having an internal volume of 6.0L using 3600g of deionized and degassed water, 1000ppm of ammonium perfluorooctanoate relative to the water, and 100g of paraffin wax under a pressure of 0.78MPa and a temperature of 70 ℃. 0.05g, 0.1g, 0.2g, 0.5g and 1.0g of a comonomer were fed into the reactor, respectively, and 0.072g of ammonium persulfate (20 ppm relative to water) was fed thereto, and TFE was continuously fed so as to maintain a polymerization pressure of 0.78 MPa. When the amount of TFE fed reached 1000g, the stirring was stopped and the pressure was released until the reactor reached atmospheric pressure. After cooling, the paraffin wax was separated, thereby obtaining an aqueous dispersion containing the resulting polymer. The resulting aqueous dispersion was stirred to precipitate a polymer, and dried at 150 ℃. The composition of the resulting polymer was calculated by appropriately combining NMR, FT-IR, elemental analysis, and fluorescent X-ray analysis depending on the type of the monomer.

The comonomer (3) having a monomer reactivity ratio of 0.1 to 8 is preferably at least one selected from the group consisting of comonomers represented by formulae (3a) to (3 d).

CH₂＝CH-Rf¹ (3a)

(wherein Rf¹Is a perfluoroalkyl group having 1 to 10 carbon atoms. )

CF₂＝CF-O-Rf² (3b)

(wherein Rf²Is a perfluoroalkyl group having 1 to 2 carbon atoms. )

CF₂＝CF-O-(CF₂)_nCF＝CF₂ (3c)

(wherein n is 1 or 2.)

[ solution 3]

(in the formula, X³And X⁴F, Cl or methoxy, Y is of formula Y1 or Y2. )

[ solution 4]

-CF＝CF- (Y1)

(in the formula Y2, Z and Z' are F or a fluoroalkyl group having 1 to 3 carbon atoms.)

The content of the comonomer (3) is preferably in the range of 0.00001 to 1.0 mass% with respect to PTFE. The lower limit is more preferably 0.0001% by mass, still more preferably 0.001% by mass, yet more preferably 0.005% by mass, and particularly preferably 0.009% by mass. The upper limit is preferably 0.90% by mass, more preferably 0.50% by mass, still more preferably 0.40% by mass, yet more preferably 0.30% by mass, particularly preferably 0.10% by mass, and particularly preferably 0.05% by mass.

The modified monomer is preferably at least one selected from the group consisting of hexafluoropropylene, vinylidene fluoride, fluoro (alkyl vinyl ether), (perfluoroalkyl) ethylene, and a modified monomer having a functional group capable of undergoing a radical polymerization reaction and a hydrophilic group, because an aqueous dispersion having a small average primary particle diameter of modified polytetrafluoroethylene particles, a small aspect ratio of primary particles, and excellent stability can be obtained. By using the modified monomer, an aqueous dispersion of PTFE having a smaller average primary particle diameter, a smaller aspect ratio of primary particles, and excellent dispersion stability can be obtained. Further, an aqueous dispersion containing a small amount of non-precipitated polymer can be obtained.

From the viewpoint of reactivity with TFE, the above-mentioned modifying monomer preferably contains at least one selected from the group consisting of hexafluoropropylene, perfluoro (alkyl vinyl ether), and (perfluoroalkyl) ethylene.

More preferably, at least one selected from the group consisting of hexafluoropropylene, perfluoro (methyl vinyl ether), perfluoro (propyl vinyl ether), (perfluorobutyl) ethylene, (perfluorohexyl) ethylene, and (perfluorooctyl) ethylene.

The total amount of the hexafluoropropylene unit, the perfluoro (alkyl vinyl ether) unit, and the (perfluoroalkyl) ethylene unit is preferably in the range of 0.00001 to 1.0 mass% with respect to PTFE. The lower limit of the total amount is more preferably 0.0001% by mass, still more preferably 0.0005% by mass, yet more preferably 0.001% by mass, yet more preferably 0.005% by mass, and particularly preferably 0.009% by mass. The upper limit is more preferably 0.50% by mass, still more preferably 0.40% by mass, yet more preferably 0.30% by mass, yet more preferably 0.10% by mass, yet more preferably 0.08% by mass, particularly preferably 0.05% by mass, and particularly preferably 0.01% by mass.

The above-mentioned modifying monomer also preferably contains a modifying monomer having a functional group capable of reacting by radical polymerization and a hydrophilic group (hereinafter referred to as "modifying monomer (a)").

The presence of the modified monomer (a) can provide PTFE particles having a small primary particle diameter, and can provide an aqueous dispersion having high dispersion stability. In addition, the amount of non-precipitated polymer can be reduced. Further, the aspect ratio of the primary particles can be reduced.

The amount of the modifying monomer (A) used is preferably an amount exceeding 0.1ppm, more preferably an amount exceeding 0.5ppm, still more preferably an amount exceeding 1.0ppm, even more preferably 5ppm or more, and particularly preferably 10ppm or more based on the aqueous medium. If the amount of the modified monomer (a) is too small, the average primary particle diameter of the PTFE to be obtained may not decrease.

The amount of the modifying monomer (A) may be in the above range, and for example, the upper limit can be set to 5000 ppm. In the above production method, the modifying monomer (a) may be added to the system during the reaction in order to improve the stability of the aqueous dispersion during or after the reaction.

Since the modified monomer (a) has high water solubility, the unreacted modified monomer (a) can be easily removed in the concentration step or the precipitation and washing step even if it remains in the aqueous dispersion.

The modified monomer (A) is incorporated into the resulting polymer during the polymerization, but the concentration of the modified monomer (A) in the polymerization system is low, and the amount of the modified monomer (A) incorporated into the polymer is small, so that there is no problem that the heat resistance of PTFE is lowered or coloring after firing is caused.

Examples of the hydrophilic group in the modified monomer (A) include-NH₂、-PO₃M、-OPO₃M、-SO₃M、-OSO₃M and-COOM (in the formula, M is H, metal atom, NR)⁷ ₄Imidazolium with or without substituents, pyridinium with or without substituents or phosphonium with or without substituents, R⁷Are H or an organic group, which may be the same or different. Any 2 of which may be bonded to each other to form a ring). As the above hydrophilic group, -SO is preferable₃M or-COOM. As R⁷Preferably H or C_1-10More preferably H or C_1-4Further preferably H or C_1-4Alkyl group of (1).

Examples of the metal atom include a metal atom having a valence of 1 and a metal atom having a valence of 2, and examples thereof include an alkali metal (group 1), an alkaline earth metal (group 2), and the like, and preferably include Na, K, and Li.

Examples of the "functional group capable of undergoing radical polymerization" in the modified monomer (a) include groups having an ethylenically unsaturated bond such as a vinyl group and an allyl group. The group having an ethylenically unsaturated bond may be represented by the formula:

CX^eX^g＝CX^fR-

(in the formula, X^e、X^fAnd X^gEach independently of the other is F, Cl, H, CF₃、CF₂H、CFH₂Or CH₃(ii) a R is a linking group). Examples of the linking group of R include the following R^aA linking group of (a). Preferably, the group-CH ═ CH ₂、-CF＝CH₂、-CH＝CF₂、-CF＝CF₂、-CH₂-CH＝CH₂、-CF₂-CF＝CH₂、-CF₂-CF＝CF₂、-(C＝O)-CH＝CH₂、-(C＝O)-CF＝CH₂、-(C＝O)-CH＝CF₂、-(C＝O)-CF＝CF₂、-(C＝O)-C(CH₃)＝CH₂、-(C＝O)-C(CF₃)＝CH₂、-(C＝O)-C(CH₃)＝CF₂、-(C＝O)-C(CF₃)＝CF₂、-O-CH₂-CH＝CH₂、-O-CF₂-CF＝CH₂、-O-CH₂-CH＝CF₂、-O-CF₂-CF＝CF₂And the like having an unsaturated bond.

Since the modified monomer (a) has a functional group capable of undergoing radical polymerization, when used in the above polymerization, it is presumed that the modified monomer (a) reacts with the fluorine-containing monomer at the initial stage of the polymerization reaction, has a hydrophilic group derived from the modified monomer (a), and can form particles having high stability. Therefore, when the polymerization is carried out in the presence of the modified monomer (a), the number of particles is considered to be increased.

In the above polymerization, the modified monomer (a) may be present in 1 kind, or may be present in 2 or more kinds.

In the above polymerization, as the modifying monomer (a), a compound having an unsaturated bond can be used.

The modifying monomer (A) is preferably of the general formula (4):

CXⁱX^k＝CX^jR^a-(CZ¹Z²)_k-Y³ (4)

(in the formula, Xⁱ、X^jAnd X^kEach independently of the others being F, Cl, H or CF₃；Y³Is a hydrophilic group; r^aIs a linking group; z¹And Z²Each independently H, F or CF₃And k is 0 or 1).

Examples of the hydrophilic group include-NH₂、-PO₃M、-OPO₃M、-SO₃M、-OSO₃M and-COOM (in the formula, M is H, metal atom, NR)⁷ ₄Imidazolium with or without substituents, pyridinium with or without substituents or phosphonium with or without substituents, R⁷Are H or an organic group, which may be the same or different. Any 2 of which may be bonded to each other to form a ring). As the above hydrophilic group, -SO is preferable ₃M or-COOM. As R⁷Preferably H or C_1-10More preferably H or C_1-4Further preferably H or C_1-4Alkyl group of (1).

Examples of the metal atom include a metal atom having a valence of 1 and a metal atom having a valence of 2, and examples thereof include an alkali metal (group 1), an alkaline earth metal (group 2), and the like, and preferably include Na, K, and Li.

By using the modified monomer (a), an aqueous dispersion having a smaller average primary particle diameter and more excellent stability can be obtained. In addition, the aspect ratio of the primary particles can be further reduced.

R is as defined above^aIs a linking group. In the present specification, "linking group" means a divalent linking group. The linking group may be a single bond, preferably contains at least 1 carbon atom, and the number of carbon atoms may be 2 or more, may be 4 or more, may be 8 or more, may be 10 or more, and may be 20 or more. The upper limit is not limited, and may be, for example, 100 or less or 50 or less.

The linking group may have a chain or branched structure, a cyclic or acyclic structure, a saturated or unsaturated structure, a substituted or unsubstituted structure, and may contain 1 or more heteroatoms selected from the group consisting of sulfur, oxygen, and nitrogen, and may contain 1 or more functional groups selected from the group consisting of esters, amides, sulfonamides, carbonyls, carbonates, carbamates, ureas, and carbamates, if desired. The linking group does not contain a carbon atom, and may be a chain hetero atom such as oxygen, sulfur or nitrogen.

R is as defined above^aPreferred is a chain hetero atom such as oxygen, sulfur, and nitrogen, or a 2-valent organic group.

R^aIn the case of a 2-valent organic group, a hydrogen atom bonded to a carbon atom may be replaced with a halogen other than fluorine, for example, chlorine, and may or may not contain a double bond. In addition, R^aThe polymer may be either a linear or branched one, or a cyclic or acyclic one. In addition, R^aFunctional groups (e.g., esters, ethers, ketones, amines, halides, etc.) may be included.

In addition, R^aMay be a non-fluorinated 2-valent organic group, or may be a partially fluorinated or perfluorinated 2-valent organic group.

As R^aThis may be, for example: a hydrocarbon group having no fluorine atom bonded to a carbon atom; a part of hydrogen atoms bonded to carbon atoms being substituted by fluorine atomsA hydrocarbon group of (a); a hydrocarbon group in which all hydrogen atoms bonded to carbon atoms are substituted with fluorine atoms; the hydrocarbon group containing- (C ═ O) -, - (C ═ O) -O-or- (C ═ O) -, may contain an oxygen atom, may contain a double bond, and may contain a functional group.

R^aThe hydrocarbon group may preferably contain a carbon number of 1 to 100, optionally a carbonyl group, and optionally an ether bond, and may contain fluorine in part or all of the hydrogen atoms bonded to the carbon atoms.

As R^aPreferably selected from- (CH)₂)_a-、-(CF₂)_a-、-O-(CF₂)_a-、-(CF₂)_a-O-(CF₂)_b-、-O(CF₂)_a-O-(CF₂)_b-、-(CF₂)_a-[O-(CF₂)_b]_c-、-O(CF₂)_a-[O-(CF₂)_b]_c-、-[(CF₂)_a-O]_b-[(CF₂)_c-O]_d-、-O[(CF₂)_a-O]_b-[(CF₂)_c-O]_d-、-O-[CF₂CF(CF₃)O]_a-(CF₂)_b-、-(C＝O)-、-(C＝O)-O-、-(C＝O)-(CH₂)_a-、-(C＝O)-(CF₂)_a-、-(C＝O)-O-(CH₂)_a-、-(C＝O)-O-(CF₂)_a-、-(C＝O)-[(CH₂)_a-O]_b-、-(C＝O)-[(CF₂)_a-O]_b-、-(C＝O)-O[(CH₂)_a-O]_b-、-(C＝O)-O[(CF₂)_a-O]_b-、-(C＝O)-O[(CH₂)_a-O]_b-(CH₂)_c-、-(C＝O)-O[(CF₂)_a-O]_b-(CF₂)_c-、-(C＝O)-(CH₂)_a-O-(CH₂)_b-、-(C＝O)-(CF₂)_a-O-(CF₂)_b-、-(C＝O)-O-(CH₂)_a-O-(CH₂)_b-、-(C＝O)-O-(CF₂)_a-O-(CF₂)_b-、-(C＝O)-O-C₆H₄-and combinations thereof.

Wherein a, b, c and d are independently at least 1 or more. a. b, c and d independently may be 2 or more, 3 or more, 4 or more, 10 or more, or 20 or more. a. The upper limit of b, c and d is, for example, 100.

As R^aA preferable specific example thereof is-CF₂-O-、-CF₂-O-CF₂-、-CF₂-O-CH₂-、-CF₂-O-CH₂CF₂-、-CF₂-O-CF₂CF₂-、-CF₂-O-CF₂CH₂-、-CF₂-O-CF₂CF₂CH₂-、-CF₂-O-CF(CF₃)-、-CF₂-O-CF(CF₃)CF₂-、-CF₂-O-CF(CF₃)CF₂-O-、-CF₂-O-CF(CF₃)CH₂-、-(C＝O)-、-(C＝O)-O-、-(C＝O)-(CH₂)-、-(C＝O)-(CF₂)-、-(C＝O)-O-(CH₂)-、-(C＝O)-O-(CF₂)-、-(C＝O)-[(CH₂)₂-O]_n-、-(C＝O)-[(CF₂)₂-O]_n-、-(C＝O)-O[(CH₂)₂-O]_n-、-(C＝O)-O[(CF₂)₂-O]_n-、-(C＝O)-O[(CH₂)₂-O]_n-(CH₂)-、-(C＝O)-O[(CF₂)₂-O]_n-(CF₂)-、-(C＝O)-(CH₂)₂-O-(CH₂)-、-(C＝O)-(CF₂)₂-O-(CF₂)-、-(C＝O)-O-(CH₂)₂-O-(CH₂)-、-(C＝O)-O-(CF₂)₂-O-(CF₂)-、-(C＝O)-O-C₆H₄-and the like. Wherein, specifically, R is as defined above^apreferably-CF₂-O-、-CF₂-O-CF₂-、-CF₂-O-CF₂CF₂-、-CF₂-O-CF(CF₃)-、-CF₂-O-CF(CF₃)CF₂-、-CF₂-O-CF(CF₃)CF₂-O-、-(C＝O)-、-(C＝O)-O-、-(C＝O)-(CH₂)-、-(C＝O)-O-(CH₂)-、-(C＝O)-O[(CH₂)₂-O]_n-、-(C＝O)-O[(CH₂)₂-O]_n-(CH₂)-、-(C＝O)-(CH₂)₂-O-(CH₂) -, or- (C ═ O) -O-C₆H₄-。

In the above formula, n is an integer of 1 to 10.

as-R in the above general formula (4)^a-(CZ¹Z²)_kpreferably-CF₂-O-CF₂-、-CF₂-O-CF(CF₃)-、-CF₂-O-C(CF₃)₂-、-CF₂-O-CF₂-CF₂-、-CF₂-O-CF₂-CF(CF₃)-、-CF₂-O-CF₂-C(CF₃)₂-、-CF₂-O-CF₂CF₂-CF₂-、-CF₂-O-CF₂CF₂-CF(CF₃)-、-CF₂-O-CF₂CF₂-C(CF₃)₂-、-CF₂-O-CF(CF₃)-CF₂-、-CF₂-O-CF(CF₃)-CF(CF₃)-、-CF₂-O-CF(CF₃)-C(CF₃)₂-、-CF₂-O-CF(CF₃)-CF₂-、-CF₂-O-CF(CF₃)-CF(CF₃)-、-CF₂-O-CF(CF₃)-C(CF₃)₂-、-CF₂-O-CF(CF₃)CF₂-CF₂-、-CF₂-O-CF(CF₃)CF₂-CF(CF₃)-、-CF₂-O-CF(CF₃)CF₂-C(CF₃)₂-、-CF₂-O-CF(CF₃)CF₂-O-CF₂-、-CF₂-O-CF(CF₃)CF₂-O-CF(CF₃)-、-CF₂-O-CF(CF₃)CF₂-O-C(CF₃)₂-、-(C＝O)-、-(C＝O)-O-、-(C＝O)-(CH₂)-、-(C＝O)-(CF₂)-、-(C＝O)-O-(CH₂)-、-(C＝O)-O-(CF₂)-、-(C＝O)-[(CH₂)₂-O]_n-(CH₂)-、-(C＝O)-[(CF₂)₂-O]_n-(CF₂)-、-(C＝O)-[(CH₂)₂-O]_n-(CH₂)-(CH₂)-、-(C＝O)-[(CF₂)₂-O]_n-(CF₂)-(CF₂)-、-(C＝O)-O[(CH₂)₂-O]_n-(CF₂)-、-(C＝O)-O[(CH₂)₂-O]_n-(CH₂)-(CH₂)-、-(C＝O)-O[(CF₂)₂-O]_n-(CF₂)-、-(C＝O)-O[(CF₂)₂-O]_n-(CF₂)-(CF₂)-、-(C＝O)-(CH₂)₂-O-(CH₂)-(CH₂)-、-(C＝O)-(CF₂)₂-O-(CF₂)-(CF₂)-、-(C＝O)-O-(CH₂)₂-O-(CH₂)-(CH₂)-、-(C＝O)-O-(CF₂)₂-O-(CF₂)-(CF₂)-、-(C＝O)-O-(CH₂)₂-O-(CH₂)-C(CF₃)₂-、-(C＝O)-O-(CF₂)₂-O-(CF₂)-C(CF₃)₂-, or- (C ═ O) -O-C₆H₄-C(CF₃)₂-, more preferably-CF₂-O-CF(CF₃)-、-CF₂-O-CF₂-CF(CF₃)-、-CF₂-O-CF₂CF₂-CF(CF₃)-、-CF₂-O-CF(CF₃)-CF(CF₃)-、-CF₂-O-CF(CF₃)CF₂-CF(CF₃)-、-CF₂-O-CF(CF₃)CF₂-O-CF(CF₃)-、-(C＝O)-、-(C＝O)-O-(CH₂)-、-(C＝O)-O-(CH₂)-(CH₂)-、-(C＝O)-O[(CH₂)₂-O]_n-(CH₂)-(CH₂)-、-(C＝O)-O-(CH₂)₂-O-(CH₂)-C(CF₃)₂-, or- (C ═ O) -O-C₆H₄-C(CF₃)₂-。

In the above formula, n is an integer of 1 to 10.

Specific examples of the compound represented by the general formula (4) include

[ solution 5]

(in the formula, X^jAnd Y³As described above. n is an integer of 1 to 10), and the like.

As R^aPreferably, the following general formula (r 1):

-(C＝O)_h-(O)_i-CF₂-O-(CX⁶ ₂)_e-{O-CF(CF₃)}_f-(O)_g- (r1)

(in the formula, X⁶Each independently H, F or CF₃E is an integer of 0 to 3, f is an integer of 0 to 3, g is 0 or 1, h is 0 or 1, i is 0 or 1), and the following general formula (r2) is also preferable:

-(C＝O)_h-(O)_i-CF₂-O-(CX⁷ ₂)_e-(O)_g- (r2)

(in the formula, X⁷Each independently H, F or CF₃E is an integer of 0 to 3, g is 0 or 1, h is 0 or 1, and i is a 2-valent group represented by 0 or 1).

as-R of the above general formula (4)^a-CZ¹Z²The following formula (t1) is also preferred:

-(C＝O)_h-(O)_i-CF₂-O-(CX⁶ ₂)_e-{O-CF(CF₃)}_f-(O)_g-CZ¹Z²-(t1)

(in the formula, X⁶Each independently H, F or CF₃E is an integer of 0 to 3, f is an integer of 0 to 3, g is 0 or 1, h is 0 or 1, i is 0 or 1, Z¹And Z²Each independently is F or CF₃) The 2-valent group shown in the formula (t1), Z¹And Z²More preferably, one is F and the other is CF₃。

In the above general formula (4), as-R^a-CZ¹Z²The following formula (t2) is also preferred:

-(C＝O)_h-(O)_i-CF₂-O-(CX⁷ ₂)_e-(O)_g-CZ¹Z²- (t2)

(in the formula, X⁷Each independently H, F or CF₃E is an integer of 0 to 3, g is 0 or 1, h is 0 or 1, i is 0 or 1, Z¹And Z²Each independently H, F or CF₃) The 2-valent group shown in the formula (t2), Z¹And Z²More preferably, one is F and the other is CF₃。

The compound represented by the formula (4) is also preferably selected in addition to the hydrophilic group (Y)³) And has no C-H bond and a C-F bond. That is, in the general formula (4), X is preferableⁱ、X^jAnd X^kAll are F, R^aThe perfluoroalkylene group may be any of a chain and a branched chain, may be any of a cyclic and an acyclic, and may contain at least 1 chain hetero atom. The number of carbon atoms of the perfluoroalkylene group may be 2 to 20, or 4 to 18.

The compounds of formula (4) may also be partially fluorinated. That is, the compound represented by the general formula (4) is also preferably selected from hydrophilic groups (Y) ³) And has at least 1 hydrogen atom bonded to a carbon atom and has at least 1 fluorine atom bonded to a carbon atom.

The compound represented by the general formula (4) is also preferably a compound represented by the following formula (4 a).

CF₂＝CF-O-Rf⁰-Y³ (4a)

(in the formula, Y³Is a hydrophilic group, Rf⁰The perfluorinated compound is a perfluorinated divalent linking group which is perfluorinated, may have a chain or branched chain structure, a cyclic or acyclic structure, a saturated or unsaturated structure, a substituted or unsubstituted structure, and optionally additionally contains 1 or more heteroatoms selected from the group consisting of sulfur, oxygen, and nitrogen. )

The compound represented by the general formula (4) is also preferably a compound represented by the following formula (4 b).

CH₂＝CH-O-Rf⁰-Y³ (4b)

(in the formula, Y³Is a hydrophilic group, Rf⁰A per-fluorinated divalent linking group as defined for formula (4 a). )

In the general formula (4), Y³is-OSO₃M is one of the preferred modes. At Y³is-OSO₃In the case of M, - [ CF ] is mentioned as a polymerization unit based on the compound represented by the general formula (4)₂CF(OCF₂CF₂CH₂OSO₃M)]-、-[CH₂CH((CF₂)₄CH₂OSO₃M)]-、-[CF₂CF(O(CF₂)₄CH₂OSO₃M)]-、-[CF₂CF(OCF₂CF(CF₃)CH₂OSO₃M)]-、-[CF₂CF(OCF₂CF(CF₃)OCF₂CF₂CH₂OSO₃M)]-、-[CH₂CH((CF₂)₄CH₂OSO₃M)]-、-[CF₂CF(OCF₂CF₂SO₂N(CH₃)CH₂CH₂OSO₃M)]-、-[CH₂CH(CF₂CF₂CH₂OSO₃M)]-、-[CF₂CF(OCF₂CF₂CF₂CF₂SO₂N(CH₃)CH₂CH₂OSO₃M)]-、-[CH₂CH(CF₂CF₂CH₂OSO₃M)]-and the like. In the above formula, M is the same as described above.

In the general formula (4), Y³is-SO₃M is also one of the preferred modes. At Y³is-SO₃In the case of M, - [ CF ] is mentioned as a polymerization unit based on the compound represented by the general formula (4)₂CF(OCF₂CF₂SO₃M)]-、-[CF₂CF(O(CF₂)₄SO₃M)]-、-[CF₂CF(OCF₂CF(CF₃)SO₃M)]-、-[CF₂CF(OCF₂CF(CF₃)OCF₂CF₂SO₃M)]-、-[CH₂CH(CF₂CF₂SO₃M)]-、-[CF₂CF(OCF₂CF(CF₃)OCF₂CF₂CF₂CF₂SO₃M)]-、-[CH₂CH((CF₂)₄SO₃M)]-、-[CH₂CH(CF₂CF₂SO₃M)]-、-[CH₂CH((CF₂)₄SO₃M)]-and the like. In the above formula, M is the same as described above.

In the general formula (4), Y³It is also one of the preferred modes to be-COOM. At Y ³In the case of-COOM, - [ CF ] is mentioned as a polymerization unit based on the compound represented by the general formula (4)₂CF(OCF₂CF₂COOM)]-、-[CF₂CF(O(CF₂)₅COOM)]-、-[CF₂CF(OCF₂CF(CF₃)COOM)]-、-[CF₂CF(OCF₂CF(CF₃)O(CF₂)_nCOOM)]- (n greater than 1), [ CH₂CH(CF₂CF₂COOM)]-、-[CH₂CH((CF₂)₄COOM)]-、-[CH₂CH(CF₂CF₂COOM)]-、-[CH₂CH((CF₂)₄COOM)]-、-[CF₂CF(OCF₂CF₂SO₂NR’CH₂COOM)]-、-[CF₂CF(O(CF₂)₄SO₂NR’CH₂COOM)]-、-[CF₂CF(OCF₂CF(CF₃)SO₂NR’CH₂COOM)]-、-[CF₂CF(OCF₂CF(CF₃)OCF₂CF₂SO₂NR’CH₂COOM)]-、-[CH₂CH(CF₂CF₂SO₂NR’CH₂COOM)]-、-[CF₂CF(OCF₂CF(CF₃)OCF₂CF₂CF₂CF₂SO₂NR’CH₂COOM)]-、-[CH₂CH((CF₂)₄SO₂NR’CH₂COOM)]-、-[CH₂CH(CF₂CF₂SO₂NR’CH₂COOM)]-、-[CH₂CH((CF₂)₄SO₂NR’CH₂COOM)]-and the like. In the above formula, R' is H or C_1-4Alkyl, M are the same as described above.

In the general formula (4), Y³is-OPO₃M is also one of the preferred modes. At Y³is-OPO₃In the case of M, - [ CF ] is mentioned as a polymerization unit based on the compound represented by the general formula (4)₂CF(OCF₂CF₂CH₂OP(O)(OM)₂)]-、-[CF₂CF(O(CF₂)₄CH₂OP(O)(OM)₂)]-、-[CF₂CF(OCF₂CF(CF₃)CH₂OP(O)(OM)₂)]-、-[CF₂CF(OCF₂CF(CF₃)OCF₂CF₂CH₂OP(O)(OM)₂)]-、-[CF₂CF(OCF₂CF₂SO₂N(CH₃)CH₂CH₂OP(O)(OM)₂)]-、-[CF₂CF(OCF₂CF₂CF₂CF₂SO₂N(CH₃)CH₂CH₂OP(O)(OM)₂)]-、-[CH₂CH(CF₂CF₂CH₂OP(O)(OM)₂)]-、-[CH₂CH((CF₂)₄CH₂OP(O)(OM)₂)]-、-[CH₂CH(CF₂CF₂CH₂OP(O)(OM)₂)]-、-[CH₂CH((CF₂)₄CH₂OP(O)(OM)₂)]-and the like. In the above formula, M is the same as described above.

In the general formula (4), Y³is-PO₃M is also one of the preferred modes. At Y³is-PO₃In the case of M, - [ CF ] is mentioned as a polymerization unit based on the compound represented by the general formula (4)₂CF(OCF₂CF₂P(O)(OM)₂)]-、-[CF₂CF(O(CF₂)₄P(O)(OM)₂)]-、-[CF₂CF(OCF₂CF(CF₃)P(O)(OM)₂)]-、-[CF₂CF(OCF₂CF(CF₃)OCF₂CF₂P(O)(OM)₂)]-、-[CH₂CH(CF₂CF₂P(O)(OM)₂)]-、-[CH₂CH((CF₂)₄P(O)(OM)₂)]-、-[CH₂CH(CF₂CF₂P(O)(OM)₂)]-, and- [ CH ]₂CH((CF₂)₄P(O)(OM)₂)]Wherein M is the same as described above.

The compound represented by the above general formula (4) is preferably at least one selected from the group consisting of the following monomers, the monomers being represented by the following general formula (5):

CX₂＝CY(-CZ₂-O-Rf-Y³) (5)

(wherein X is the same or different and is-H or-F, Y is-H, -F, alkyl or fluoroalkyl, and Z is the same or different and is-H, -F, alkyl or fluoroalkyl Rf is a fluoroalkylene group having 1 to 40 carbon atoms or a fluoroalkylene group having 2 to 100 carbon atoms and having an ether bond.Y³The same as described above). ) A monomer as shown; the following general formula (6):

CX₂＝CY(-O-Rf-Y³) (6)

(wherein X is-H or-F, Y is-H, -F, alkyl or fluoroalkyl, and Rf is a C1-40 fluoroalkylene group or a C2-100 fluoroalkylene group having an ether bond.) Y ³The same as above); and the following general formula (7):

CX₂＝CY(-Rf-Y³) (7)

(wherein X is-H or-F, Y is-H, -F, alkyl or fluoroalkyl, and Rf is a C1-40 fluoroalkylene group or a C2-100 fluoroalkylene group having an ether bond.) Y³The same as described above).

In the general formula (5), X is-H or-F. X may be both-F or at least one of-H. For example, one may be-F and the other may be-H, or both may be-H.

In the general formula (5), Y is-H, -F, alkyl or fluoroalkyl.

The alkyl group may be an alkyl group containing no fluorine atom and having 1 or more carbon atoms. The number of carbon atoms of the alkyl group is preferably 6 or less, more preferably 4 or less, and still more preferably 3 or less.

The fluoroalkyl group may be an alkyl group containing at least 1 fluorine atom and having 1 or more carbon atoms. The number of carbon atoms of the fluoroalkyl group is preferably 6 or less, more preferably 4 or less, and still more preferably 3 or less.

As Y, preferred is-H, -F or-CF₃And more preferably-F.

In the above general formula (5), Z, which may be the same or different, is-H, -F, alkyl or fluoroalkyl.

The alkyl group may be an alkyl group containing no fluorine atom and having 1 or more carbon atoms. The number of carbon atoms of the alkyl group is preferably 6 or less, more preferably 4 or less, and still more preferably 3 or less.

The fluoroalkyl group may be an alkyl group containing at least 1 fluorine atom and having 1 or more carbon atoms. The number of carbon atoms of the fluoroalkyl group is preferably 6 or less, more preferably 4 or less, and still more preferably 3 or less.

As the above Z, preferred is-H, -F or-CF₃And more preferably-F.

In the above general formula (5), at least one of X, Y and Z preferably contains a fluorine atom. For example, X may be-H, and Y and Z may be-F.

In the general formula (5), Rf is a C1-40 fluoroalkylene group or a C2-100 fluoroalkylene group having an ether bond.

The number of carbon atoms of the fluorinated alkylene group is preferably 2 or more. Further, it is preferably 30 or less, more preferably 20 or less, and still more preferably 10 or less. Examples of the fluoroalkylene group include-CF₂-、-CH₂CF₂-、-CF₂CF₂-、-CF₂CH₂-、-CF₂CF₂CH₂-、-CF(CF₃)-、-CF(CF₃)CF₂-、-CF(CF₃)CH₂-and the like. The above-mentioned fluoroalkylene group is preferably a perfluoroalkylene group.

The number of carbon atoms of the fluorinated alkylene group having an ether bond is preferably 3 or more. Further, it is preferably 60 or less, more preferably 30 or less, and further preferably 12 or less.

For example, the following formula is also preferred:

[ solution 6]

(in the formula, Z¹Is F or CF₃；Z²And Z³Are H or F respectively; z⁴Is H, F or CF₃(ii) a p1+ q1+ r1 is an integer of 0-10; s1 is 0 or 1; t1 is an integer of 0 to 5, wherein, in Z ³And Z⁴P1+ q1+ r1+ s1 are not all H) 2-valent groups.

Specific examples of the fluorinated alkylene group having an ether bond include-CF (CF)₃)CF₂-O-CF(CF₃)-、-(CF(CF₃)CF₂-O)_n-CF(CF₃) - (wherein n is an integer of 1 to 10), -CF (CF)₃)CF₂-O-CF(CF₃)CH₂-、-(CF(CF₃)CF₂-O)_n-CF(CF₃)CH₂- (wherein n is an integer of 1 to 10), -CH₂CF₂CF₂O-CH₂CF₂CH₂-、-CF₂CF₂CF₂O-CF₂CF₂-、-CF₂CF₂CF₂O-CF₂CF₂CH₂-、-CF₂CF₂O-CF₂-、-CF₂CF₂O-CF₂CH₂-、-CF(CF₃)CH₂-and the like.

The fluorine-containing alkylene group having an ether bond is preferably a perfluoroalkylene group.

In the above general formula (5), Y³is-COOM, -SO₃M or-OSO₃M (M is H, a metal atom, NR)⁷ ₄Imidazolium with or without substituents, pyridinium with or without substituents or phosphonium with or without substituents, R⁷Are H or an organic group, which may be the same or different. Any 2 may be bonded to each other to form a ring. ).

As R⁷Preferably H or C_1-10Organic group of (2)A group, more preferably H or C_1-4Further preferably H or C_1-4Alkyl group of (1).

Examples of the metal atom include alkali metals (group 1), alkaline earth metals (group 2), and the like, and Na, K, and Li are preferable.

As the above M, preferred is-H, a metal atom or-NR⁷ ₄More preferably-H, alkali metal (group 1), alkaline earth metal (group 2) or-NR⁷ ₄Further, it is preferably-H, -Na, -K, -Li or-NH₄Further more preferably-Na, -K or-NH₄Particularly preferred is-Na or-NH₄Most preferably-NH ₄。

As the above Y³preferably-COOM or-SO₃M, more preferably-COOM.

Examples of the monomer represented by the general formula (5) include the following formula (5 a):

CX^h ₂＝CFCF₂-O-(CF(CF₃)CF₂O)_n5-CF(CF₃)-Y³ (5a)

(in the formula, each X^hThe same indicates F or H. n5 represents 0 or an integer of 1 to 10, Y³The same as defined above) as a preferred substance.

In the general formula (5a), n5 is preferably 0 or an integer of 1 to 5, more preferably 0, 1 or 2, and still more preferably 0 or 1, from the viewpoint of obtaining PTFE particles having a small primary particle diameter. From the viewpoint of obtaining appropriate water solubility and surface activity, Y is³preferably-COOM, and M is preferably H or NH, from the viewpoint of being less likely to remain as an impurity and improving the heat resistance of the obtained composition and the drawn body obtained from the composition₄。

The monomer represented by the general formula (5) is preferably a monomer (5b) represented by the following general formula (5 b).

CH₂＝CF(-CF₂-O-Rf-Y³) (5b)

(wherein Rf and Y³As described above. )

Specific examples of the monomer represented by the general formula (5b) include

[ solution 7]

(in the formula, Z¹Is F or CF₃；Z²And Z³Are H or F respectively; z⁴Is H, F or CF₃(ii) a p1+ q1+ r1 is an integer of 0-10; s1 is 0 or 1; t1 is an integer of 0 to 5, Y³As described above. Wherein Z is³And Z⁴P1+ q1+ r1+ s1 is not 0) in all cases. More specifically, preferred examples thereof include

[ solution 8]

CH₂＝CFCF₂OCH₂CF₂-Y³，CH₂＝CFCF₂O(CH₂CF₂CF₂O)CH₂CF₂-Y³，

CH₂＝CFCF₂OCH₂CF₂CH₂-Y³，

CH₂＝CFCF₂O(CH₂CF₂CF₂O)CH₂CF₂CH₂-Y³，

CH₂＝CFCF₂OCF₂CF₂-Y³，CH₂＝CFCF₂O(CF₂CF₂CF₂O)CF₂CF₂-Y³，

CH₂＝CFCF₂OCF₂CF₂CH₂-Y³，

CH₂＝CFCF₂O(CF₂CF₂CF₂O)CF₂CF₂CH₂-Y³，

CH₂＝CFCF₂OCF₂-Y³，CH₂＝CFCF₂O(CF₂CF₂O)CF₂-Y³，

CH₂＝CFCF₂OCF₂CH₂-Y³，

CH₂＝CFCF₂O(CF₂CF₂O)CF₂CH₂-Y³，

Etc., among them, preferred are

[ solution 9]

As the monomer represented by the above general formula (5b), Y in the formula (5b) is preferable³is-COOM, particularly preferably selected from the group consisting of CH₂＝CFCF₂OCF(CF₃) COOM and CH₂＝CFCF₂OCF(CF₃)CF₂OCF(CF₃) COOM (wherein M is as defined above), more preferably CH₂＝CFCF₂OCF(CF₃)COOM。

The monomer represented by the general formula (5) is preferably a monomer (5c) represented by the following general formula (5 c).

CX² ₂＝CFCF₂-O-(CF(CF₃)CF₂O)_n5-CF(CF₃)-Y³ (5c)

(in the formula, each X²The same indicates F or H. n5 represents 0 or an integer of 1 to 10, Y³As defined above. )

In the formula (5c), n5 is preferably 0 or an integer of 1 to 5, more preferably 0, 1 or 2, and even more preferably 0 or 1, from the viewpoint of stability of the aqueous dispersion obtained. The above Y is a group of compounds having a suitable water solubility and stability of the aqueous dispersion³preferably-COOM¹In view of the difficulty of remaining as impurities and the improvement in heat resistance of the molded article obtained, the above M is used¹Preferably H or NH₄。

As the perfluorovinyl alkyl compound represented by the above formula (5c)Examples of the compound include CH₂＝CFCF₂OCF(CF₃)COOM¹、CH₂＝CFCF₂OCF(CF₃)CF₂OCF(CF₃)COOM¹(in the formula, M¹Same as defined above).

Examples of the monomer represented by the general formula (5) include a monomer represented by the following general formula (5d) and a monomer represented by the following general formula (5 e).

CF₂＝CFCF₂-O-Rf-Y³ (5d)

CF₂＝CF-Rf-Y³ (5e)

(wherein Rf and Y ³As described above. )

More specifically, there may be mentioned

[ solution 10]

CF₂＝CFCF₂OCF₂CF₂CF₂-Y³，

CF₂＝CFCF₂OCF₂CF₂CF₂CH₂-Y³，

And the like.

In the above general formula (6), X is-H or-F. X may be both-F or at least one of-H. For example, one may be-F and the other may be-H, or both may be-H.

In the general formula (6), Y is-H, -F, alkyl or fluoroalkyl.

The alkyl group may be an alkyl group containing no fluorine atom and having 1 or more carbon atoms. The number of carbon atoms of the alkyl group is preferably 6 or less, more preferably 4 or less, and still more preferably 3 or less.

The fluoroalkyl group may be an alkyl group containing at least 1 fluorine atom and having 1 or more carbon atoms. The number of carbon atoms of the fluoroalkyl group is preferably 6 or less, more preferably 4 or less, and still more preferably 3 or less.

As Y, preferred is-H, -F or-CF₃And more preferably-F.

In the above general formula (6), at least one of the above X and Y preferably contains a fluorine atom. For example, X may be-H, and Y and Z may be-F.

In the general formula (6), Rf is a C1-40 fluoroalkylene group or a C2-100 fluoroalkylene group having an ether bond.

The number of carbon atoms of the fluorinated alkylene group is preferably 2 or more. Further, it is preferably 30 or less, more preferably 20 or less, and still more preferably 10 or less. Examples of the fluoroalkylene group include-CF ₂-、-CH₂CF₂-、-CF₂CF₂-、-CF₂CH₂-、-CF₂CF₂CH₂-、-CF(CF₃)-、-CF(CF₃)CF₂-、-CF(CF₃)CH₂-and the like. The above-mentioned fluoroalkylene group is preferably a perfluoroalkylene group.

The monomer represented by the above general formula (6) is preferably at least one selected from the group consisting of monomers represented by the following general formulae (6a), (6b), (6c) and (6 d).

CF₂＝CF-(CF₂)_n1-Y³ (6a)

(wherein n1 represents an integer of 1 to 10, and Y represents³represents-SO₃M¹or-COOM¹，M¹Represents H, a metal atom, NR⁷ ₄Imidazolium with or without substituents, pyridinium with or without substituents or phosphonium with or without substituents, R⁷Represents H or an organic group. )

CF₂＝CF-(CF₂C(CF₃)F)_n2-Y³ (6b)

(wherein n2 represents an integer of 1 to 5, and Y represents³As defined above. )

CF₂＝CF-O-(CFX¹)_n3-Y³ (6c)

(in the formula, X¹Represents F or CF₃N3 represents an integer of 1 to 10, Y³As defined above. )

CF₂＝CF-O-(CF₂CFX¹O)_n4-CF₂CF₂-Y³ (6d)

(wherein n4 represents an integer of 1 to 10, and Y represents³And X¹As defined above. )

In the above formula (6a), n1 is preferably an integer of 5 or less, more preferably an integer of 2 or less. The above Y is a group of compounds having a suitable water solubility and stability of the aqueous dispersion³preferably-COOM¹M is difficult to remain as impurities and improves the heat resistance of the resulting molded article¹Preferably H or NH₄。

Examples of the perfluorovinyl alkyl compound represented by the formula (6a) include CF₂＝CFCF₂COOM¹(in the formula, M ¹Same as defined above).

In the above formula (6b), n2 is preferably an integer of 3 or less from the viewpoint of stability of the aqueous dispersion to be obtained, and Y is an integer of appropriate water solubility and stability of the aqueous dispersion to be obtained³preferably-COOM¹M is difficult to remain as impurities and improves the heat resistance of the resulting molded article¹Preferably H or NH₄。

In the above formula (6c), n3 is preferably an integer of 5 or less from the viewpoint of water solubility, and Y is an integer of 5 or less from the viewpoint of obtaining appropriate water solubility and stability of the aqueous dispersion³preferably-COOM¹From the viewpoint of improving dispersion stability, M is¹Preferably H or NH₄。

In the above formula (6d), the X is a group represented by the formula¹preferably-CF₃In terms of water solubility, n4 is preferably an integer of 5 or less, and Y is an integer of 5 or less in terms of obtaining appropriate water solubility and stability of the aqueous dispersion³preferably-COOM¹M above¹Preferably H or NH₄。

Examples of the perfluorovinyl ether compound represented by the formula (6d) include CF₂＝CFOCF₂CF(CF₃)OCF₂CF₂COOM¹(in the formula, M¹Representation H, NH₄Or an alkali metal).

In the general formula (7), Rf is preferably a C1-40 fluoroalkylene group. In the general formula (7), at least one of X and Y preferably contains a fluorine atom.

The monomer represented by the above general formula (7) is preferably selected from the group consisting of the following general formula (7 a):

CF₂＝CF-(CF₂)_n1-Y³ (7a)

(wherein n1 represents an integer of 1 to 10, and Y represents³The same as defined above), and the following general formula (7 b):

CF₂＝CF-(CF₂C(CF₃)F)_n2-Y³ (7b)

(wherein n2 represents an integer of 1 to 5, and Y represents³Same as defined above) of the above-mentioned monomers.

Y is above³preferably-SO₃M¹or-COOM¹，M¹Preferably H, a metal atom, NR⁷ ₄An imidazolium with or without substituents, a pyridinium with or without substituents or a phosphonium with or without substituents. R is as defined above⁷Represents H or an organic group.

In the formula (7a), n1 is preferably an integer of 5 or less, more preferably an integer of 2 or less. The above Y is a group of compounds having a suitable water solubility and stability of the aqueous dispersion³preferably-COOM¹M is difficult to remain as impurities and improves the heat resistance of the resulting molded article¹Preferably H or NH₄。

Examples of the perfluorovinyl alkyl compound represented by the formula (7a) include CF₂＝CFCF₂COOM¹(in the formula, M¹Same as defined above).

In the above formula (7b), n2 is preferably an integer of 3 or less from the viewpoint of stability of the aqueous dispersion to be obtained, and Y is an integer of appropriate water solubility and stability of the aqueous dispersion to be obtained ³preferably-COOM¹M is difficult to remain as impurities and improves the heat resistance of the resulting molded article¹Preferably H or NH₄。

The modifying monomer preferably contains the modifying monomer (a), preferably contains at least one selected from the group consisting of compounds represented by general formula (5c), general formula (6a), general formula (6b), general formula (6c), and general formula (6d), and more preferably contains a compound represented by general formula (5 c).

The content of the modifying monomer (a) is preferably in the range of 0.00001 to 1.0 mass%. The lower limit is more preferably 0.0001% by mass, still more preferably 0.0005% by mass, yet more preferably 0.001% by mass, yet more preferably 0.005% by mass, and particularly preferably 0.009% by mass. The upper limit is preferably 0.90% by mass, more preferably 0.50% by mass, even more preferably 0.40% by mass, even more preferably 0.30% by mass, even more preferably 0.10% by mass, even more preferably 0.08% by mass, particularly preferably 0.05% by mass, and particularly preferably 0.01% by mass.

The modified monomer is preferably at least one selected from the group consisting of hexafluoropropylene, vinylidene fluoride, fluoro (alkyl vinyl ether), (perfluoroalkyl) ethylene and ethylene, more preferably at least one selected from the group consisting of perfluoro (methyl vinyl ether), perfluoro (propyl vinyl ether), (perfluorobutyl) ethylene, (perfluorohexyl) ethylene and (perfluorooctyl) ethylene, and even more preferably perfluoro (methyl vinyl ether), because a high-strength stretched body can be obtained.

The modified PTFE preferably has a modified monomer unit content in the range of 0.00001 to 1.0 mass%. The lower limit of the modifying monomer unit is more preferably 0.0001% by mass, still more preferably 0.0005% by mass, yet more preferably 0.001% by mass, still more preferably 0.005% by mass, and particularly preferably 0.009% by mass. The upper limit of the modifying monomer unit is preferably 0.90% by mass, more preferably 0.50% by mass, still more preferably 0.30% by mass, yet more preferably 0.10% by mass, yet more preferably 0.08% by mass, particularly preferably 0.05% by mass, and particularly preferably 0.01% by mass. In the present specification, the modified monomer unit refers to a portion derived from a modified monomer that is a part of the molecular structure of the modified PTFE, and the total monomer unit refers to a portion derived from a total monomer in the molecular structure of the modified PTFE.

In the present specification, the content of each monomer constituting PTFE can be calculated by appropriately combining NMR, FT-IR, elemental analysis, and fluorescent X-ray analysis depending on the type of the monomer.

The PTFE is preferably PTFE that has not been heated at a temperature equal to or higher than the primary peak temperature.

The PTFE may be either unfired PTFE or semi-fired PTFE. In view of the ease of the process and the ease of controlling the thickness and pore size, the preferred PTFE is unfired. From the viewpoint of enhancing the strength of the biaxially oriented film or reducing the pore diameter, semi-fired PTFE is preferable.

Examples of the unfired PTFE include polymerized PTFE.

The above-mentioned unfired PTFE means PTFE that has not been heated to a temperature of the secondary peak temperature or higher, and the semi-fired PTFE is PTFE that has not been heated to a temperature of the primary peak temperature or higher, and that has been heated to a temperature of the primary peak temperature or lower and the secondary peak temperature or higher.

The primary peak temperature is a maximum peak temperature of an endothermic curve appearing on a crystal melting curve when the unfired PTFE is measured by a differential scanning calorimeter.

The secondary peak temperature is a maximum peak temperature of an endothermic curve appearing on a crystal melting curve when PTFE heated to a temperature equal to or higher than the primary peak temperature (for example, 360 ℃) is measured by a differential scanning calorimeter.

In the present specification, the endothermic curve is an endothermic curve obtained by heating with a differential scanning calorimeter at a temperature-raising rate of 10 ℃/min.

The PTFE may have a core-shell structure. Examples of the polytetrafluoroethylene having a core-shell structure include modified polytetrafluoroethylene in which particles contain a core of high molecular weight polytetrafluoroethylene and a shell of lower molecular weight polytetrafluoroethylene or modified polytetrafluoroethylene.

Examples of such modified polytetrafluoroethylene include polytetrafluoroethylene described in Japanese patent application laid-open No. 2005-527652.

The PTFE of the present invention is obtained by a production method comprising the steps of: a step of emulsion-polymerizing tetrafluoroethylene alone or tetrafluoroethylene and a modifying monomer copolymerizable with tetrafluoroethylene in an aqueous medium in the presence of a specific hydrocarbon surfactant; and a step of continuously adding a specific hydrocarbon surfactant in the step. The PTFE of the present invention is preferably obtained by the above-described production method.

The continuous addition of the specific hydrocarbon surfactant means, for example, that the specific hydrocarbon surfactant is not added all at once but is added over time or in portions. The specific hydrocarbon surfactant is, for example, a hydrocarbon surfactant having 1 or more carbonyl groups (excluding the carbonyl group in the carboxyl group), or a hydrocarbon surfactant obtained by subjecting a hydrocarbon surfactant having 1 or more carbonyl groups (excluding the carbonyl group in the carboxyl group) to radical treatment or oxidation treatment. The radical treatment may be a treatment for generating radicals in a hydrocarbon surfactant having 1 or more carbonyl groups (excluding a carbonyl group in a carboxyl group), and examples of the radical treatment include the following treatments: adding deionized water and hydrocarbon surfactant into a reactor, sealing the reactor, replacing the system with nitrogen, heating and pressurizing the reactor, adding a polymerization initiator, stirring for a certain time, depressurizing the reactor until the pressure reaches atmospheric pressure, and cooling. The oxidation treatment is a treatment in which an oxidizing agent is added to a hydrocarbon surfactant having 1 or more carbonyl groups (excluding a carbonyl group in a carboxyl group). Examples of the oxidizing agent include oxygen, ozone, hydrogen peroxide, manganese (IV) oxide, potassium permanganate, potassium dichromate, nitric acid, and sulfur dioxide. The PTFE of the present invention obtained by such a production method can have SSG of 2.175 or less and can have excellent stretchability even when obtained in the presence of a hydrocarbon-based surfactant. That is, by the above-mentioned production method using a specific hydrocarbon surfactant, it is surprisingly possible to produce PTFE having a molecular weight equivalent to that of the production method using a conventional fluorosurfactant without using a conventional fluorosurfactant.

Further, the present invention provides a polytetrafluoroethylene obtained by a production method comprising the steps of: a step of emulsion-polymerizing tetrafluoroethylene alone or tetrafluoroethylene and a modifying monomer copolymerizable with tetrafluoroethylene in an aqueous medium in the presence of a specific hydrocarbon surfactant; and a step of continuously adding a specific hydrocarbon surfactant in the step.

In the above production method, the step of continuously adding the specific hydrocarbon surfactant is preferably performed such that the addition of the hydrocarbon surfactant to the aqueous medium is started when the solid content of PTFE formed in the aqueous medium is less than 0.60 mass%. It is preferable to start adding the specific hydrocarbon surfactant to the aqueous medium when the amount of the surfactant is 0.5% by mass or less. The specific hydrocarbon surfactant is preferably added at the start of the addition when the solid content is 0.3% by mass or less, more preferably at the start of the addition when the solid content is 0.2% by mass or less, still more preferably at the start of the addition when the solid content is 0.1% by mass or less, and particularly preferably at the start of the polymerization. The solid content is a concentration based on the total of the aqueous medium and PTFE.

In the step of continuously adding the specific hydrocarbon surfactant, the amount of the specific hydrocarbon surfactant added is preferably 0.01 to 10% by mass based on 100% by mass of the aqueous medium. The lower limit is more preferably 0.05% by mass, the lower limit is still more preferably 0.1% by mass, the upper limit is still more preferably 5% by mass, and the upper limit is still more preferably 1% by mass.

In the step of emulsion-polymerizing tetrafluoroethylene alone or tetrafluoroethylene and a modifying monomer copolymerizable with tetrafluoroethylene in an aqueous medium in the presence of the specific hydrocarbon surfactant, the amount of the specific hydrocarbon surfactant is preferably large and preferably 0.0001 to 10% by mass based on 100% by mass of the aqueous medium. The lower limit is more preferably 0.001 mass%, and the upper limit is more preferably 1 mass%. If the amount is less than 0.0001% by mass, the dispersing power may be insufficient, and if it exceeds 10% by mass, the effect corresponding to the amount may not be obtained, and conversely, the polymerization rate may be lowered or the reaction may be stopped. The amount of the specific hydrocarbon surfactant is appropriately determined depending on the kind of the monomer to be used, the molecular weight of the target PTFE, and the like.

The specific hydrocarbon surfactant is preferably represented by the formula: R-X (wherein R is a non-fluorine-containing organic group having 1 to 2000 carbon atoms and having 1 or more carbonyl groups (excluding carbonyl groups in the carboxyl group), and X is-OSO₃X¹、-COOX¹or-SO₃X¹(X¹Is H, a metal atom, NR¹ ₄Imidazolium with or without substituents, pyridinium with or without substituents or phosphonium with or without substituents, R¹H or an organic group, which may be the same or different)). The number of carbon atoms of R is preferably 500 or less, more preferably 100 or less, further preferably 50 or less, and further more preferably 30 or less.

The specific hydrocarbon surfactant is more preferably selected from the group consisting of the following formula (a):

[ solution 11]

(in the formula, R^1aIs a linear or branched alkyl group having 1 or more carbon atoms or a cyclic alkyl group having 3 or more carbon atoms, the hydrogen atom bonded to the carbon atom may be substituted by a hydroxyl group or a 1-valent organic group containing an ester bond, and the carbon number is 2 or moreThe compound (b) may contain a carbonyl group, and may contain a heterocyclic ring having a valence of 1 or 2 or may form a ring when the number of carbon atoms is 3 or more. R^2aAnd R^3aIndependently a single bond or a 2-valent linking group. R ^1a、R^2aAnd R^3aThe total number of carbon atoms of (2) is 6 or more. X^aIs H, a metal atom, NR^4a ₄Imidazolium with or without substituents, pyridinium with or without substituents or phosphonium with or without substituents, R^4aAre H or organic radicals, which may be identical or different. R^1a、R^2aAnd R^3aAny two of which may be bonded to each other to form a ring), and the following formula (b):

[ solution 12]

(in the formula, R^1bThe alkyl group may be a linear or branched alkyl group having 1 or more carbon atoms, which may have a substituent, or a cyclic alkyl group having 3 or more carbon atoms, which may have a substituent, and may contain a heterocyclic ring having 1 or 2 valences or may form a ring when the number of carbon atoms is 3 or more. R^2bAnd R^4bIndependently is H or a substituent. R^3bIs an alkylene group having 1 to 10 carbon atoms, which may have a substituent. n is an integer of 1 or more. p and q are independently integers of 0 or more. X^bIs H, a metal atom, NR^5b ₄Imidazolium with or without substituents, pyridinium with or without substituents or phosphonium with or without substituents, R^5bAre H or organic radicals, which may be identical or different. R^1b、R^2b、R^3bAnd R^4bAny two of which may be bonded to each other to form a ring. L is a single bond, -CO ₂-B-*、-OCO-B-*、-CONR^6b-B-*、-NR^6bCO-B-, or-CO- (excluding-CO)₂-B-、-OCO-B-、-CONR^6b-B-、-NR⁶Carbonyl group contained in CO-B-), B being a single bond or having or not having a substituentAn alkylene group of 1 to 10 carbon atoms, R^6bH or an alkyl group having 1 to 4 carbon atoms with or without a substituent. is-OSO in the formula₃X^bBonded side), the following formula (c):

[ solution 13]

(in the formula, R^1cThe alkyl group may be a linear or branched alkyl group having 1 or more carbon atoms or a cyclic alkyl group having 3 or more carbon atoms, and the hydrogen atom bonded to the carbon atom may be substituted with a hydroxyl group or a 1-valent organic group containing an ester bond, and may contain a carbonyl group when the carbon number is 2 or more, or may contain a 1-valent or 2-valent heterocyclic ring when the carbon number is 3 or more, or may form a ring. R^2cAnd R^3cIndependently a single bond or a 2-valent linking group. R^1c、R^2cAnd R^3cThe total number of carbon atoms of (2) is 5 or more. A. the^cis-COOX^cor-SO₃X^c(X^cIs H, a metal atom, NR^4c ₄Imidazolium with or without substituents, pyridinium with or without substituents or phosphonium with or without substituents, R^4cIs H or an organic group, which may be the same or different). R^1c、R^2cAnd R^3cAny two of which may be bonded to each other to form a ring), and the following formula (d):

[ solution 14]

(in the formula, R^1dThe alkyl group may be a linear or branched alkyl group having 1 or more carbon atoms, which may have a substituent, or a cyclic alkyl group having 3 or more carbon atoms, which may have a substituent, and may contain a heterocyclic ring having 1 or 2 valences or may form a ring when the number of carbon atoms is 3 or more. R^2dAnd R^4dIndependently is H or a substituent. R^3dIs an alkylene group having 1 to 10 carbon atoms, which may have a substituent. n is an integer of 1 or more. p and q are independently integers of 0 or more. A. the^dis-SO₃X^dor-COOX^d(X^dIs H, a metal atom, NR^5d ₄Imidazolium with or without substituents, pyridinium with or without substituents or phosphonium with or without substituents, R^5dIs H or an organic group, which may be the same or different). R^1d、R^2d、R^3dAnd R^4dAny two of which may be bonded to each other to form a ring. L is a single bond, -CO₂-B-*、-OCO-B-*、-CONR^6d-B-*、-NR^6dCO-B-, or-CO- (excluding-CO)₂-B-、-OCO-B-、-CONR^6d-B-、-NR^6dCarbonyl group contained in CO-B-), B is a single bond or alkylene group having 1 to 10 carbon atoms with or without a substituent, R^6dH or an alkyl group having 1 to 4 carbon atoms, which may have a substituent. Is represented by A in the formula^dThe side to which the surfactant (d) is bonded), and the following formula (e):

[ solution 15]

(in the formula, R^1e～R^5eRepresents H or a monovalent substituent, wherein R^1eAnd R^3eRepresents the general formula: -Y^e-R^6eA group shown, R^2eAnd R^5eRepresents the general formula: -X^e-A^eA group or formula shown: -Y^e-R^6eThe groups shown.

In addition, X^eThe same or different at each occurrence, represents a 2-valent linking group or bond;

A^eidentical or different at each occurrence and denotes-COOM^e、-SO₃M^eor-OSO₃M^e(M^eIs H, a metal atom, NR^7e ₄Imidazolium with or without substituents, pyridinium with or without substituents or phosphonium with or without substituents, R^7eIs H or an organic group);

Y^eidentical or different at each occurrence and represents a residue selected from the group consisting of-S (═ O)₂-、-O-、-COO-、-OCO-、-CONR^8e-and-NR^8e2-valent linking groups or bonds in the group consisting of CO-, R^8eIs H or an organic group;

R^6ethe alkyl group having 2 or more carbon atoms, which may be the same or different at each occurrence, may or may not contain at least one selected from the group consisting of a carbonyl group, an ester group, an amide group and a sulfonyl group between carbon-carbon atoms.

R^1e～R^5eAny two of which may be bonded to each other to form a ring. ) At least one of the group consisting of the surfactants (e) shown.

The surfactant (a) will be explained.

In the formula (a), R ^1aIs a linear or branched alkyl group having 1 or more carbon atoms or a cyclic alkyl group having 3 or more carbon atoms.

When the number of carbon atoms of the alkyl group is 3 or more, a carbonyl group (-C (═ O) -) may be contained between 2 carbon atoms. When the alkyl group has 2 or more carbon atoms, the carbonyl group may be contained at the end of the alkyl group. I.e. CH₃Acyl groups such as an acetyl group represented by — C (═ O) -, are also included in the above alkyl groups.

When the number of carbon atoms of the alkyl group is 3 or more, the alkyl group may contain a heterocyclic ring having a valence of 1 or 2, or may form a ring. The heterocyclic ring is preferably an unsaturated heterocyclic ring, more preferably an oxygen-containing unsaturated heterocyclic ring, and examples thereof include furan rings and the like. R^1aIn the above formula, a 2-valent heterocyclic ring may be inserted between 2 carbon atoms, a 2-valent heterocyclic ring may be located at the terminal and bonded to — C (═ O) -, and a 1-valent heterocyclic ring may be located at the terminal of the alkyl group.

In the present specification, the "number of carbon atoms" of the alkyl group also includes the constituent carbonyl groupThe number of carbon atoms of the group and the number of carbon atoms constituting the above-mentioned heterocycle. E.g. CH₃-C(＝O)-CH₂-the number of carbon atoms of the group represented is 3, CH₃-C(＝O)-C₂H₄-C(＝O)-C₂H₄-the number of carbon atoms of the group represented is 7, CH ₃The number of carbon atoms of the group represented by — C (═ O) — is 2.

In the above alkyl group, the hydrogen atom bonded to the carbon atom may be substituted with a functional group, for example, a hydroxyl group (-OH) or a 1-valent organic group containing an ester bond, but is preferably not substituted with any functional group.

Examples of the 1-valent organic group containing an ester bond include the following: -O-C (═ O) -R^101a(in the formula, R^101aIs an alkyl group).

In the above alkyl groups, 75% or less of hydrogen atoms bonded to carbon atoms may be substituted with a halogen atom, 50% or less may be substituted with a halogen atom, and 25% or less may be substituted with a halogen atom, but a non-halogenated alkyl group containing no halogen atom such as a fluorine atom or a chlorine atom is preferable.

In the formula, R^2aAnd R^3aIndependently a single bond or a 2-valent linking group.

R^2aAnd R^3aPreferably a single bond, a linear or branched alkylene group having 1 or more carbon atoms, or a cyclic alkylene group having 3 or more carbon atoms.

Form R^2aAnd R^3aThe above alkylene group of (a) preferably does not contain a carbonyl group.

In the above alkylene group, the hydrogen atom bonded to the carbon atom may be substituted with a functional group, for example, a hydroxyl group (-OH) or a 1-valent organic group containing an ester bond, but is preferably not substituted with any functional group.

Examples of the 1-valent organic group containing an ester bond include the following: -O-C (═ O) -R^102a(in the formula, R^102aIs an alkyl group).

Of the above alkylene groups, 75% or less of hydrogen atoms bonded to carbon atoms may be substituted with halogen atoms, 50% or less may be substituted with halogen atoms, and 25% or less may be substituted with halogen atoms, but a non-halogenated alkylene group containing no halogen atom such as a fluorine atom or chlorine atom is preferable.

R^1a、R^2aAnd R^3aThe total number of carbon atoms of (2) is 6 or more. The total number of carbon atoms is preferably 8 or more, more preferably 9 or more, further preferably 10 or more, and preferably 20 or less, more preferably 18 or less, further preferably 15 or less.

R^1a、R^2aAnd R^3aAny two of which may be bonded to each other to form a ring.

In the formula (a), X^aIs H, a metal atom, NR^4a ₄Imidazolium with or without substituents, pyridinium with or without substituents or phosphonium with or without substituents, R^4aIs H or an organic group. 4R^4aMay be the same or different. As R^4aThe organic group in (1) is preferably an alkyl group. As R^4aPreferably, H or an organic group having 1 to 10 carbon atoms, more preferably H or an organic group having 1 to 4 carbon atoms, and further preferably H or an alkyl group having 1 to 4 carbon atoms. Examples of the metal atom include alkali metals (group 1), alkaline earth metals (group 2), and the like, and Na, K, and Li are preferable.

As X^aPreferably H, alkali metal (group 1), alkaline earth metal (group 2) or NR^4a ₄For reasons of easy solubility in water, H, Na, K, Li or NH are more preferred₄Further, Na, K or NH is preferable for the reason of being more soluble in water₄Particularly preferred is Na or NH₄For reasons of easy removal, NH is most preferred₄。X^aIs NH₄In the case of the surfactant, the surfactant has excellent solubility in an aqueous medium, and a metal component is not likely to remain in PTFE or a final product.

As R^1aPreferably, the alkyl group is a linear or branched alkyl group having 1 to 8 carbon atoms and not containing a carbonyl group, a cyclic alkyl group having 3 to 8 carbon atoms and not containing a carbonyl group, a linear or branched alkyl group having 2 to 45 carbon atoms and containing 1 to 10 carbonyl groups, a cyclic alkyl group having 3 to 45 carbon atoms and containing a carbonyl group, or a C3 to C45 cyclic alkyl group3 to 45 alkyl groups containing a heterocyclic ring having a valence of 1 or 2.

In addition, as R^1aMore preferably, the following formula:

[ solution 16]

(in the formula, n^11aIs an integer of 0 to 10, R^11aIs a linear or branched alkyl group having 1 to 5 carbon atoms or a cyclic alkyl group having 3 to 5 carbon atoms, R^12aIs an alkylene group having 0 to 3 carbon atoms. n is^11aWhen R is an integer of 2 to 10^12aEach may be the same or different).

As n^11aPreferably an integer of 0 to 5, more preferably an integer of 0 to 3, and further preferably an integer of 1 to 3.

As R^11aThe above alkyl group of (a) preferably does not contain a carbonyl group.

As R^11aIn the above alkyl group, the hydrogen atom bonded to the carbon atom may be substituted with a functional group, for example, a hydroxyl group (-OH) or a 1-valent organic group containing an ester bond, but is preferably not substituted with any functional group.

Examples of the 1-valent organic group containing an ester bond include the following: -O-C (═ O) -R^103a(in the formula, R^103aIs an alkyl group).

As R^11aIn the above alkyl groups, 75% or less of the hydrogen atoms bonded to the carbon atoms may be substituted with a halogen atom, 50% or less may be substituted with a halogen atom, and 25% or less may be substituted with a halogen atom, but a non-halogenated alkyl group containing no halogen atom such as a fluorine atom or a chlorine atom is preferable.

R^12aIs an alkylene group having 0 to 3 carbon atoms. The number of carbon atoms is preferably 1 to 3.

As R^12aThe alkylene group in (b) may be linear or branched.

As R^12aThe above alkylene group of (a) preferably does not contain a carbonyl group. AsR^12aMore preferably an ethylene group (-C)₂H₄-) or propylene (-C)₃H₆-)。

As R^12aIn the above alkylene group, the hydrogen atom bonded to the carbon atom may be substituted with a functional group, for example, a hydroxyl group (-OH) or a 1-valent organic group containing an ester bond, but is preferably not substituted with any functional group.

Examples of the 1-valent organic group containing an ester bond include the following: -O-C (═ O) -R^104a(in the formula, R^104aIs an alkyl group).

As R^12aIn the above alkylene group, 75% or less of hydrogen atoms bonded to carbon atoms may be substituted with a halogen atom, 50% or less may be substituted with a halogen atom, and 25% or less may be substituted with a halogen atom, but a non-halogenated alkylene group containing no halogen atom such as a fluorine atom or a chlorine atom is preferable.

As R^2aAnd R^3aThe alkylene group having 1 or more carbon atoms and not containing a carbonyl group is preferable, the alkylene group having 1 to 3 carbon atoms and not containing a carbonyl group is more preferable, and the ethylene group (-C) is further preferable₂H₄-) or propylene (-C)₃H₆-)。

As the surfactant (a), the following surfactants can be exemplified. In each formula, X^aAs described above.

[ solution 17]

[ solution 18]

[ solution 19]

[ solution 20]

[ solution 21]

[ solution 22]

[ solution 23]

[ solution 24]

The surfactant (a) is a novel compound, and can be produced, for example, by the production method described below.

The surfactant (a) can be produced by a production method comprising the following steps (11a), (12a), (13a) and (14a),

the step (11a) is a step of reacting:

[ solution 25]

(in the formula, R^3aAs described above, E^aIs a leaving group), lithium, and a compound of formula (10 a): r ^201a ₃Si-Cl (in the formula, R)^201aIndependently an alkyl or aryl) to yield a chlorosilane compound of the formula:

[ solution 26]

(in the formula, R^3a、R^201aAnd E^aAs described above) of the compound (11a),

the step (11b) is carried out by reacting the compound (11a) with a compound represented by the formula:

[ solution 27]

(in the formula, R^1aAs mentioned above, R^21aIs a single bond or a 2-valent linking group) to give an olefin of the formula:

[ solution 28]

(in the formula, R^1a、R^21a、R^3aAnd E^aAs described above) of the compound (12a),

step (13a) is to remove the leaving group of compound (12a) to obtain a compound of formula (la):

[ solution 29]

(in the formula, R^1a、R^21aAnd R^3aAs described above) of the compound (13a),

step (14a) is performed by reacting compound (13a) with a compound of formula (la):

[ solution 30]

(in the formula, X^aAs described above) to yield a compound of formula:

[ solution 31]

(in the formula, R^1a、R^21a、R^3aAnd X^aAs described above) of the compound (14 a).

R^1aWhen the furan ring is contained in (b), the furan ring can be opened by an acid to convert into a dicarbonyl derivative, for example. Examples of the acid include acetic acid, hydrochloric acid, and p-tolylsulfone, and among them, acetic acid is preferable.

In the step (11a), it is preferable that lithium and the chlorosilane compound are reacted in advance to obtain a siloxysithium compound, and then the siloxysithium compound is reacted with the compound (10a) to obtain the compound (11 a).

E^aRepresents a leaving group. Examples of the leaving group include t-butyldimethylsilyl (TBS), Triethylsilyl (TES), Triisopropylsilyl (TIPS), t-butyldiphenylsilyl (TBDPS), and benzyl (Bn).

As R^21aPreferably, it is a single bond or a linear or branched alkylene group having 1 or more carbon atoms.

Examples of the chlorosilane compound include

[ solution 32]

All reactions in step (11a) can be carried out in a solvent. The solvent is preferably an organic solvent, more preferably an aprotic polar solvent, and still more preferably an ether. Examples of the ether include ethyl methyl ether, diethyl ether, monoglyme (ethylene glycol dimethyl ether), diglyme (diethylene glycol dimethyl ether), triglyme (triethylene glycol dimethyl ether), tetrahydrofuran, tetraglyme (tetraethylene glycol dimethyl ether), crown ether (15-crown-5, 18-crown-6), and the like, and among them, tetrahydrofuran and diethyl ether are preferable.

The temperature of the reaction between lithium and the chlorosilane compound in step (11a) is preferably 10 to 40 ℃, and more preferably 20 to 30 ℃.

The reaction temperature of the siloxysithium compound and the compound (10a) in the step (11a) is preferably-100 to 0 ℃ and more preferably-80 to-50 ℃.

The pressure for the reaction between lithium and the chlorosilane compound in step (11a) is preferably 0.1 to 5MPa, more preferably 0.1 to 1 MPa.

The pressure for the reaction between the siloxysithium compound and the compound (10a) in the step (11a) is preferably 0.1 to 5MPa, more preferably 0.1 to 1 MPa.

The time for the reaction between lithium and the chlorosilane compound in step (11a) is preferably 0.1 to 72 hours, and more preferably 6 to 10 hours.

The reaction time of the siloxysithium compound and the compound (10a) in the step (11a) is preferably 0.1 to 72 hours, more preferably 1 to 2 hours.

In the step (12a), the ratio of the olefin to be reacted with the compound (11a) is preferably 1 to 2 moles, more preferably 1 to 1.1 moles, of the olefin based on 1 mole of the compound (11a) in view of improvement in yield and reduction in waste.

The reaction in the step (12a) may be carried out in a solvent in the presence of a thiazolium salt and a base.

Examples of the thiazolium salt include 3-ethyl-5- (2-hydroxyethyl) -4-methylthiazolium bromide, 3-benzyl-5- (2-hydroxyethyl) -4-methylthiazolium chloride, and the like.

Examples of the base include 1, 8-diazabicyclo [5.4.0] -7-undecene and triethylamine.

The solvent is preferably an organic solvent, more preferably an aprotic polar solvent, and further preferably an alcohol or an ether.

Examples of the alcohol include methanol, ethanol, 1-propanol, and isopropanol.

Examples of the ether include ethyl methyl ether, diethyl ether, monoglyme (ethylene glycol dimethyl ether), diglyme (diethylene glycol dimethyl ether), triglyme (triethylene glycol dimethyl ether), tetrahydrofuran, tetraglyme (tetraethylene glycol dimethyl ether), crown ether (15-crown-5, 18-crown-6), and the like, and among them, tetrahydrofuran and diethyl ether are preferable.

The temperature of the reaction in the step (12a) is preferably 40 to 60 ℃, more preferably 50 to 55 ℃.

The pressure of the reaction in the step (12a) is preferably 0.1 to 5MPa, more preferably 0.1 to 1 MPa.

The reaction time in the step (12a) is preferably 0.1 to 72 hours, more preferably 6 to 10 hours.

The leaving group elimination reaction in the step (13a) can be carried out by using a fluoride ion or an acid. Examples of the method for detaching a leaving group include: a method using hydrofluoric acid; a method using an amine complex of hydrogen fluoride such as pyridine nHF or triethylamine nHF; cesium fluoride, potassium fluoride, lithium fluoroborate (LiBF) are used ₄) A method of using an inorganic salt such as ammonium fluoride; a method using an organic salt such as tetrabutylammonium fluoride (TBAF).

The leaving group elimination reaction in the step (13a) may be carried out in a solvent. The solvent is preferably an organic solvent, more preferably an aprotic polar solvent, and still more preferably an ether.

Examples of the ether include ethyl methyl ether, diethyl ether, monoglyme (ethylene glycol dimethyl ether), diglyme (diethylene glycol dimethyl ether), triglyme (triethylene glycol dimethyl ether), tetrahydrofuran, tetraglyme (tetraethylene glycol dimethyl ether), crown ether (15-crown-5, 18-crown-6), and the like, and among them, tetrahydrofuran and diethyl ether are preferable.

The temperature of the reaction in the step (13a) is preferably 0 to 40 ℃ and more preferably 0 to 20 ℃.

The pressure of the reaction in the step (13a) is preferably 0.1 to 5MPa, more preferably 0.1 to 1 MPa.

The reaction time in the step (13a) is preferably 0.1 to 72 hours, more preferably 3 to 8 hours.

In the step (14a), the reaction ratio of the compound (13a) and chlorosulfonic acid is preferably 1 to 2 moles, more preferably 1 to 1.1 moles, based on 1 mole of the compound (13a), in view of improvement in yield and reduction in waste.

The reaction in step (14a) is preferably carried out in the presence of a base. Examples of the base include alkali metal hydroxides, alkaline earth metal hydroxides, and amines, and among them, amines are preferable.

Examples of the amine in the step (14a) include tertiary amines such as trimethylamine, triethylamine, tributylamine, N, N-dimethylaniline, dimethylbenzylamine and N, N, N ', N' -tetramethyl-1, 8-naphthalenediamine, heteroaromatic amines such as pyridine, pyrrole, uracil, collidine and lutidine, cyclic amines such as 1, 8-diaza-bicyclo [5.4.0] -7-undecene and 1, 5-diaza-bicyclo [4.3.0] -5-nonene, and the like. Among them, triethylamine and pyridine are preferable.

The amount of the base used in the step (14a) is preferably 1 to 2 moles, more preferably 1 to 1.1 moles, based on 1 mole of the compound (13a), in view of improvement in yield and reduction in waste.

The reaction in step (14a) may be carried out in a polar solvent. The solvent is preferably an organic solvent, more preferably an aprotic polar solvent, and still more preferably an ether.

Examples of the ether include ethyl methyl ether, diethyl ether, monoglyme (ethylene glycol dimethyl ether), diglyme (diethylene glycol dimethyl ether), triglyme (triethylene glycol dimethyl ether), tetrahydrofuran, tetraglyme (tetraethylene glycol dimethyl ether), crown ether (15-crown-5, 18-crown-6), and the like, and among them, diethyl ether is preferable.

The temperature of the reaction in the step (14a) is preferably 0 to 40 ℃ and more preferably 0 to 20 ℃.

The pressure of the reaction in the step (14a) is preferably 0.1 to 5MPa, more preferably 0.1 to 1 MPa.

The reaction time in the step (14a) is preferably 0.1 to 72 hours, more preferably 3 to 12 hours.

When the reaction in step (14a) is carried out in a solvent, a solution containing compound (14a) is obtained after the reaction is completed. After water was added to the solution, the mixture was allowed to stand to separate into two phases, and the aqueous phase was recovered and the solvent was distilled off, whereby the compound (14a) having a high purity was recovered. Compound (14a) has-OSO₃When the group represented by H (that is, when X is H), the-OSO can be converted to a group represented by-OSO by using an aqueous alkali solution such as an aqueous sodium hydrogencarbonate solution or aqueous ammonia solution instead of water₃H is converted to a sulfate group.

After completion of each step, the purity of the obtained compound can be improved by removing the solvent by distillation, or by performing distillation, purification, or the like.

The surfactant (a) can also be produced by a production method comprising the following steps (21a), (22a) and (23a),

the step (21a) is a step of reacting:

[ solution 33]

(in the formula, R^3aAs mentioned above, R^22aIs a 1-valent organic radical, E^aIs a leaving group) with a ketone of formula (la):

[ chemical 34]

(in the formula, R^1aAs mentioned above, R^23aIs a 1-valent organic group) to yield a carboxylic acid ester of the formula:

[ solution 35]

(in the formula, R^1a、R^3aAnd E^aAs mentioned above, R^24aA single bond or a 2-valent linking group),

step (22a) is a step of removing the leaving group of compound (21a) to obtain a compound represented by the formula:

[ solution 36]

(in the formula, R^1a、R^24aAnd R^3aAs described above) of the compound (22a),

step (23a) is performed by reacting compound (22a) with a compound of formula (la):

[ solution 37]

(in the formula, X^aAs described above) to yield a compound of formula:

[ solution 38]

(in the formula, R^1a、R^24a、R^3aAnd X^aAs described above) of the compound (23 a).

R^1aWhen the furan ring is contained in (b), the furan ring can be opened by an acid to convert into a dicarbonyl derivative, for example. Examples of the acid include acetic acid, hydrochloric acid, and p-toluenesulfonic acid, and among them, acetic acid is preferable.

E^aRepresents a leaving group. Examples of the leaving group include t-butyldimethylsilyl (TBS), Triethylsilyl (TES), Triisopropylsilyl (TIPS), t-butyldiphenylsilyl (TBDPS), and benzyl (Bn).

As R^22aThe alkyl group is preferably a linear or branched alkyl group having 1 or more carbon atoms, and more preferably a methyl group.

As R^23aPreferably straight with 1 or more carbon atomsThe linear or branched alkyl group is preferably a methyl group.

As R^24aThe alkylene group is preferably a linear or branched alkylene group having 1 or more carbon atoms, and more preferably a methylene group (-CH)₂-)。

The reaction in the step (21a) may be carried out in a solvent in the presence of a base.

Examples of the base include sodium amide, sodium hydride, sodium methoxide, sodium ethoxide, and the like.

The solvent is preferably an organic solvent, more preferably an aprotic polar solvent, and further preferably an alcohol or an ether.

Examples of the alcohol include methanol, ethanol, 1-propanol, and isopropanol.

Examples of the ether include ethyl methyl ether, diethyl ether, monoglyme (ethylene glycol dimethyl ether), diglyme (diethylene glycol dimethyl ether), triglyme (triethylene glycol dimethyl ether), tetrahydrofuran, tetraglyme (tetraethylene glycol dimethyl ether), crown ether (15-crown-5, 18-crown-6), and the like, and among them, tetrahydrofuran and diethyl ether are preferable.

The temperature of the reaction in the step (21a) is preferably 0 to 40 ℃ and more preferably 0 to 20 ℃.

The pressure of the reaction in the step (21a) is preferably 0.1 to 5MPa, more preferably 0.1 to 1 MPa.

The reaction time in the step (21a) is preferably 0.1 to 72 hours, more preferably 3 to 8 hours.

The leaving group elimination reaction in the step (22a) can be carried out by using a fluoride ion or an acid. Examples of the method for detaching a leaving group include: a method using hydrofluoric acid; a method using an amine complex of hydrogen fluoride such as pyridine nHF or triethylamine nHF; cesium fluoride, potassium fluoride, lithium fluoroborate (LiBF) are used₄) A method of using an inorganic salt such as ammonium fluoride; a method using an organic salt such as tetrabutylammonium fluoride (TBAF).

The leaving group elimination reaction in the step (22a) may be carried out in a solvent. The solvent is preferably an organic solvent, more preferably an aprotic polar solvent, and still more preferably an ether.

Examples of the ether include ethyl methyl ether, diethyl ether, monoglyme (ethylene glycol dimethyl ether), diglyme (diethylene glycol dimethyl ether), triglyme (triethylene glycol dimethyl ether), tetrahydrofuran, tetraglyme (tetraethylene glycol dimethyl ether), crown ether (15-crown-5, 18-crown-6), and the like, and among them, tetrahydrofuran and diethyl ether are preferable.

The temperature of the reaction in the step (22a) is preferably 0 to 40 ℃ and more preferably 0 to 20 ℃.

The pressure of the reaction in the step (22a) is preferably 0.1 to 5MPa, more preferably 0.1 to 1 MPa.

The reaction time in the step (22a) is preferably 0.1 to 72 hours, more preferably 3 to 8 hours.

In the step (23a), the reaction ratio of the compound (22a) and chlorosulfonic acid is preferably 1 to 2 moles, more preferably 1 to 1.1 moles, based on 1 mole of the compound (22a), in view of improvement of yield and reduction of waste.

The reaction in step (23a) is preferably carried out in the presence of a base. Examples of the base include alkali metal hydroxides, alkaline earth metal hydroxides, and amines, and among them, amines are preferable.

Examples of the amine in the step (23a) include tertiary amines such as trimethylamine, triethylamine, tributylamine, N, N-dimethylaniline, dimethylbenzylamine and N, N, N ', N' -tetramethyl-1, 8-naphthalenediamine, heteroaromatic amines such as pyridine, pyrrole, uracil, collidine and lutidine, cyclic amines such as 1, 8-diaza-bicyclo [5.4.0] -7-undecene and 1, 5-diaza-bicyclo [4.3.0] -5-nonene, and the like. Among them, triethylamine and pyridine are preferable.

The amount of the base used in the step (23a) is preferably 1 to 2 moles, more preferably 1 to 1.1 moles, based on 1 mole of the compound (22a), in view of improvement in yield and reduction in waste.

The reaction in step (23a) may be carried out in a polar solvent. The solvent is preferably an organic solvent, more preferably an aprotic polar solvent, and still more preferably an ether.

Examples of the ether include ethyl methyl ether, diethyl ether, monoglyme (ethylene glycol dimethyl ether), diglyme (diethylene glycol dimethyl ether), triglyme (triethylene glycol dimethyl ether), tetrahydrofuran, tetraglyme (tetraethylene glycol dimethyl ether), crown ether (15-crown-5, 18-crown-6), and the like, and among them, diethyl ether is preferable.

The temperature of the reaction in the step (23a) is preferably 0 to 40 ℃ and more preferably 0 to 20 ℃.

The pressure of the reaction in the step (23a) is preferably 0.1 to 5MPa, more preferably 0.1 to 1 MPa.

The reaction time in the step (23a) is preferably 0.1 to 72 hours, more preferably 3 to 12 hours.

When the reaction in step (23a) is carried out in a solvent, a solution containing compound (23a) is obtained after the reaction is completed. After water was added to the solution, the mixture was allowed to stand to separate into two phases, and the aqueous phase was recovered and the solvent was distilled off, whereby the compound (23a) having a high purity was recovered. Compound (23a) has-OSO₃When the group represented by H (that is, when X is H), the-OSO can be converted to a group represented by-OSO by using an aqueous alkali solution such as an aqueous sodium hydrogencarbonate solution or aqueous ammonia solution instead of water ₃H is converted to a sulfate group.

After completion of each step, the purity of the obtained compound can be improved by removing the solvent by distillation, or by performing distillation, purification, or the like.

The surfactant (a) can be produced by a production method comprising the following steps (31a), (32a), (33a) and (34a),

the step (31a) is a step of reacting: y is^a-R^3a-OE^a

(in the formula, R^3aAs described above, Y^aIs a halogen atom, E^aIs a leaving group) with a haloalkyl group of the formula:

[ solution 39]

(in the formula, R^1aLithium acetylene reaction as described above)Should, the formula be obtained:

[ solution 40]

(in the formula, R^1a、R^3aAnd E^aAs described above) of the compound (31a),

step (32a) is to oxidize compound (31a) to obtain the compound of formula (la)

[ solution 41]

(in the formula, R^1a、R^3aAnd E^aAs described above) of the compound (32a),

step (33a) is a step of removing the leaving group of compound (32a) to obtain a compound represented by the formula:

[ solution 42]

(in the formula, R^1aAnd R^3aAs described above) of the compound (33a),

step (34a) is performed by reacting compound (33a) with a compound of formula (la):

[ solution 43]

(in the formula, X^aAs described above) to yield a compound of formula:

[ solution 44]

(in the formula, R^1a、R^3aAnd X^aAs described above) of the compound (34 a).

R^1aWhen the furan ring is contained in (b), the furan ring can be opened by an acid to convert into a dicarbonyl derivative, for example. Examples of the acid include acetic acid, hydrochloric acid, and p-toluenesulfonic acid, and among them, acetic acid is preferable.

E^aRepresents a leaving group. Examples of the leaving group include t-butyldimethylsilyl (TBS), Triethylsilyl (TES), Triisopropylsilyl (TIPS), t-butyldiphenylsilyl (TBDPS), and benzyl (Bn).

In the step (31a), the ratio of the halogenated alkyl group to the lithium acetylide is preferably 1 to 2 moles, more preferably 1 to 1.2 moles, of the lithium acetylide to 1 mole of the halogenated alkyl group, in view of improvement of yield and reduction of waste.

The reaction in step (31a) may be carried out in a solvent. As the solvent, hexane is preferable.

The temperature of the reaction in the step (31a) is preferably-100 to-40 ℃ and more preferably-80 to-50 ℃.

The pressure of the reaction in the step (31a) is preferably 0.1 to 5MPa, more preferably 0.1 to 1 MPa.

The reaction time in the step (31a) is preferably 0.1 to 72 hours, more preferably 6 to 10 hours.

The oxidation in the step (32a) can be carried out as follows: will [ (Cn)^*)Ru^III(CF₃CO₂)₃]·H₂O (in the formula, Cn)^*Represents the utilization of (NH) by 1,4, 7-trimethyl-1, 4, 7-triazabicyclononane₄)₂Ce(NO₃)₆And trifluoroacetic acid treatment, sodium perchlorate is added to form a complex, and the oxidation is carried out in a nitrile solvent using the complex.

After the termination of the oxidation, the compound (32a) can be extracted by neutralizing with a base and using an organic solvent such as ether.

The temperature of the reaction in the step (32a) is preferably 30 to 100 ℃, more preferably 40 to 90 ℃.

The pressure of the reaction in the step (32a) is preferably 0.1 to 5MPa, more preferably 0.1 to 1 MPa.

The reaction time in the step (32a) is preferably 0.1 to 72 hours, more preferably 3 to 8 hours.

The leaving group elimination reaction in the step (33a) can be carried out by using a fluoride ion or an acid. Examples of the method for detaching a leaving group include: a method using hydrofluoric acid; a method using an amine complex of hydrogen fluoride such as pyridine nHF or triethylamine nHF; cesium fluoride, potassium fluoride, lithium fluoroborate (LiBF) are used₄) A method of using an inorganic salt such as ammonium fluoride; a method using an organic salt such as tetrabutylammonium fluoride (TBAF).

The leaving group elimination reaction in the step (33a) may be carried out in a solvent. The solvent is preferably an organic solvent, more preferably an aprotic polar solvent, and still more preferably an ether.

Examples of the ether include ethyl methyl ether, diethyl ether, monoglyme (ethylene glycol dimethyl ether), diglyme (diethylene glycol dimethyl ether), triglyme (triethylene glycol dimethyl ether), tetrahydrofuran, tetraglyme (tetraethylene glycol dimethyl ether), crown ether (15-crown-5, 18-crown-6), and the like, and among them, tetrahydrofuran and diethyl ether are preferable.

The temperature of the reaction in the step (33a) is preferably 0 to 40 ℃ and more preferably 0 to 20 ℃.

The pressure of the reaction in the step (33a) is preferably 0.1 to 5MPa, more preferably 0.1 to 1 MPa.

The reaction time in the step (33a) is preferably 0.1 to 72 hours, more preferably 3 to 8 hours.

In the step (34a), the reaction ratio of the compound (33a) and chlorosulfonic acid is preferably 1 to 2 moles, more preferably 1 to 1.1 moles, based on 1 mole of the compound (33a), in view of improvement of yield and reduction of waste.

The reaction in the step (34a) is preferably carried out in the presence of a base. Examples of the base include alkali metal hydroxides, alkaline earth metal hydroxides, and amines, and among them, amines are preferable.

Examples of the amine in the step (34a) include tertiary amines such as trimethylamine, triethylamine, tributylamine, N, N-dimethylaniline, dimethylbenzylamine and N, N, N ', N' -tetramethyl-1, 8-naphthalenediamine, heteroaromatic amines such as pyridine, pyrrole, uracil, collidine and lutidine, cyclic amines such as 1, 8-diaza-bicyclo [5.4.0] -7-undecene and 1, 5-diaza-bicyclo [4.3.0] -5-nonene, and the like. Among them, triethylamine and pyridine are preferable.

The amount of the base used in the step (34a) is preferably 1 to 2 moles, more preferably 1 to 1.1 moles, based on 1 mole of the compound (33a), in view of improvement in yield and reduction in waste.

The reaction in step (34a) may be carried out in a polar solvent. The solvent is preferably an organic solvent, more preferably an aprotic polar solvent, and still more preferably an ether.

Examples of the ether include ethyl methyl ether, diethyl ether, monoglyme (ethylene glycol dimethyl ether), diglyme (diethylene glycol dimethyl ether), triglyme (triethylene glycol dimethyl ether), tetrahydrofuran, tetraglyme (tetraethylene glycol dimethyl ether), crown ether (15-crown-5, 18-crown-6), and the like, and among them, diethyl ether is preferable.

The temperature of the reaction in the step (34a) is preferably 0 to 40 ℃, more preferably 0 to 20 ℃.

The pressure of the reaction in the step (34a) is preferably 0.1 to 5MPa, more preferably 0.1 to 1 MPa.

The reaction time in the step (34a) is preferably 0.1 to 72 hours, more preferably 3 to 12 hours.

When the reaction in step (34a) is carried out in a solvent, a solution containing compound (34a) is obtained after the reaction is completed. After water was added to the solution, the mixture was allowed to stand to separate into two phases, and the aqueous phase was recovered and the solvent was distilled off, whereby the compound (34a) having a high purity was recovered. having-OSO in the compound (34a)₃When the group represented by H (that is, when X is H), the-OSO can be converted to a group represented by-OSO by using an aqueous alkali solution such as an aqueous sodium hydrogencarbonate solution or aqueous ammonia solution instead of water ₃H is converted to a sulfate group.

After completion of each step, the purity of the obtained compound can be improved by removing the solvent by distillation, or by performing distillation, purification, or the like.

The surfactant (a) can also be produced by a production method comprising the step (41a) and the step (42a), wherein,

the step (41a) is a step of reacting:

[ solution 45]

(in the formula, R^1aAs mentioned above, R^21aIs a single bond or a 2-valent linking group) with an olefin of the formula:

[ solution 46]

(in the formula, Y^51aIs alkoxy) to give an alkyne of the formula:

[ solution 47]

(in the formula, R^1aAnd R^21aAs described above) of the compound (41a),

the step (42a) is performed by reacting the compound (41a) with a compound represented by the formula:

[ solution 48]

(in the formula, X^aAs described above) to yield a compound of formula:

[ solution 49]

(in the formula, R^1a、R^21aAnd X^aAs described above) of the compound (42 a).

R^1aWhen the furan ring is contained in (b), the furan ring can be opened by an acid to convert into a dicarbonyl derivative, for example. Examples of the acid include acetic acid, hydrochloric acid, and p-toluenesulfonic acid, and among them, acetic acid is preferable.

As R^21aA single bond or a linear or branched alkylene group having 1 or more carbon atoms is preferable.

In the step (41a), the ratio of the olefin to the alkyne in the reaction is preferably 0.5 to 2 moles, more preferably 0.6 to 1.2 moles, of the olefin to 1 mole of the alkyne in view of improvement of yield and reduction of waste.

The reaction in the step (41a) is preferably carried out in the presence of a metal catalyst. Examples of the metal include ruthenium.

The amount of the metal catalyst used in the step (41a) is preferably 0.01 to 0.4 mol, more preferably 0.05 to 0.1 mol, based on 1 mol of the olefin, in view of improvement of yield and reduction of waste.

The reaction in step (41a) may be carried out in a polar solvent. The solvent is preferably water, acetonitrile, dimethylacetamide or dimethylformamide.

The temperature of the reaction in the step (41a) is preferably 20 to 160 ℃ and more preferably 40 to 140 ℃.

The pressure of the reaction in the step (41a) is preferably 0.1 to 5MPa, more preferably 0.1 to 1 MPa.

The reaction time in the step (41a) is preferably 0.1 to 72 hours, more preferably 4 to 8 hours.

In the step (42a), the reaction ratio of the compound (41a) and chlorosulfonic acid is preferably 1 to 2 moles, more preferably 1 to 1.1 moles, based on 1 mole of the compound (41a), in view of improvement of yield and reduction of waste.

The reaction in the step (42a) is preferably carried out in the presence of a base. Examples of the base include alkali metal hydroxides, alkaline earth metal hydroxides, and amines, and among them, amines are preferable.

Examples of the amine in the step (42a) include tertiary amines such as trimethylamine, triethylamine, tributylamine, N, N-dimethylaniline, dimethylbenzylamine and N, N, N ', N' -tetramethyl-1, 8-naphthalenediamine, heteroaromatic amines such as pyridine, pyrrole, uracil, collidine and lutidine, cyclic amines such as 1, 8-diaza-bicyclo [5.4.0] -7-undecene and 1, 5-diaza-bicyclo [4.3.0] -5-nonene, and the like. Among them, triethylamine and pyridine are preferable.

The amount of the base used in the step (42a) is preferably 1 to 2 moles, more preferably 1 to 1.1 moles, based on 1 mole of the compound (41a), in view of improvement in yield and reduction in waste.

The reaction in the step (42a) may be carried out in a polar solvent. The solvent is preferably an organic solvent, more preferably an aprotic polar solvent, and still more preferably an ether.

Examples of the ether include ethyl methyl ether, diethyl ether, monoglyme (ethylene glycol dimethyl ether), diglyme (diethylene glycol dimethyl ether), triglyme (triethylene glycol dimethyl ether), tetrahydrofuran, tetraglyme (tetraethylene glycol dimethyl ether), crown ether (15-crown-5, 18-crown-6), and the like, and among them, diethyl ether is preferable.

The temperature of the reaction in the step (42a) is preferably 0 to 40 ℃ and more preferably 0 to 20 ℃.

The pressure of the reaction in the step (42a) is preferably 0.1 to 5MPa, more preferably 0.1 to 1 MPa.

The reaction time in the step (42a) is preferably 0.1 to 72 hours, more preferably 3 to 12 hours.

When the reaction in step (42a) is carried out in a solvent, a solution containing compound (42a) is obtained after the reaction is completed. After water was added to the solution, the mixture was allowed to stand to separate into two phases, and the aqueous phase was recovered and the solvent was distilled off, whereby the compound (42a) having a high purity was recovered. Compound (42a) has-OSO₃In the case of a group represented by H (that is, in the case where X is H), an aqueous alkaline solution such as an aqueous sodium hydrogencarbonate solution or aqueous ammonia is used in place of waterIt is also possible to convert-OSO₃H is converted to a sulfate group.

After completion of each step, the purity of the obtained compound can be improved by removing the solvent by distillation, or by performing distillation, purification, or the like.

Next, the surfactant (b) will be described.

In the formula (b), R^1bIs a linear or branched alkyl group having 1 or more carbon atoms, which may have a substituent, or a cyclic alkyl group having 3 or more carbon atoms, which may have a substituent.

When the number of carbon atoms of the alkyl group is 3 or more, the alkyl group may contain a heterocyclic ring having a valence of 1 or 2, or may form a ring. The heterocyclic ring is preferably an unsaturated heterocyclic ring, more preferably an oxygen-containing unsaturated heterocyclic ring, and examples thereof include furan rings and the like. R ^1bIn the above formula, a 2-valent heterocyclic ring may be inserted between 2 carbon atoms, a 2-valent heterocyclic ring may be located at the terminal and bonded to — C (═ O) -, and a 1-valent heterocyclic ring may be located at the terminal of the alkyl group.

In the present specification, the "number of carbon atoms" of the alkyl group also includes the number of carbon atoms constituting the heterocyclic ring.

With respect to as R^1bThe substituent which the alkyl group may have is preferably a halogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, a cyclic alkyl group having 3 to 10 carbon atoms or a hydroxyl group, and particularly preferably a methyl group or an ethyl group.

As R^1bThe above alkyl group of (a) preferably does not contain a carbonyl group.

In the above alkyl groups, 75% or less of hydrogen atoms bonded to carbon atoms may be substituted with a halogen atom, 50% or less may be substituted with a halogen atom, and 25% or less may be substituted with a halogen atom, but a non-halogenated alkyl group containing no halogen atom such as a fluorine atom or a chlorine atom is preferable.

The above alkyl group preferably does not have any substituent.

As R^1bThe alkyl group is preferably a linear or branched alkyl group having 1 to 10 carbon atoms, which may have a substituent, or a cyclic alkyl group having 3 to 10 carbon atoms, which may have a substituent, more preferablyThe alkyl group is preferably a linear or branched alkyl group having 1 to 10 carbon atoms and not containing a carbonyl group, or a cyclic alkyl group having 3 to 10 carbon atoms and not containing a carbonyl group, more preferably a linear or branched alkyl group having 1 to 10 carbon atoms and not containing a substituent group, still more preferably a linear or branched alkyl group having 1 to 3 carbon atoms and not containing a substituent group, and particularly preferably a methyl group (-CH) ₃) Or ethyl (-C)₂H₅) Most preferred is methyl (-CH)₃)。

In the formula (b), R^2bAnd R^4bIndependently is H or a substituent. More than 2R^2bAnd R^4bEach may be the same or different.

With respect to as R^2bAnd R^4bThe substituent(s) is preferably a halogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, a cyclic alkyl group having 3 to 10 carbon atoms, or a hydroxyl group, and particularly preferably a methyl group or an ethyl group.

As R^2bAnd R^4bThe above alkyl group of (a) preferably does not contain a carbonyl group.

In the above alkyl groups, 75% or less of hydrogen atoms bonded to carbon atoms may be substituted with a halogen atom, 50% or less may be substituted with a halogen atom, and 25% or less may be substituted with a halogen atom, but a non-halogenated alkyl group containing no halogen atom such as a fluorine atom or a chlorine atom is preferable.

The above alkyl group preferably does not have any substituent.

With respect to as R^2bAnd R^4bThe alkyl group (C) is preferably a linear or branched alkyl group having 1 to 10 carbon atoms and not containing a carbonyl group or a cyclic alkyl group having 3 to 10 carbon atoms and not containing a carbonyl group, more preferably a linear or branched alkyl group having 1 to 10 carbon atoms and not containing a carbonyl group, further preferably a linear or branched alkyl group having 1 to 3 carbon atoms and not containing a substituent, and particularly preferably a methyl group (-CH) ₃) Or ethyl (-C)₂H₅)。

As R^2bAnd R^4bPreferably independently H or a linear or branched alkyl group having 1 to 10 carbon atoms and not containing a carbonyl group, more preferably H or one having no substituentA linear or branched alkyl group having 1 to 3 carbon atoms, more preferably H or methyl (-CH)₃) Or ethyl (-C)₂H₅) H is particularly preferred.

In the formula (b), R^3bIs an alkylene group having 1 to 10 carbon atoms, which may have a substituent. R^3bWhen there are 2 or more, they may be the same or different.

The alkylene group preferably does not contain a carbonyl group.

In the above alkylene group, 75% or less of hydrogen atoms bonded to carbon atoms may be substituted with a halogen atom, 50% or less may be substituted with a halogen atom, and 25% or less may be substituted with a halogen atom, but a non-halogenated alkyl group containing no halogen atom such as a fluorine atom or a chlorine atom is preferable.

The above alkylene group preferably does not have any substituent.

The alkylene group is preferably a linear or branched alkylene group having 1 to 10 carbon atoms which may have a substituent or may not have a substituent or a cyclic alkylene group having 3 to 10 carbon atoms which may have a substituent or not, more preferably a linear or branched alkylene group having 1 to 10 carbon atoms which may not contain a carbonyl group or a cyclic alkylene group having 3 to 10 carbon atoms which may not contain a carbonyl group, more preferably a linear or branched alkylene group having 1 to 10 carbon atoms which may not have a substituent, and still more preferably methylene (-CH) ₂-) ethylene (-C), ethylene (-C)₂H₄-) isopropylidene (-CH (CH)₃)CH₂-) or propylene (-C)₃H₆-)。

R^1b、R^2b、R^3bAnd R^4bAny two of them may be bonded to each other to form a ring, but preferably they do not form a ring.

In the formula (b), n is an integer of 1 or more. The number n is preferably an integer of 1 to 40, more preferably an integer of 1 to 30, further preferably an integer of 5 to 25, particularly preferably an integer of 5 to 9 or 11 to 25.

In the formula (b), p and q are independently integers of 0 or more. P is preferably an integer of 0 to 10, more preferably 0 or 1. Q is preferably an integer of 0 to 10, more preferably an integer of 0 to 5.

The sum of n, p and q is preferably an integer of 5 or more. The sum of n, p and q is more preferably an integer of 8 or more. The total of n, p and q is preferably an integer of 60 or less, more preferably an integer of 50 or less, and still more preferably an integer of 40 or less.

In the formula (b), X^bIs H, a metal atom, NR^5b ₄Imidazolium with or without substituents, pyridinium with or without substituents or phosphonium with or without substituents, R^5bIs H or an organic group. 4R^5bMay be the same or different. As R^5bThe organic group in (1) is preferably an alkyl group. As R^5bPreferably, H or an organic group having 1 to 10 carbon atoms, more preferably H or an organic group having 1 to 4 carbon atoms, and further preferably H or an alkyl group having 1 to 4 carbon atoms. Examples of the metal atom include alkali metals (group 1), alkaline earth metals (group 2), and the like, and Na, K, and Li are preferable. X ^bMay be a metal atom or NR^5b ₄(R^5bAs described above).

As X^bPreferably H, alkali metal (group 1), alkaline earth metal (group 2) or NR^5b ₄For reasons of easy solubility in water, H, Na, K, Li or NH are more preferred₄Further, Na, K or NH is preferable for the reason of being more soluble in water₄Particularly preferred is Na or NH₄For reasons of easy removal, NH is most preferred₄。X^bIs NH₄In the case of the surfactant, the surfactant has excellent solubility in an aqueous medium, and a metal component is not likely to remain in PTFE or a final product.

In the formula (b), L is a single bond, -CO₂-B-*、-OCO-B-*、-CONR^6b-B-*、-NR^6bCO-B-, or-CO- (excluding-CO)₂-B-、-OCO-B-、-CONR^6b-B-、-NR⁶A carbonyl group contained in CO-B-), B is a single bond or an alkylene group having 1 to 10 carbon atoms and having or not having a substituent, R^6bH or an alkyl group having 1 to 4 carbon atoms, which may have a substituent. The number of carbon atoms of the alkylene group is more preferably 1 to 5. In addition, the above R⁶More preferably H or methyl. Means thatand-OSO in the formula₃X^bOne side of the bond.

L is preferably a single bond.

As the surfactant (b), the following formula is preferable:

[ solution 50]

(in the formula, R^1b、R^2bL, n and X^bAs described above).

The above-mentioned surfactant (b) is in¹The integral value of all peak intensities observed in a region of chemical shift 2.0 to 5.0ppm in the H-NMR spectrum is preferably 10% or more.

The above-mentioned surfactant (b) is in¹The integral value of all peak intensities observed in a region of chemical shift 2.0 to 5.0ppm in the H-NMR spectrum is preferably within the above range. In this case, the surfactant preferably has a ketone structure in the molecule.

In the surfactant (b), the integrated value is more preferably 15 or more, preferably 95 or less, more preferably 80 or less, and still more preferably 70 or less.

The integral value was measured at room temperature using a heavy water solvent. The amount of heavy water was 4.79 ppm.

Examples of the surfactant (b) include

CH₃C(O)CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂OSO₃Na、

CH₃C(O)CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂OSO₃Na、

CH₃C(O)CH₂CH₂CH₂CH₂CH₂CH₂CH₂OSO₃Na、

CH₃C(O)CH₂CH₂CH₂CH₂CH₂CH₂OSO₃Na、

CH₃C(O)CH₂CH₂CH₂CH₂CH₂OSO₃Na、

CH₃C(O)CH₂CH₂CH₂CH₂OSO₃Na、

(CH₃)₃CC(O)CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂OSO₃Na、

(CH₃)₂CHC(O)CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂OSO₃Na、

(CH₂)₅CHC(O)CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂OSO₃Na、

CH₃CH₂C(O)CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂OSO₃Na、

CH₃CH₂CH₂C(O)CH₂CH₂CH₂CH₂CH₂CH₂CH₂OSO₃Na、

CH₃CH₂CH₂CH₂C(O)CH₂CH₂CH₂CH₂CH₂CH₂OSO₃Na、

CH₃CH₂CH₂CH₂CH₂C(O)CH₂CH₂CH₂CH₂CH₂OSO₃Na、

CH₃CH₂CH₂CH₂CH₂CH₂C(O)CH₂CH₂CH₂CH₂OSO₃Na、

CH₃CH₂CH₂CH₂CH₂CH₂CH₂C(O)CH₂CH₂CH₂OSO₃Na、

CH₃CH₂CH₂CH₂CH₂CH₂CH₂CH₂C(O)CH₂CH₂OSO₃Na、

CH₃CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂C(O)CH₂OSO₃Na、

CH₃C(O)CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂OCH₂CH₂OSO₃Na、

CH₃C(O)CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂C(O)NHCH₂OSO₃Na、

CH₃C(O)CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂NHC(O)CH₂OSO₃Na、

CH₃C(O)CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂C(O)OSO₃Na、

CH₃C(O)CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂C(O)OCH₂OSO₃Na、

CH₃C(O)CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂OC(O)CH₂OSO₃Na、

CH₃C(O)CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂OSO₃H、

CH₃C(O)CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂OSO₃Li、

CH₃C(O)CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂OSO₃K、

CH₃C(O)CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂OSO₃NH₄、

CH₃C(O)CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH(CH₃)₂OSO₃Na、

CH₃C(O)CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂OSO₃Na、

CH₃C(O)CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂OSO₃Na、

CH₃C(O)CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂OSO₃Na、

CH₃C(O)CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂OSO₃Na、

CH₃C(O)CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂OSO₃Na、

CH₃C(O)CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂OSO₃Na、

CH₃C(O)CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂OSO₃Na、

CH₃C(O)CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂OSO₃Na、

(CH₃)₃CC(O)CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂OSO₃Na、

(CH₃)₂CHC(O)CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂OSO₃Na、

(CH₂)₅CHC(O)CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂OSO₃Na、

CH₃CH₂C(O)CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂OSO₃Na、

CH₃CH₂CH₂CH₂CH₂C(O)CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂OSO₃Na、

CH₃CH₂CH₂CH₂CH₂CH₂CH₂CH₂C(O)CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂OSO₃Na、

CH₃CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂C(O)CH₂CH₂CH₂CH₂CH₂CH₂CH₂OSO₃Na、

CH₃CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂C(O)CH₂CH₂CH₂CH₂OSO₃Na、

CH₃CH₂C(O)CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂OCH₂CH₂OSO₃Na、

CH₃CH₂C(O)CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂C(O)NHCH₂CH₂OSO₃Na、

CH₃CH₂C(O)CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂NHC(O)CH₂CH₂OSO₃Na、

CH₃CH₂C(O)CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂C(O)OCH₂CH₂OSO₃Na、

CH₃CH₂C(O)CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂OC(O)CH₂CH₂OSO₃Na、

CH₃CH₂C(O)CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂C(O)OSO₃Na、

CH₃CH₂C(O)CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂OSO₃H、

CH₃CH₂C(O)CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂OSO₃Li、

CH₃CH₂C(O)CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂OSO₃K、

CH₃CH₂C(O)CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂OSO₃NH₄、

CH₃C(O)CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂OSO₃Na and the like.

The surfactant (b) is a novel compound, and can be produced, for example, by the production method described below.

The surfactant (b) can be produced by a production method comprising the step (11b), the step (12b) and the step (13b),

the step (11b) is a step of reacting a compound represented by the formula:

R^11b-CH＝CH-(CR^2b ₂)n-(OR^3b)_p-(CR^4b ₂)_q-L-OH

(in the formula, R^2b～R^4bN, p and q are as described above. R^11bIs H, a linear or branched alkyl group having 1 or more carbon atoms with or without a substituent, or a cyclic alkyl group having 3 or more carbon atoms with or without a substituent, and when the number of carbon atoms is 3 or more, a heterocyclic ring having 1 or 2 valences may be included, or a ring may be formed. L is a single bond, -CO ₂-B-*、-OCO-B-*、-CONR^6b-B-*、-NR^6bCO-B-, or-CO- (excluding-CO)₂-B-、-OCO-B-、-CONR^6b-B-、-NR^6bIn CO-B-Containing carbonyl group), B is a single bond or an alkylene group having 1 to 10 carbon atoms with or without a substituent, R^6bH or an alkyl group having 1 to 4 carbon atoms, which may have a substituent. One side bonded to-OH in the formula) to give the following formula:

[ solution 51]

(in the formula, L, R^2b～R^4b、R^11bN, p and q are as defined above) in the presence of a compound (11b),

step (12b) is to oxidize compound (11b) to obtain the following formula:

[ solution 52]

(in the formula, L, R^2b～R^4b、R^11bN, p and q are as defined above) in the presence of a compound (12b),

step (13b) is to sulfate compound (12b) to obtain the following formula:

[ Hua 53]

(in the formula, L, R^2b～R^4b、R^11bN, p, q and X^bAs described above) of the compound (13 b).

As R^11bThe above alkyl group of (a) preferably does not contain a carbonyl group.

As R^11bIn the above alkyl group, 75% or less of the hydrogen atoms bonded to the carbon atom may be substituted with a halogen atom, 50% or less may be substituted with a halogen atom, and 25% or less may be substituted with a halogen atom, but it is preferably not substituted with a halogen atom such as a fluorine atom or chlorine atomA non-halogenated alkyl group.

The above alkyl group preferably does not have any substituent.

As R^11bThe alkyl group is preferably H, a linear or branched alkyl group having 1 to 9 carbon atoms with or without a substituent, or a cyclic alkyl group having 3 to 9 carbon atoms with or without a substituent, more preferably H, a linear or branched alkyl group having 1 to 9 carbon atoms which does not include a carbonyl group, or a cyclic alkyl group having 3 to 9 carbon atoms which does not include a carbonyl group, still more preferably H, or a linear or branched alkyl group having 1 to 9 carbon atoms which does not include a substituent, and still more preferably H or a methyl group (-CH)₃) Or ethyl (-C)₂H₅) Particularly preferred is H or methyl (-CH)₃) Most preferably, H.

The hydroxylation in the step (11b) can be carried out, for example, by the following method: (1) a method of allowing iron (II) phthalocyanine (fe (pc)) and sodium borohydride to act on the compound (10b) in an oxygen atmosphere; (2) reacting isopinocampheylborane (IpcBH)₂) A method in which the compound (10b) is allowed to act thereon, and then the obtained intermediate (dialkylboron) is oxidized.

In the method (1), the amount of the iron (II) phthalocyanine may be a catalyst amount, and may be used in an amount of 0.001 to 1.2 mol based on 1 mol of the compound (10 b).

In the method (1), sodium borohydride may be used in an amount of 0.5 to 20 mol based on 1 mol of the compound (10 b).

The reaction of the process (1) may be carried out in a solvent. The solvent is preferably an organic solvent, and examples thereof include ethers, halogenated hydrocarbons, aromatic hydrocarbons, nitriles, nitrogen-containing polar organic compounds, and the like.

Examples of the ether include diethyl ether, tetrahydrofuran, dioxane, diethylene glycol diethyl ether, and the like, and among them, diethyl ether and tetrahydrofuran are preferable.

Examples of the halogenated hydrocarbon include dichloromethane, dichloroethane, chloroform, chlorobenzene, and o-dichlorobenzene, and dichloromethane and chloroform are preferable among them.

The aromatic hydrocarbon includes benzene, toluene, xylene, etc., and among them, benzene and toluene are preferable.

The nitrile includes acetonitrile, propionitrile, butyronitrile, isobutyronitrile, benzonitrile and the like, and among them, acetonitrile is preferable.

Examples of the nitrogen-containing polar organic compound include N, N-dimethylformamide, N-dimethylacetamide, N-methyl-2-pyrrolidone, 1, 3-dimethyl-2-imidazolidinone, and the like, and among them, N-dimethylformamide, N-dimethylacetamide, and N-methyl-2-pyrrolidone are preferable.

The reaction temperature in the method (1) is preferably-78 to 200 ℃ and more preferably 0 to 150 ℃.

The pressure of the reaction in the process (1) is preferably 0 to 5.0MPa, more preferably 0.1 to 1.0 MPa.

The reaction time in the method (1) is preferably 0.1 to 72 hours, more preferably 0.1 to 48 hours.

In the method (2), isopinocampheylborane may be used in an amount of 1.0 to 10.0 mol based on 1 mol of the compound (10 b).

The reaction of compound (10b) with isopinocampheylborane may be carried out in a solvent. The solvent is preferably an organic solvent, and examples thereof include ethers, halogenated hydrocarbons, aromatic hydrocarbons, and the like.

Examples of the ether include diethyl ether, tetrahydrofuran, dioxane, diethylene glycol diethyl ether, and the like, and among them, diethyl ether and tetrahydrofuran are preferable.

Examples of the halogenated hydrocarbon include dichloromethane, dichloroethane, chloroform, chlorobenzene, and o-dichlorobenzene, and dichloromethane and chloroform are preferable among them.

The aromatic hydrocarbon includes benzene, toluene, xylene, etc., and among them, benzene and toluene are preferable.

The reaction temperature of the compound (10b) with isopinocampheylborane is preferably-78 to 200 ℃ and more preferably 0 to 150 ℃.

The pressure for the reaction of the compound (10b) with isopinocampheylborane is preferably 0 to 5.0MPa, more preferably 0.1 to 1.0 MPa.

The reaction time of the compound (10b) with isopinocampheylborane is preferably 0.1 to 72 hours, more preferably 0.1 to 48 hours.

The oxidation in the method (2) can be carried out by allowing an oxidizing agent to act on the intermediate. Examples of the oxidizing agent include hydrogen peroxide. The oxidizing agent may be used in an amount of 0.7 to 10 mol based on 1 mol of the intermediate.

The oxidation in the method (2) may be carried out in a solvent. Examples of the solvent include water, methanol, and ethanol, and among them, water is preferable.

The temperature for the oxidation in the method (2) is preferably 0 to 100 ℃ and more preferably 0 to 80 ℃.

The pressure for the oxidation in the process (2) is preferably 0 to 5.0MPa, more preferably 0.1 to 1.0 MPa.

The time for the oxidation in the method (2) is preferably 0.1 to 72 hours, more preferably 0.1 to 48 hours.

In the step (12b), examples of the method for oxidizing the compound (11b) include: (a) using Jones reagent (CrO)₃/H₂SO₄) Method (jones oxidation); (b) methods using dess-martin periodinane (DMP) (dess-martin oxidation); (c) a method using pyridinium chlorochromate (PCC); (d) in NiCl₂A method of allowing a bleaching agent (about 5 to 6% aqueous solution of NaOCl) to act in the presence of a nickel compound; (e) in Al (CH)₃)₃、Al[OCH(CH₃)₂]₃And a method of allowing a hydrogen acceptor such as an aldehyde or a ketone to act in the presence of an aluminum catalyst (W-type oxidation).

The oxidation in the step (12b) may be carried out in a solvent. The solvent is preferably water or an organic solvent, and examples thereof include water, ketones, ethers, halogenated hydrocarbons, aromatic hydrocarbons, and nitriles.

Examples of the ketone include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, diacetone alcohol, and the like, and among them, acetone is preferable.

Examples of the ether include diethyl ether, tetrahydrofuran, dioxane, diethylene glycol diethyl ether, and the like, and among them, diethyl ether and tetrahydrofuran are preferable.

Examples of the halogenated hydrocarbon include dichloromethane, dichloroethane, chloroform, chlorobenzene, and o-dichlorobenzene, and dichloromethane and chloroform are preferable among them.

The aromatic hydrocarbon includes benzene, toluene, xylene, etc., and among them, benzene and toluene are preferable.

The nitrile includes acetonitrile, propionitrile, butyronitrile, isobutyronitrile, benzonitrile and the like, and among them, acetonitrile is preferable.

The temperature of the oxidation in the step (12b) is preferably-78 to 200 ℃, and may be suitably selected depending on the method used.

The pressure for the oxidation in the step (12b) is preferably 0 to 5.0MPa, and can be suitably selected depending on the method used.

The time for oxidation in the step (12b) is preferably 0.1 to 72 hours, and can be appropriately selected depending on the method used.

The sulfation in the step (13b) can be carried out by reacting the compound (12b) with a sulfating agent. Examples of the sulfating agent include sulfur trioxide amine complexes such as sulfur trioxide pyridine complex, sulfur trioxide trimethylamine complex, and sulfur trioxide triethylamine complex, sulfur trioxide amide complexes such as sulfur trioxide dimethylformamide complex, sulfuric acid-dicyclohexylcarbodiimide, chlorosulfuric acid, concentrated sulfuric acid, and sulfamic acid. The amount of the sulfating agent to be used is preferably 0.5 to 10 mol, more preferably 0.5 to 5 mol, and still more preferably 0.7 to 4 mol, based on 1 mol of the compound (12 b).

The sulfation in the step (13b) may be carried out in a solvent. The solvent is preferably an organic solvent, and examples thereof include ethers, halogenated hydrocarbons, aromatic hydrocarbons, pyridine, dimethyl sulfoxide, sulfolane, and nitriles.

Examples of the ether include diethyl ether, tetrahydrofuran, dioxane, diethylene glycol diethyl ether, and the like, and among them, diethyl ether and tetrahydrofuran are preferable.

Examples of the halogenated hydrocarbon include dichloromethane, dichloroethane, chloroform, chlorobenzene, and o-dichlorobenzene, and dichloromethane and chloroform are preferable among them.

The aromatic hydrocarbon includes benzene, toluene, xylene, etc., and among them, benzene and toluene are preferable.

The nitrile includes acetonitrile, propionitrile, butyronitrile, isobutyronitrile, benzonitrile and the like, and among them, acetonitrile is preferable.

The temperature of the sulfation in the step (13b) is preferably-78 to 200 ℃, more preferably-20 to 150 ℃.

The pressure for sulfation in the step (13b) is preferably 0 to 10MPa, more preferably 0.1 to 5 MPa.

The time for sulfation in the step (13b) is preferably 0.1 to 72 hours, more preferably 0.1 to 48 hours.

The surfactant (b) can be produced by a production method comprising the step (21b) and the step (22b),

the step (21b) is a step of reacting a compound represented by the formula:

[ solution 54]

(in the formula, L, R^1b～R^4bN, p and q are as described above. R^101bIs an organic group) to give the following formula:

[ solution 55]

(in the formula, L, R^1b～R^4bN, p and q are as defined above) in the presence of a compound (21b),

step (22b) is a step of sulfating compound (21b) to obtain the following formula:

[ solution 56]

(in the formula, L, R^1b～R^4bN, p, q and X^bAs described above) of the compound (22 b).

As R^101bPreferably, the alkyl group has 1 to 20 carbon atoms. 2R ^101bMay be the same or different.

The ozonolysis in step (21b) can be carried out by subjecting the compound (20b) to an action of ozone and then to a post-treatment with a reducing agent.

Ozone can be generated by silent discharge in oxygen.

Examples of the reducing agent used in the above-mentioned post-treatment include zinc, dimethyl sulfide, thiourea, phosphines, etc., and among them, phosphines are preferable.

The ozonolysis in step (21b) may be carried out in a solvent. The solvent is preferably water or an organic solvent, and examples thereof include water, alcohols, carboxylic acids, ethers, halogenated hydrocarbons, and aromatic hydrocarbons.

Examples of the alcohol include methanol, ethanol, 1-propanol, and isopropanol. Among them, methanol and ethanol are preferable.

Examples of the carboxylic acids include acetic acid and propionic acid. Among them, acetic acid is preferred.

Examples of the ether include diethyl ether, tetrahydrofuran, dioxane, diethylene glycol diethyl ether, and the like, and among them, diethyl ether and tetrahydrofuran are preferable.

Examples of the halogenated hydrocarbon include dichloromethane, dichloroethane, chloroform, chlorobenzene, and o-dichlorobenzene, and dichloromethane and chloroform are preferable among them.

The aromatic hydrocarbon includes benzene, toluene, xylene, etc., and among them, benzene and toluene are preferable.

The temperature for the ozonolysis in the step (21b) is preferably-78 to 200 ℃, more preferably 0 to 150 ℃.

The pressure for ozonolysis in step (21b) is preferably 0 to 5.0MPa, more preferably 0.1 to 1.0 MPa.

The time for the ozonolysis in step (21b) is preferably 0.1 to 72 hours, more preferably 0.1 to 48 hours.

The sulfation in the step (22b) can be carried out by reacting the compound (21b) with a sulfating agent, and the same conditions as those for the sulfation in the step (13b) can be employed.

The surfactant (b) can be produced by a production method comprising the steps (31b), (32b), (33b) and (34b),

the step (31b) is a step of reacting a compound represented by the formula:

R^21b-CH＝CH-(CR^2b ₂)n-(OR^3b)_p-(CR^4b ₂)_q-L-OH

(in the formula, L, R^2b～R^4bN, p and q are as described above. R^21bA compound (30b) represented by H, a linear or branched alkyl group having 1 or more carbon atoms with or without a substituent, or a cyclic alkyl group having 3 or more carbon atoms with or without a substituent, and which may contain a heterocyclic ring having 1 or 2 valences or may form a ring when the number of carbon atoms is 3 or more) is epoxidized to obtain the following formula:

[ solution 57]

(in the formula, L, R^2b～R^4b、R^21bN, p and q are as defined above) in the presence of a compound (31b),

The step (32b) is to react the compound (31b) with R^22b ₂CuLi(R^22bA linear or branched alkyl group having 1 or more carbon atoms, which may have a substituent, or a cyclic alkyl group having 3 or more carbon atoms, which may have a substituent, and which may contain a heterocyclic ring having 1 or 2 valences or may form a ring when the number of carbon atoms is 3 or more), to obtain the following formula:

[ solution 58]

(in the formula, L, R^2b～R^4b、R^21b、R^22bN, p and q are as defined aboveThe above) is described in (a) is described in (b),

step (33b) is to oxidize compound (32b) to obtain the following formula:

[ chemical 59]

(in the formula, L, R^2b～R^4b、R^21b、R^22bN, p and q are as defined above) in the presence of a compound (33b),

step (34b) is a step of sulfating compound (33b) to obtain the following formula:

[ solution 60]

(in the formula, L, R^2b～R^4b、R^21b、R^22bN, p, q and X^bAs described above) of the compound (34 b).

As R^21bThe above alkyl group of (a) preferably does not contain a carbonyl group.

As R^21bIn the above alkyl groups, 75% or less of the hydrogen atoms bonded to the carbon atoms may be substituted with a halogen atom, 50% or less may be substituted with a halogen atom, and 25% or less may be substituted with a halogen atom, but a non-halogenated alkyl group containing no halogen atom such as a fluorine atom or a chlorine atom is preferable.

The above alkyl group preferably does not have any substituent.

As R^21bThe alkyl group is preferably H, a linear or branched alkyl group having 1 to 8 carbon atoms with or without a substituent, or a cyclic alkyl group having 3 to 8 carbon atoms with or without a substituent, more preferably H, a linear or branched alkyl group having 1 to 8 carbon atoms which does not include a carbonyl group, or a cyclic alkyl group having 3 to 8 carbon atoms which does not include a carbonyl group, still more preferably H, or a linear or branched alkyl group having 1 to 8 carbon atoms which does not include a substituent, and particularly preferably H, a linear or branched alkyl group having 1 to 8 carbon atoms which does not include a carbonyl groupH or methyl (-CH)₃) Most preferably, H.

As R^22bThe above alkyl group of (a) preferably does not contain a carbonyl group.

As R^22bIn the above alkyl groups, 75% or less of the hydrogen atoms bonded to the carbon atoms may be substituted with a halogen atom, 50% or less may be substituted with a halogen atom, and 25% or less may be substituted with a halogen atom, but a non-halogenated alkyl group containing no halogen atom such as a fluorine atom or a chlorine atom is preferable.

The above alkyl group preferably does not have any substituent.

As R^22bThe alkyl group is preferably a linear or branched alkyl group having 1 to 9 carbon atoms, which may or may not have a substituent, or a cyclic alkyl group having 3 to 9 carbon atoms, more preferably a linear or branched alkyl group having 1 to 9 carbon atoms, which may or may not include a carbonyl group, or a cyclic alkyl group having 3 to 9 carbon atoms, which may not include a carbonyl group, even more preferably a linear or branched alkyl group having 1 to 9 carbon atoms, which may not have a substituent, and particularly preferably a methyl group (-CH) ₃) Or ethyl (-C)₂H₅) Most preferred is methyl (-CH)₃)。

2R^22bMay be the same or different.

R^21bAnd R^22bThe total number of carbon atoms of (a) is preferably 1 to 7, more preferably 1 to 2, and most preferably 1.

The epoxidation in the step (31b) can be carried out by allowing an epoxidizing agent to act on the compound (30 b).

Examples of the epoxidizing agent include m-chloroperbenzoic acid (m-CPBA), perbenzoic acid, peracids such as hydrogen peroxide and t-butyl hydroperoxide, dimethyldioxirane and methyltrifluoromethyldioxirane, among which peracids are preferred and m-chloroperbenzoic acid is more preferred.

The epoxidizing agent may be used in an amount of 0.5 to 10.0 mol based on 1 mol of the compound (30 b).

The epoxidation in the step (31b) may be carried out in a solvent. The solvent is preferably an organic solvent, and examples thereof include ketones, ethers, halogenated hydrocarbons, aromatic hydrocarbons, nitriles, pyridine, nitrogen-containing polar organic compounds, and dimethyl sulfoxide, and among them, dichloromethane is preferable.

Examples of the ketone include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, diacetone alcohol, and the like, and among them, acetone is preferable.

Examples of the ether include diethyl ether, tetrahydrofuran, dioxane, diethylene glycol diethyl ether, and the like, and among them, diethyl ether and tetrahydrofuran are preferable.

Examples of the halogenated hydrocarbon include dichloromethane, dichloroethane, chloroform, chlorobenzene, and o-dichlorobenzene, and dichloromethane and chloroform are preferable among them.

The aromatic hydrocarbon includes benzene, toluene, xylene, etc., and among them, benzene and toluene are preferable.

The nitrile includes acetonitrile, propionitrile, butyronitrile, isobutyronitrile, benzonitrile and the like, and among them, acetonitrile is preferable.

Examples of the nitrogen-containing polar organic compound include N, N-dimethylformamide, N-dimethylacetamide, N-methyl-2-pyrrolidone, 1, 3-dimethyl-2-imidazolidinone, and the like, and among them, N-dimethylformamide, N-dimethylacetamide, and N-methyl-2-pyrrolidone are preferable.

The temperature of epoxidation in the step (31b) is preferably-78 to 200 ℃, more preferably-40 to 150 ℃.

The pressure for epoxidation in the step (31b) is preferably 0 to 5.0MPa, more preferably 0.1 to 1.0 MPa.

The time for the epoxidation in the step (31b) is preferably 0.1 to 72 hours, more preferably 0.1 to 48 hours.

In the step (32b), the lithium dialkylcopper may be used in an amount of 0.5 to 10.0 mol based on 1 mol of the compound (31 b).

The reaction of step (32b) may be carried out in a solvent. The solvent is preferably an organic solvent, and examples thereof include ethers, halogenated hydrocarbons, aromatic hydrocarbons, and the like.

Examples of the ether include diethyl ether, tetrahydrofuran, dioxane, diethylene glycol diethyl ether, and the like, and among them, diethyl ether and tetrahydrofuran are preferable.

Examples of the halogenated hydrocarbon include dichloromethane, dichloroethane, chloroform, chlorobenzene, and o-dichlorobenzene, and dichloromethane and chloroform are preferable among them.

The aromatic hydrocarbon includes benzene, toluene, xylene, etc., and among them, benzene and toluene are preferable.

The temperature of the reaction in the step (32b) is preferably-78 to 200 ℃ and more preferably-40 to 150 ℃.

The pressure of the reaction in the step (32b) is preferably 0 to 5.0MPa, more preferably 0.1 to 1.0 MPa.

The reaction time in the step (32b) is preferably 0.1 to 72 hours, more preferably 0.1 to 48 hours.

In the step (33b), examples of the method for oxidizing the compound (32b) include: (a) using Jones reagent (CrO)₃/H₂SO₄) Method (jones oxidation); (b) methods using dess-martin periodinane (DMP) (dess-martin oxidation); (c) a method using pyridinium chlorochromate (PCC); (d) in NiCl₂A method of allowing a bleaching agent (about 5 to 6% aqueous solution of NaOCl) to act in the presence of a nickel compound; (e) in Al (CH)₃)₃、Al[OCH(CH₃)₂]₃And a method of allowing a hydrogen acceptor such as an aldehyde or a ketone to act in the presence of an aluminum catalyst (W-type oxidation).

The oxidation in the step (33b) may be carried out in a solvent. The solvent is preferably water or an organic solvent, and examples thereof include water, ketones, alcohols, ethers, halogenated hydrocarbons, aromatic hydrocarbons, and nitriles.

Examples of the ketone include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, diacetone alcohol, and the like, and among them, acetone is preferable.

Examples of the alcohol include methanol, ethanol, 1-propanol, and isopropanol. Among them, methanol and ethanol are preferable.

Examples of the ether include diethyl ether, tetrahydrofuran, dioxane, diethylene glycol diethyl ether, and the like, and among them, diethyl ether and tetrahydrofuran are preferable.

Examples of the halogenated hydrocarbon include dichloromethane, dichloroethane, chloroform, chlorobenzene, and o-dichlorobenzene, and dichloromethane and chloroform are preferable among them.

The aromatic hydrocarbon includes benzene, toluene, xylene, etc., and among them, benzene and toluene are preferable.

The nitrile includes acetonitrile, propionitrile, butyronitrile, isobutyronitrile, benzonitrile and the like, and among them, acetonitrile is preferable.

The temperature of the oxidation in the step (33b) is preferably-78 to 200 ℃, and may be suitably selected depending on the method used.

The pressure for the oxidation in the step (33b) is preferably 0 to 5.0MPa, and can be suitably selected depending on the method used.

The time for oxidation in the step (33b) is preferably 0.1 to 72 hours, and can be selected appropriately according to the method used.

The sulfation in the step (34b) can be carried out by reacting the compound (33b) with a sulfating agent, and the same conditions as those for the sulfation in the step (13b) can be employed.

The surfactant (b) can be produced by a production method comprising the step (41b) and the step (42b),

the step (41b) is a step of reacting a compound represented by the formula:

R^11b-CH＝CH-(CR^2b ₂)n-(OR^3b)_p-(CR^4b ₂)_q-L-OH

(in the formula, L, R^2b～R^4b、R^11bN, p and q are as defined above) to give the following formula:

[ solution 61]

(in the formula, L, R^2b～R^4b、R^11bN, p and q are as defined above) in the presence of a compound (41b),

step (42b) is to sulfate compound (41b) to obtain the following formula:

[ solution 62]

(in the formula, L, R^2b～R^4b、R^11bN, p, q and X^bAs described above) of the compound (42 b).

The oxidation in the step (41b) can be carried out by allowing an oxidizing agent to act on the compound (10b) in the presence of water and a palladium compound.

Examples of the oxidizing agent include monovalent or divalent copper salts such as copper chloride, copper acetate, copper cyanide and copper trifluoromethanesulfonate, iron salts such as iron chloride, iron acetate, iron cyanide, iron trifluoromethanesulfonate and iron hexacyanoferrate, benzoquinones such as 1, 4-benzoquinone, 2, 3-dichloro-5, 6-dicyano-1, 4-benzoquinone, tetrachloro-1, 2-benzoquinone and tetrachloro-1, 4-benzoquinone, H ₂O₂、MnO₂、KMnO₄、RuO₄Meta-chloroperbenzoic acid, oxygen, etc. Among them, copper salts, iron salts and benzoquinones are preferable, and copper chloride, iron chloride and 1, 4-benzoquinone are more preferable.

The oxidizing agent may be used in an amount of 0.001 to 10 mol based on 1 mol of the compound (10 b).

The water may be used in an amount of 0.5 to 1000 mol based on 1 mol of the compound (10 b).

The palladium compound may be palladium dichloride. The amount of the palladium compound may be a catalyst amount, and may be used in an amount of 0.0001 to 1.0 mol based on 1 mol of the compound (10 b).

The oxidation in the step (41b) may be carried out in a solvent. Examples of the solvent include water, esters, aliphatic hydrocarbons, aromatic hydrocarbons, alcohols, carboxylic acids, ethers, halogenated hydrocarbons, nitrogen-containing polar organic compounds, nitriles, dimethyl sulfoxide, and sulfolane.

Examples of the ester include ethyl acetate, butyl acetate, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate (PGMEA; also known as 1-methoxy-2-acetoxypropane), and ethyl acetate is preferable.

Examples of the aliphatic hydrocarbon include hexane, cyclohexane, heptane, octane, nonane, decane, undecane, dodecane, mineral spirits, and the like, and cyclohexane and heptane are preferable among them.

The aromatic hydrocarbon includes benzene, toluene, xylene, etc., and among them, benzene and toluene are preferable.

Examples of the alcohol include methanol, ethanol, 1-propanol, and isopropanol.

Examples of the carboxylic acids include acetic acid and propionic acid. Among them, acetic acid is preferred.

Examples of the ether include diethyl ether, tetrahydrofuran, dioxane, diethylene glycol diethyl ether, and the like, and among them, diethyl ether and tetrahydrofuran are preferable.

Examples of the halogenated hydrocarbon include dichloromethane, dichloroethane, chloroform, chlorobenzene, and o-dichlorobenzene, and dichloromethane and chloroform are preferable among them.

Examples of the nitrogen-containing polar organic compound include N, N-dimethylformamide, N-dimethylacetamide, N-methyl-2-pyrrolidone, 1, 3-dimethyl-2-imidazolidinone, and the like, and among them, N-dimethylformamide, N-dimethylacetamide, and N-methyl-2-pyrrolidone are preferable.

The nitrile includes acetonitrile, propionitrile, butyronitrile, isobutyronitrile, benzonitrile and the like, and among them, acetonitrile is preferable.

The temperature of the oxidation in the step (41b) is preferably-78 to 200 ℃, more preferably-20 to 150 ℃.

The pressure for the oxidation in the step (41b) is preferably 0 to 10MPa, more preferably 0.1 to 5.0 MPa.

The time for oxidation in the step (41b) is preferably 0.1 to 72 hours, more preferably 0.1 to 48 hours.

The sulfation in the step (42b) can be carried out by reacting the compound (41b) with a sulfating agent, and the same conditions as those for the sulfation in the step (13b) can be employed.

The surfactant (b) can be produced by a production method comprising the steps (51b), (52b), (53b) and (54b),

the step (51b) is a step of reacting a compound represented by the formula:

R^11b-CH＝CH-(CR^2b ₂)_n-OH

(in the formula, R^2b、R^11bAnd n is as described above) with a halogenating agent to give a compound of the formula:

R^11b-CH＝CH-(CR^2b ₂)_n-Z^51b

(in the formula, R^2b、R^11bAnd n is as described above. Z^51bA halogen atom) in the reaction mixture,

the step (52b) is a step of reacting the compound (51b) with HO-R^3b-L-OH(L、R^3bAs described above) to give the following formula:

R^11b-CH＝CH-(CR^2b ₂)_n-O-R^3b-L-OH

(in the formula, L, R^2b、R^3b、R^11bAnd n is as defined above) to a compound (52b),

the step (53b) is to oxidize the compound (52b) to obtain the following formula:

[ solution 63]

(in the formula, L, R^2b、R^3b、R^11bAnd n is as defined above) to a compound (53b),

step (54b) is to sulfate compound (53b) to obtain the following formula:

[ solution 64]

(in the formula, L, R^2b、R^3b、R^11bN and X^bAs described above) of the compound (54b)) The process (2).

As Z^51bPreferably F, Cl, Br or I, more preferably Br.

Examples of the halogenating agent used in the step (51b) include N-bromosuccinimide, N-chlorosuccinimide and the like.

The halogenating agent may be used in an amount of 0.5 to 10.0 mol based on 1 mol of the compound (50 b).

The reaction in the step (51b) may be carried out in the presence of a phosphine such as triphenylphosphine.

The phosphine may be used in an amount of 0.5 to 10.0 mol based on 1 mol of the compound (50 b).

The reaction of step (51b) may be carried out in a solvent. The solvent is preferably an organic solvent, and examples thereof include ethers, halogenated hydrocarbons, aromatic hydrocarbons, and the like.

Examples of the ether include diethyl ether, tetrahydrofuran, dioxane, diethylene glycol diethyl ether, and the like, and among them, diethyl ether and tetrahydrofuran are preferable.

Examples of the halogenated hydrocarbon include dichloromethane, dichloroethane, chloroform, chlorobenzene, and o-dichlorobenzene, and dichloromethane and chloroform are preferable among them.

The aromatic hydrocarbon includes benzene, toluene, xylene, etc., and among them, benzene and toluene are preferable.

The temperature of the reaction in the step (51b) is preferably-78 to 200 ℃ and more preferably-40 to 150 ℃.

The pressure of the reaction in the step (51b) is preferably 0 to 5.0MPa, more preferably 0.1 to 1.0 MPa.

The reaction time in the step (51b) is preferably 0.1 to 72 hours, more preferably 0.1 to 48 hours.

In the step (52b), the alkylene glycol may be used in an amount of 0.5 to 10.0 mol based on 1 mol of the compound (51 b).

The reaction in the step (52b) may be carried out in the presence of a base. Examples of the base include sodium hydride, sodium hydroxide, and potassium hydroxide.

The base may be used in an amount of 0.5 to 10.0 mol based on 1 mol of the compound (51 b).

The reaction of step (52b) may be carried out in a solvent. The solvent is preferably an organic solvent, and examples thereof include nitrogen-containing polar organic compounds, ethers, halogenated hydrocarbons, aromatic hydrocarbons, and the like.

Examples of the nitrogen-containing polar organic compound include N, N-dimethylformamide, N-dimethylacetamide, N-methyl-2-pyrrolidone, 1, 3-dimethyl-2-imidazolidinone, and the like, and among them, N-dimethylformamide, N-dimethylacetamide, and N-methyl-2-pyrrolidone are preferable.

Examples of the ether include diethyl ether, tetrahydrofuran, dioxane, diethylene glycol diethyl ether, and the like, and among them, diethyl ether and tetrahydrofuran are preferable.

Examples of the halogenated hydrocarbon include dichloromethane, dichloroethane, chloroform, chlorobenzene, and o-dichlorobenzene, and dichloromethane and chloroform are preferable among them.

The aromatic hydrocarbon includes benzene, toluene, xylene, etc., and among them, benzene and toluene are preferable.

The temperature of the reaction in the step (52b) is preferably-78 to 200 ℃ and more preferably-40 to 150 ℃.

The pressure of the reaction in the step (52b) is preferably 0 to 5.0MPa, more preferably 0.1 to 1.0 MPa.

The reaction time in the step (52b) is preferably 0.1 to 72 hours, more preferably 0.1 to 48 hours.

The oxidation in the step (53b) can be carried out by allowing an oxidizing agent to act on the compound (52b) in the presence of water and a palladium compound, and the same conditions as those for the oxidation in the step (41b) can be employed.

The sulfation in the step (54b) can be carried out by reacting the compound (53b) with a sulfating agent, and the same conditions as those for the sulfation in the step (13b) can be employed.

In any of the above-mentioned production methods, after completion of each step, the purity of the obtained compound can be improved by removing the solvent by distillation, or by performing distillation, purification, or the like. In addition, the resulting compound has-OSO₃In the case of the group represented by H (i.e. X)^bIn the case of H) the-OSO may be obtained by contacting with a base such as sodium carbonate or ammonia₃H is converted to a sulfate group.

Among the methods for producing the surfactant (b), the production method including the steps (41b) and (42b) is preferable.

The surfactant (c) will be explained.

In the formula (c), R^1cIs a linear or branched alkyl group having 1 or more carbon atoms or a cyclic alkyl group having 3 or more carbon atoms.

When the number of carbon atoms of the alkyl group is 3 or more, a carbonyl group (-C (═ O) -) may be contained between 2 carbon atoms. When the alkyl group has 2 or more carbon atoms, the terminal of the alkyl group may contain the carbonyl group. I.e. CH₃Acyl groups such as an acetyl group represented by — C (═ O) -, are also included in the above alkyl groups.

When the number of carbon atoms of the alkyl group is 3 or more, the alkyl group may contain a heterocyclic ring having a valence of 1 or 2, or may form a ring. The heterocyclic ring is preferably an unsaturated heterocyclic ring, more preferably an oxygen-containing unsaturated heterocyclic ring, and examples thereof include furan rings and the like. R^1cIn the above formula, a 2-valent heterocyclic ring may be inserted between 2 carbon atoms, a 2-valent heterocyclic ring may be located at the terminal and bonded to — C (═ O) -, and a 1-valent heterocyclic ring may be located at the terminal of the alkyl group.

In the present specification, the "number of carbon atoms" of the alkyl group also includes the number of carbon atoms constituting the carbonyl group and the number of carbon atoms constituting the heterocycle. E.g. CH₃-C(＝O)-CH₂-the group having 3 carbon atoms and CH ₃-C(＝O)-C₂H₄-C(＝O)-C₂H₄-the number of carbon atoms of the group represented is 7, CH₃The number of carbon atoms of the group represented by — C (═ O) — is 2.

In the above alkyl group, the hydrogen atom bonded to the carbon atom may be substituted with a functional group, for example, a hydroxyl group (-OH) or a 1-valent organic group containing an ester bond, but is preferably not substituted with any functional group.

Examples of the 1-valent organic group containing an ester bond include the following: -O-C (═ O) -R^101c(in the formula，R^101cIs an alkyl group).

In the above alkyl groups, 75% or less of hydrogen atoms bonded to carbon atoms may be substituted with a halogen atom, 50% or less may be substituted with a halogen atom, and 25% or less may be substituted with a halogen atom, but a non-halogenated alkyl group containing no halogen atom such as a fluorine atom or a chlorine atom is preferable.

In the formula (c), R^2cAnd R^3cIndependently a single bond or a 2-valent linking group.

R^2cAnd R^3cPreferably a single bond, a linear or branched alkylene group having 1 or more carbon atoms, or a cyclic alkylene group having 3 or more carbon atoms.

Form R^2cAnd R^3cThe above alkylene group of (a) preferably does not contain a carbonyl group.

In the above alkylene group, the hydrogen atom bonded to the carbon atom may be substituted with a functional group, for example, a hydroxyl group (-OH) or a 1-valent organic group containing an ester bond, but is preferably not substituted with any functional group.

Examples of the 1-valent organic group containing an ester bond include the following: -O-C (═ O) -R^102c(in the formula, R^102cIs an alkyl group).

Of the above alkylene groups, 75% or less of hydrogen atoms bonded to carbon atoms may be substituted with halogen atoms, 50% or less may be substituted with halogen atoms, and 25% or less may be substituted with halogen atoms, but a non-halogenated alkylene group containing no halogen atom such as a fluorine atom or chlorine atom is preferable.

R^1c、R^2cAnd R^3cThe total number of carbon atoms of (2) is 5 or more. The total number of carbon atoms is preferably 7 or more, more preferably 9 or more, preferably 20 or less, more preferably 18 or less, and further preferably 15 or less.

R^1c、R^2cAnd R^3cAny two of which may be bonded to each other to form a ring.

In the formula (c), A in the formula^cis-COOX^cor-SO₃X^c(X^cIs H, a metal atom, NR^4c ₄With or without access toImidazolium, pyridinium, with or without substituents or phosphonium, R^4cIs H or an organic group, which may be the same or different). As R^4cThe organic group in (1) is preferably an alkyl group. As R^4cPreferably, H or an organic group having 1 to 10 carbon atoms, more preferably H or an organic group having 1 to 4 carbon atoms, and further preferably H or an alkyl group having 1 to 4 carbon atoms. Examples of the metal atom include alkali metals (group 1), alkaline earth metals (group 2), and the like, and Na, K, and Li are preferable.

As X^cPreferably H, alkali metal (group 1), alkaline earth metal (group 2) or NR^4c ₄For reasons of easy solubility in water, H, Na, K, Li or NH are more preferred₄Further, Na, K or NH is preferable for the reason of being more soluble in water₄Particularly preferred is Na or NH₄For reasons of easy removal, NH is most preferred₄。X^cIs NH₄In the case of the surfactant, the surfactant has excellent solubility in an aqueous medium, and a metal component is not likely to remain in PTFE or a final product.

As R^1cPreferably, the alkyl group is a linear or branched alkyl group having 1 to 8 carbon atoms, which does not include a carbonyl group, a cyclic alkyl group having 3 to 8 carbon atoms, which does not include a carbonyl group, a linear or branched alkyl group having 2 to 45 carbon atoms, which includes 1 to 10 carbonyl groups, a cyclic alkyl group having 3 to 45 carbon atoms, which includes a carbonyl group, or an alkyl group having 3 to 45 carbon atoms, which includes a heterocyclic ring having 1 or 2 valences.

In addition, as R^1cMore preferably, the following formula:

[ solution 65]

(in the formula, n^11cIs an integer of 0 to 10, R^11cIs a linear or branched alkyl group having 1 to 5 carbon atoms or a cyclic alkyl group having 3 to 5 carbon atoms, R^12cIs an alkylene group having 0 to 3 carbon atoms. n is^11cIs an integer of 2 to 10In the case of (1), R^12cEach may be the same or different).

As n^11cPreferably an integer of 0 to 5, more preferably an integer of 0 to 3, and further preferably an integer of 1 to 3.

As R^11cThe above alkyl group of (a) preferably does not contain a carbonyl group.

As R^11cIn the above alkyl group, the hydrogen atom bonded to the carbon atom may be substituted with a functional group, for example, a hydroxyl group (-OH) or a 1-valent organic group containing an ester bond, but is preferably not substituted with any functional group.

Examples of the 1-valent organic group containing an ester bond include the following: -O-C (═ O) -R^103c(in the formula, R^103cIs an alkyl group).

As R^11cIn the above alkyl groups, 75% or less of the hydrogen atoms bonded to the carbon atoms may be substituted with a halogen atom, 50% or less may be substituted with a halogen atom, and 25% or less may be substituted with a halogen atom, but a non-halogenated alkyl group containing no halogen atom such as a fluorine atom or a chlorine atom is preferable.

R^12cIs an alkylene group having 0 to 3 carbon atoms. The number of carbon atoms is preferably 1 to 3.

As R^12cThe alkylene group in (b) may be linear or branched.

As R^12cThe above alkylene group of (a) preferably does not contain a carbonyl group. As R^12cMore preferably an ethylene group (-C)₂H₄-) or propylene (-C)₃H₆-)。

As R^12cIn the above alkylene group, the hydrogen atom bonded to the carbon atom may be substituted with a functional group, for example, a hydroxyl group (-OH) or a 1-valent organic group containing an ester bond, but is preferably not substituted with any functional group.

Examples of the 1-valent organic group containing an ester bond include the following: -O-C (═ O) -R^104c(in the formula, R^104cIs an alkyl group).

As R^12cOf the above alkylene groups, having hydrogen atoms bonded to carbon atoms75% or less, 50% or less and 25% or less of the total amount of the non-halogenated alkylene group may be substituted with a halogen atom, but it is preferably a non-halogenated alkylene group containing no halogen atom such as a fluorine atom or chlorine atom.

As R^2cAnd R^3cThe alkylene group having 1 or more carbon atoms and not containing a carbonyl group is preferable, the alkylene group having 1 to 3 carbon atoms and not containing a carbonyl group is more preferable, and the ethylene group (-C) is further preferable₂H₄-) or propylene (-C)₃H₆-)。

The surfactant (c) may be the following surfactant. In the formulae A^cAs described above.

[ solution 66]

[ solution 67]

[ solution 68]

[ solution 69]

[ solution 70]

[ solution 71]

[ chemical formula 72]

[ solution 73]

The surfactant (c) is a novel compound, and can be produced, for example, by the production method described below.

The surfactant (c) can be suitably produced by a production method comprising the step (11c), the step (12c), the step (13c) and the step (14c),

the step (11c) is a step of reacting:

[ chemical formula 74]

(in the formula, R^3cAs described above, E^cIs a leaving group) with lithium and a compound of formula (10 c): r ^201c ₃Si-Cl (in the formula, R)^201cIndependently an alkyl or aryl) to yield a chlorosilane compound of the formula:

[ solution 75]

(in the formula, R^3c、R^201cAnd E^cAs described above) of the compound (11c),

step (12c) is performed by reacting compound (11c) with a compound of formula (la):

[ 76]

(in the formula, R^1cAs mentioned above, R^21cIs a single bond or a 2-valent linking group) to give an olefin of the formula:

[ solution 77]

(in the formula, R^1c、R^21c、R^3cAnd E^cAs described above) of the compound (12c),

step (13c) is a step of removing the leaving group of compound (12c) to obtain a compound represented by the formula:

[ solution 78]

(in the formula, R^1c、R^21cAnd R^3cAs described above) of the compound (13c),

step (14c) is to oxidize compound (13c) to obtain a compound of formula (la):

[ solution 79]

(in the formula, R^1c、R^21cAnd R^3cAs described above) of the compound (14 c).

R^1cWhen the furan ring is contained in (b), the furan ring can be opened by an acid to convert into a dicarbonyl derivative, for example. Examples of the acid include acetic acid, hydrochloric acid, and p-toluenesulfonic acid, and among them, acetic acid is preferable.

In the step (11c), it is preferable that lithium and the chlorosilane compound are reacted in advance to obtain a siloxysithium compound, and then the siloxysithium compound is reacted with the compound (10c) to obtain the compound (11 c).

E^cRepresents a leaving group. Examples of the leaving group include t-butyldimethylsilyl (TBS), Triethylsilyl (TES), Triisopropylsilyl (TIPS), t-butyldiphenylsilyl (TBDPS), and benzyl (Bn).

As R^21cPreferably, it is a single bond or a linear or branched alkylene group having 1 or more carbon atoms.

Examples of the chlorosilane compound include

[ solution 80]

Any reaction in the step (11c) may be carried out in a solvent. The solvent is preferably an organic solvent, more preferably an aprotic polar solvent, and still more preferably an ether. Examples of the ether include ethyl methyl ether, diethyl ether, monoglyme (ethylene glycol dimethyl ether), diglyme (diethylene glycol dimethyl ether), triglyme (triethylene glycol dimethyl ether), tetrahydrofuran, tetraglyme (tetraethylene glycol dimethyl ether), crown ether (15-crown-5, 18-crown-6), and the like, and among them, tetrahydrofuran and diethyl ether are preferable.

The temperature of the reaction between lithium and the chlorosilane compound in step (11c) is preferably-78 to 100 ℃ and more preferably 10 to 40 ℃.

The reaction temperature of the siloxysithium compound and the compound (10c) in the step (11c) is preferably-100 to 0 ℃ and more preferably-80 to-50 ℃.

The pressure for the reaction between lithium and the chlorosilane compound in step (11c) is preferably 0.1 to 5MPa, more preferably 0.1 to 1 MPa.

The pressure for the reaction between the siloxysithium compound and the compound (10c) in the step (11c) is preferably 0.1 to 5MPa, more preferably 0.1 to 1 MPa.

The time for the reaction between lithium and the chlorosilane compound in step (11c) is preferably 0.1 to 72 hours, and more preferably 6 to 10 hours.

The reaction time of the siloxysithium compound and the compound (10c) in the step (11c) is preferably 0.1 to 72 hours, more preferably 1 to 2 hours.

In the step (12c), the ratio of the reaction between the compound (11c) and the olefin is preferably 1 to 2 moles, more preferably 1 to 1.1 moles, of the olefin based on 1 mole of the compound (11c) in view of improvement in yield and reduction in waste.

The reaction in the step (12c) may be carried out in a solvent in the presence of a thiazolium salt and a base.

Examples of the thiazolium salt include 3-ethyl-5- (2-hydroxyethyl) -4-methylthiazolium bromide, 3-benzyl-5- (2-hydroxyethyl) -4-methylthiazolium chloride, and the like.

Examples of the base include 1, 8-diazabicyclo [5.4.0] -7-undecene and triethylamine.

The solvent is preferably an organic solvent, more preferably an aprotic polar solvent, and further preferably an alcohol or an ether.

Examples of the alcohol include methanol, ethanol, 1-propanol, and isopropanol.

Examples of the ether include ethyl methyl ether, diethyl ether, monoglyme (ethylene glycol dimethyl ether), diglyme (diethylene glycol dimethyl ether), triglyme (triethylene glycol dimethyl ether), tetrahydrofuran, tetraglyme (tetraethylene glycol dimethyl ether), crown ether (15-crown-5, 18-crown-6), and the like, and among them, tetrahydrofuran and diethyl ether are preferable.

The temperature of the reaction in the step (12c) is preferably 40 to 60 ℃, more preferably 50 to 55 ℃.

The pressure of the reaction in the step (12c) is preferably 0.1 to 5MPa, more preferably 0.1 to 1 MPa.

The reaction time in the step (12c) is preferably 0.1 to 72 hours, more preferably 6 to 10 hours.

The leaving group elimination reaction in the step (13c) can be carried out by using a fluoride ion or an acid. Examples of the method for detaching a leaving group include: a method using hydrofluoric acid; method for producing amine complex using hydrogen fluoride such as pyridine nHF, triethylamine nHF and the likeA method; cesium fluoride, potassium fluoride, lithium fluoroborate (LiBF) are used ₄) A method of using an inorganic salt such as ammonium fluoride; a method using an organic salt such as tetrabutylammonium fluoride (TBAF).

The leaving group elimination reaction in the step (13c) may be carried out in a polar solvent. The solvent is preferably an organic solvent, more preferably an aprotic polar solvent, and still more preferably an ether.

Examples of the ether include ethyl methyl ether, diethyl ether, monoglyme (ethylene glycol dimethyl ether), diglyme (diethylene glycol dimethyl ether), triglyme (triethylene glycol dimethyl ether), tetrahydrofuran, tetraglyme (tetraethylene glycol dimethyl ether), crown ether (15-crown-5, 18-crown-6), and the like, and among them, tetrahydrofuran and diethyl ether are preferable.

The temperature of the reaction in the step (13c) is preferably 0 to 40 ℃ and more preferably 0 to 20 ℃.

The pressure of the reaction in the step (13c) is preferably 0.1 to 5MPa, more preferably 0.1 to 1 MPa.

The reaction time in the step (13c) is preferably 0.1 to 72 hours, more preferably 3 to 8 hours.

The oxidation in the step (14c) may be carried out in a solvent in the presence of sodium chlorite.

As the solvent, alcohols such as methanol, ethanol, 1-propanol, isopropanol, 1-butanol and tert-butanol, and water can be used. As the buffer, a disodium hydrogen phosphate solution can be used.

Compound (14c) can be contacted with a base to convert-COOH to a salt form. Examples of the base include sodium hydroxide, potassium hydroxide, lithium hydroxide, and ammonia, and an aqueous solution of ammonia is preferably used.

After completion of each step, the purity of the obtained compound can be improved by removing the solvent by distillation, or by performing distillation, purification, or the like.

The surfactant (c) can also be suitably produced by a production method comprising the step (21c), the step (22c) and the step (23c), wherein,

the step (21c) is a step of reacting:

[ solution 81]

(in the formula, R^3cAs mentioned above, R^22cIs a 1-valent organic radical, E^cIs a leaving group) with a ketone of formula (la):

[ solution 82]

(in the formula, R^1cAs mentioned above, R^23cIs a 1-valent organic group) to yield a carboxylic acid ester of the formula:

[ solution 83]

(in the formula, R^1c、R^3cAnd E^cAs mentioned above, R^24cA single bond or a 2-valent linking group),

step (22c) is a step of removing the leaving group of compound (21c) to obtain a compound represented by the formula:

[ solution 84]

(in the formula, R^1c、R^24cAnd R^3cAs described above) of the compound (22c),

step (23c) is to oxidize compound (22c) to give a compound of formula (la):

[ solution 85]

(in the formula, R^1c、R^24cAnd R^3cAs described above) of the compound (23 c).

R^1cWhen the furan ring is contained in (b), the furan ring can be opened by an acid to convert into a dicarbonyl derivative, for example. Examples of the acid include acetic acid, hydrochloric acid, and p-toluenesulfonic acid, and among them, acetic acid is preferable.

E^cRepresents a leaving group. Examples of the leaving group include t-butyldimethylsilyl (TBS), Triethylsilyl (TES), Triisopropylsilyl (TIPS), t-butyldiphenylsilyl (TBDPS), and benzyl (Bn).

As R^22cThe alkyl group is preferably a linear or branched alkyl group having 1 or more carbon atoms, and more preferably a methyl group.

As R^23cThe alkyl group is preferably a linear or branched alkyl group having 1 or more carbon atoms, and more preferably a methyl group.

As R^24cThe alkylene group is preferably a linear or branched alkylene group having 1 or more carbon atoms, and more preferably a methylene group (-CH)₂-)。

The reaction in the step (21c) may be carried out in a solvent in the presence of a base.

Examples of the base include sodium amide, sodium hydride, sodium methoxide, sodium ethoxide, and the like.

The solvent is preferably an organic solvent, more preferably an aprotic polar solvent, and further preferably an alcohol or an ether.

Examples of the alcohol include methanol, ethanol, 1-propanol, and isopropanol.

Examples of the ether include ethyl methyl ether, diethyl ether, monoglyme (ethylene glycol dimethyl ether), diglyme (diethylene glycol dimethyl ether), triglyme (triethylene glycol dimethyl ether), tetrahydrofuran, tetraglyme (tetraethylene glycol dimethyl ether), crown ether (15-crown-5, 18-crown-6), and the like, and tetrahydrofuran and diethyl ether are preferable.

The temperature of the reaction in the step (21c) is preferably 0 to 40 ℃ and more preferably 0 to 20 ℃.

The pressure of the reaction in the step (21c) is preferably 0.1 to 5MPa, more preferably 0.1 to 1 MPa.

The reaction time in the step (21c) is preferably 0.1 to 72 hours, more preferably 3 to 8 hours.

The leaving group elimination reaction in the step (22c) can be carried out by using a fluoride ion or an acid. Examples of the method for detaching a leaving group include: a method using hydrofluoric acid; a method using an amine complex of hydrogen fluoride such as pyridine nHF or triethylamine nHF; cesium fluoride, potassium fluoride, lithium fluoroborate (LiBF) are used₄) A method of using an inorganic salt such as ammonium fluoride; a method using an organic salt such as tetrabutylammonium fluoride (TBAF).

The leaving group elimination reaction in the step (22c) may be carried out in a solvent. The solvent is preferably an organic solvent, more preferably an aprotic polar solvent, and still more preferably an ether.

Examples of the ether include ethyl methyl ether, diethyl ether, monoglyme (ethylene glycol dimethyl ether), diglyme (diethylene glycol dimethyl ether), triglyme (triethylene glycol dimethyl ether), tetrahydrofuran, tetraglyme (tetraethylene glycol dimethyl ether), crown ether (15-crown-5, 18-crown-6), and the like, and among them, tetrahydrofuran and diethyl ether are preferable.

The temperature of the reaction in the step (22c) is preferably 0 to 40 ℃ and more preferably 0 to 20 ℃.

The pressure of the reaction in the step (22c) is preferably 0.1 to 5MPa, more preferably 0.1 to 1 MPa.

The reaction time in the step (22c) is preferably 0.1 to 72 hours, more preferably 3 to 8 hours.

The oxidation in the step (23c) may be carried out in a solvent in the presence of sodium chlorite.

As the solvent, alcohol and water can be used. As the buffer, a disodium hydrogen phosphate solution can be used.

Compound (23c) can be contacted with a base to convert-COOH into a salt form. Examples of the base include sodium hydroxide, potassium hydroxide, lithium hydroxide, and ammonia, and an aqueous solution of ammonia is preferably used.

After completion of each step, the purity of the obtained compound can be improved by removing the solvent by distillation, or by performing distillation, purification, or the like.

The surfactant (c) can also be suitably produced by a production method comprising the step (31c), the step (32c), the step (33c) and the step (34c),

the step (31c) is a step of reacting: y is^c-R^3c-CH₂-OE^c

(in the formula, R^3cAs described above, Y^cIs a halogen atom, E^cIs a leaving group) with a haloalkyl group of the formula:

[ solution 86]

(in the formula, R^1cAs described above) to give a compound of formula:

[ solution 87]

(in the formula, R^1c、R^3cAnd E^cAs described above) of the compound (31c),

step (32c) is to oxidize compound (31c) to obtain the compound of formula (II)

[ solution 88]

(in the formula, R^1c、R^3cAnd E^cAs described above) of the compound (32c),

step (33c) is a step of removing the leaving group of compound (32c) to obtain a compound represented by the formula:

[ solution 89]

(in the formula, R^1cAnd R^3cAs described above) of the compound (33c),

step (34c) is to oxidize compound (33c) to obtain a compound of formula (la):

[ solution 90]

(in the formula, R^1cAnd R^3cAs described above) of the compound (34 c).

R^1cWhen the furan ring is contained in (b), the furan ring can be opened by an acid to convert into a dicarbonyl derivative, for example. Examples of the acid include acetic acid, hydrochloric acid, and p-toluenesulfonic acid, and among them, acetic acid is preferable.

E^cRepresents a leaving group. Examples of the leaving group include t-butyldimethylsilyl (TBS), Triethylsilyl (TES), Triisopropylsilyl (TIPS), t-butyldiphenylsilyl (TBDPS), and benzyl (Bn).

In the step (31c), the ratio of the halogenated alkyl group to the lithium acetylide is preferably 1 to 2 moles, more preferably 1 to 1.2 moles, of the lithium acetylide to 1 mole of the halogenated alkyl group, in view of improvement of yield and reduction of waste.

The reaction in step (31c) may be carried out in a solvent. As the solvent, hexane is preferable.

The temperature of the reaction in the step (31c) is preferably-100 to-40 ℃ and more preferably-80 to-50 ℃.

The pressure of the reaction in the step (31c) is preferably 0.1 to 5MPa, more preferably 0.1 to 1 MPa.

The reaction time in the step (31c) is preferably 0.1 to 72 hours, more preferably 6 to 10 hours.

The oxidation in the step (32c) can be carried out as follows: will [ (Cn)^*)Ru^III(CF₃CO₂)₃]·H₂O (in the formula, Cn)^*Is represented by 1(NH) utilization of 4, 7-trimethyl-1, 4, 7-triazabicyclononane₄)₂Ce(NO₃)₆And trifluoroacetic acid treatment, sodium perchlorate is added to form a complex, and the oxidation is carried out in a nitrile solvent using the complex.

After the termination of the oxidation, the compound (32c) can be extracted by neutralizing with a base and using an organic solvent such as ether.

The temperature of the reaction in the step (32c) is preferably 30 to 100 ℃ and more preferably 40 to 90 ℃.

The pressure of the reaction in the step (32c) is preferably 0.1 to 5MPa, more preferably 0.1 to 1 MPa.

The reaction time in the step (32c) is preferably 0.1 to 72 hours, more preferably 3 to 8 hours.

The leaving group elimination reaction in the step (33c) can be carried out by using a fluoride ion or an acid. Examples of the method for detaching a leaving group include: a method using hydrofluoric acid; a method using an amine complex of hydrogen fluoride such as pyridine nHF or triethylamine nHF; cesium fluoride, potassium fluoride, lithium fluoroborate (LiBF) are used ₄) A method of using an inorganic salt such as ammonium fluoride; a method using an organic salt such as tetrabutylammonium fluoride (TBAF).

The leaving group elimination reaction in the step (33c) may be carried out in a solvent. The solvent is preferably an organic solvent, more preferably an aprotic polar solvent, and still more preferably an ether.

Examples of the ether include ethyl methyl ether, diethyl ether, monoglyme (ethylene glycol dimethyl ether), diglyme (diethylene glycol dimethyl ether), triglyme (triethylene glycol dimethyl ether), tetrahydrofuran, tetraglyme (tetraethylene glycol dimethyl ether), crown ether (15-crown-5, 18-crown-6), and the like, and among them, tetrahydrofuran and diethyl ether are preferable.

The temperature of the reaction in the step (33c) is preferably 0 to 40 ℃ and more preferably 0 to 20 ℃.

The pressure of the reaction in the step (33c) is preferably 0.1 to 5MPa, more preferably 0.1 to 1 MPa.

The reaction time in the step (33c) is preferably 0.1 to 72 hours, more preferably 3 to 8 hours.

The oxidation in the step (34c) may be carried out in a solvent in the presence of sodium chlorite.

As the solvent, alcohol and water can be used. As the buffer, a disodium hydrogen phosphate solution can be used.

Compound (34c) can be contacted with a base to convert-COOH to a salt form. Examples of the base include sodium hydroxide, potassium hydroxide, lithium hydroxide, and ammonia, and an aqueous solution of ammonia is preferably used.

After completion of each step, the purity of the obtained compound can be improved by removing the solvent by distillation, or by performing distillation, purification, or the like.

The surfactant (c) can also be suitably produced by a production method comprising the step (51c), the step (52c), the step (53c) and the step (54c), wherein,

the step (51c) is a step of reacting:

[ solution 91]

A divinylketone is disclosed having the formula:

[ solution 92]

The 2-methylfuran shown reacts to give the formula:

[ solution 93]

The step of preparing the compound (51c) shown below,

step (52c) is performed by reacting compound (51c) with a compound of formula (la):

[ solution 94]

The furan shown reacts to give the formula:

[ solution 95]

The step of preparing the compound (52c) shown below,

step (53c) is to heat compound (52c) in the presence of an acid, thereby obtaining formula (la):

[ solution 96]

The step of preparing the compound (53c) shown below,

step (54c) is to oxidize compound (53c) to give a compound of formula (la):

[ solution 97]

The step of preparing the compound (54 c).

In the step (51c), the reaction ratio of divinyl ketone to 2-methylfuran is preferably 0.5 to 1 mol, and more preferably 0.6 to 0.9 mol, based on 1 mol of divinyl ketone, in view of improvement in yield and reduction in waste.

The reaction in the step (51c) is preferably carried out in the presence of an acid. Examples of the acid include acetic acid, hydrochloric acid, and p-toluenesulfonic acid, and among them, acetic acid is preferable.

The amount of the acid used in the step (51c) is preferably 0.1 to 2 moles, more preferably 0.1 to 1 mole, based on 1 mole of the divinylketone, in view of improvement in yield and reduction in waste.

The reaction in the step (51c) may be carried out in a polar solvent. The solvent is preferably water or acetonitrile.

The temperature of the reaction in the step (51c) is preferably 20 to 100 ℃, more preferably 40 to 100 ℃.

The pressure of the reaction in the step (51c) is preferably 0.1 to 5MPa, more preferably 0.1 to 1 MPa.

The reaction time in the step (51c) is preferably 0.1 to 72 hours, more preferably 4 to 8 hours.

In the step (52c), the reaction ratio of the compound (51c) and furan is preferably 1 to 2 moles, more preferably 1 to 1.1 moles of furan to 1 mole of the compound (51c) in view of improvement of yield and reduction of waste.

The reaction in the step (52c) is preferably carried out in the presence of an acid. Examples of the acid include acetic acid, hydrochloric acid, and p-toluenesulfonic acid, and among them, acetic acid is preferable.

The amount of the acid used in the step (52c) is preferably 0.1 to 2 moles, more preferably 0.1 to 1 mole, based on 1 mole of the compound (51c), in view of improvement in yield and reduction in waste.

The reaction in the step (52c) may be carried out in a polar solvent. As the solvent, water is preferable.

The temperature of the reaction in the step (52c) is preferably 20 to 100 ℃, more preferably 40 to 100 ℃.

The pressure of the reaction in the step (52c) is preferably 0.1 to 5MPa, more preferably 0.1 to 1 MPa.

The reaction time in the step (52c) is preferably 0.1 to 72 hours, more preferably 4 to 8 hours.

In the step (53c), the compound (52c) is heated in the presence of an acid to open the furan ring.

The acid is preferably hydrochloric acid or sulfuric acid.

The reaction in the step (53c) may be carried out in a polar solvent. As the solvent, water is preferable.

The temperature of the reaction in the step (53c) is preferably 50 to 100 ℃, more preferably 70 to 100 ℃.

The pressure of the reaction in the step (53c) is preferably 0.1 to 5MPa, more preferably 0.1 to 1 MPa.

The reaction time in the step (53c) is preferably 0.1 to 72 hours, more preferably 1 to 12 hours.

The oxidation in the step (54c) may be carried out in a solvent in the presence of sodium chlorite.

As the solvent, t-butanol and water can be used. As the buffer, a disodium hydrogen phosphate solution can be used.

Compound (54c) may be contacted with a base to convert-COOH to a salt form. Examples of the base include sodium hydroxide, potassium hydroxide, lithium hydroxide, and ammonia, and an aqueous solution of ammonia is preferably used.

After completion of each step, the purity of the obtained compound can be improved by removing the solvent by distillation, or by performing distillation, purification, or the like.

The surfactant (c) can also be suitably produced by a production method comprising the step (61c) and the step (62c) wherein,

the step (61c) is a step of reacting:

[ solution 98]

(in the formula, R^1cAs mentioned above, R^21cIs a single bond or a 2-valent linking group) with an olefin of the formula:

[ solution 99]

(in the formula, Y^61cIs an alkyl ester group) to give an alkyne of the formula:

[ solution 100]

(in the formula, R^1c、R^21cAnd Y^61cAs described above) areA step of forming an object (61c),

the step (62c) is a step of allowing a base to act on the compound (61c) and then allowing an acid to act thereon to obtain a compound represented by the formula:

[ solution 101]

(in the formula, R^1cAnd R^21cAs described above) and a compound (62 c).

R^1cWhen the furan ring is contained in (b), the furan ring can be opened by an acid to convert into a dicarbonyl derivative, for example. Examples of the acid include acetic acid, hydrochloric acid, and p-toluenesulfonic acid, and among them, acetic acid is preferable.

As R^21cPreferably, it is a single bond or a linear or branched alkylene group having 1 or more carbon atoms.

In the step (61c), the ratio of the olefin to the alkyne is preferably 0.5 to 2 moles, more preferably 0.6 to 1.2 moles, of the olefin to 1 mole of the alkyne in view of improvement of yield and reduction of waste.

The reaction in the step (61c) is preferably carried out in the presence of a metal catalyst. Examples of the metal include ruthenium.

The amount of the metal catalyst used in the step (61c) is preferably 0.01 to 0.4 mol, more preferably 0.05 to 0.1 mol, based on 1 mol of the olefin, in view of improvement of yield and reduction of waste.

The reaction in the step (61c) may be carried out in a polar solvent. The solvent is preferably water, acetonitrile, dimethylacetamide or dimethylformamide.

The temperature of the reaction in the step (61c) is preferably 20 to 160 ℃ and more preferably 40 to 140 ℃.

The pressure of the reaction in the step (61c) is preferably 0.1 to 5MPa, more preferably 0.1 to 1 MPa.

The reaction time in the step (61c) is preferably 0.1 to 72 hours, more preferably 4 to 8 hours.

In the step (62c), the proportion of the base to be reacted with the compound (61c) is preferably 0.6 to 2 moles, more preferably 0.8 to 1.1 moles, based on 1 mole of the compound (61c), in view of improvement in yield and reduction in waste.

The amount of the acid used in the step (62c) is preferably 1.0 to 20.0 mol, more preferably 1.0 to 10.0 mol, based on 1 mol of the compound (61c), from the viewpoints of improvement in yield and reduction in waste.

The reaction in step (62c) may be carried out in a polar solvent. As the solvent, water is preferable.

The temperature of the reaction in the step (62c) is preferably 0 to 100 ℃, more preferably 20 to 100 ℃.

The pressure of the reaction in the step (62c) is preferably 0.1 to 5MPa, more preferably 0.1 to 1 MPa.

The reaction time in the step (62c) is preferably 0.1 to 72 hours, more preferably 4 to 8 hours.

Compound (62c) may be contacted with a base to convert-COOH to a salt form. Examples of the base include sodium hydroxide, potassium hydroxide, lithium hydroxide, and ammonia, and an aqueous solution of ammonia is preferably used.

After completion of each step, the purity of the obtained compound can be improved by removing the solvent by distillation, or by performing distillation, purification, or the like.

The surfactant (d) will be explained.

In the formula (d), R^1dIs a linear or branched alkyl group having 1 or more carbon atoms, which may have a substituent, or a cyclic alkyl group having 3 or more carbon atoms, which may have a substituent.

When the number of carbon atoms of the alkyl group is 3 or more, the alkyl group may contain a heterocyclic ring having a valence of 1 or 2, or may form a ring. The heterocyclic ring is preferably an unsaturated heterocyclic ring, more preferably an oxygen-containing unsaturated heterocyclic ring, and examples thereof include furan rings and the like. R ^1dIn the above formula, a 2-valent heterocyclic ring may be inserted between 2 carbon atoms, a 2-valent heterocyclic ring may be located at the terminal and bonded to — C (═ O) -, and a 1-valent heterocyclic ring may be located at the terminal of the alkyl group.

In the present specification, the "number of carbon atoms" of the alkyl group also includes the number of carbon atoms constituting the heterocyclic ring.

With respect to as R^1dThe substituent which the alkyl group may have is preferably a halogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, a cyclic alkyl group having 3 to 10 carbon atoms or a hydroxyl group, and particularly preferably a methyl group or an ethyl group.

As R^1dThe above alkyl group of (a) preferably does not contain a carbonyl group.

In the above alkyl groups, 75% or less of hydrogen atoms bonded to carbon atoms may be substituted with a halogen atom, 50% or less may be substituted with a halogen atom, and 25% or less may be substituted with a halogen atom, but a non-halogenated alkyl group containing no halogen atom such as a fluorine atom or a chlorine atom is preferable.

The above alkyl group preferably does not have any substituent.

As R^1dThe alkyl group is preferably a linear or branched alkyl group having 1 to 10 carbon atoms, which may or may not have a substituent, or a cyclic alkyl group having 3 to 10 carbon atoms, more preferably a linear or branched alkyl group having 1 to 10 carbon atoms, which may or may not include a carbonyl group, or a cyclic alkyl group having 3 to 10 carbon atoms, which may not include a carbonyl group, further preferably a linear or branched alkyl group having 1 to 10 carbon atoms, which may not have a substituent, further more preferably a linear or branched alkyl group having 1 to 3 carbon atoms, which may not have a substituent, and particularly preferably a methyl group (-CH) ₃) Or ethyl (-C)₂H₅) Most preferred is methyl (-CH)₃)。

In the formula (d), R^2dAnd R^4dIndependently is H or a substituent. More than 2R^2dAnd R^4dEach may be the same or different.

With respect to as R^2dAnd R^4dThe substituent(s) is preferably a halogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, a cyclic alkyl group having 3 to 10 carbon atoms, or a hydroxyl group, and particularly preferably a methyl group or an ethyl group.

As R^2dAnd R^4dUpper part ofThe alkyl group preferably does not contain a carbonyl group.

In the above alkyl groups, 75% or less of hydrogen atoms bonded to carbon atoms may be substituted with a halogen atom, 50% or less may be substituted with a halogen atom, and 25% or less may be substituted with a halogen atom, but a non-halogenated alkyl group containing no halogen atom such as a fluorine atom or a chlorine atom is preferable.

The above alkyl group preferably does not have any substituent.

With respect to as R^2dAnd R^4dThe alkyl group (C) is preferably a linear or branched alkyl group having 1 to 10 carbon atoms and not containing a carbonyl group or a cyclic alkyl group having 3 to 10 carbon atoms and not containing a carbonyl group, more preferably a linear or branched alkyl group having 1 to 10 carbon atoms and not containing a carbonyl group, further preferably a linear or branched alkyl group having 1 to 3 carbon atoms and not containing a substituent, and particularly preferably a methyl group (-CH) ₃) Or ethyl (-C)₂H₅)。

As R^2dAnd R^4dPreferably independently H or a linear or branched alkyl group having 1 to 10 carbon atoms and not containing a carbonyl group, more preferably H or a linear or branched alkyl group having 1 to 3 carbon atoms and not containing a substituent, and still more preferably H or a methyl group (-CH)₃) Or ethyl (-C)₂H₅) H is particularly preferred.

In the formula (d), R^3dIs an alkylene group having 1 to 10 carbon atoms, which may have a substituent. R^3dWhen there are 2 or more, they may be the same or different.

The alkylene group preferably does not contain a carbonyl group.

In the above alkylene group, 75% or less of hydrogen atoms bonded to carbon atoms may be substituted with a halogen atom, 50% or less may be substituted with a halogen atom, and 25% or less may be substituted with a halogen atom, but a non-halogenated alkyl group containing no halogen atom such as a fluorine atom or a chlorine atom is preferable.

The above alkylene group preferably does not have any substituent.

The alkylene group is preferably a linear or branched alkylene group having 1 to 10 carbon atoms, which may have a substituent, or a linear or branched alkylene group having a substituent, which may have a substituentA cyclic alkylene group having 3 to 10 carbon atoms and having no substituent, more preferably a linear or branched alkylene group having 1 to 10 carbon atoms and not containing a carbonyl group or a cyclic alkylene group having 3 to 10 carbon atoms and not containing a carbonyl group, still more preferably a linear or branched alkylene group having 1 to 10 carbon atoms and not containing a substituent, and further more preferably a methylene group (-CH) ₂-) ethylene (-C), ethylene (-C)₂H₄-) isopropylidene (-CH (CH)₃)CH₂-) or propylene (-C)₃H₆-)。

R^1d、R^2d、R^3dAnd R^4dAny two of which may be bonded to each other to form a ring.

In the formula (d), n is an integer of 1 or more. The number n is preferably an integer of 1 to 40, more preferably an integer of 1 to 30, and still more preferably an integer of 5 to 25.

In the formula (d), p and q are independently integers of 0 or more. P is preferably an integer of 0 to 10, more preferably 0 or 1. Q is preferably an integer of 0 to 10, more preferably an integer of 0 to 5.

The sum of n, p and q is preferably an integer of 6 or more. The sum of n, p and q is more preferably an integer of 8 or more. The total of n, p and q is preferably an integer of 60 or less, more preferably an integer of 50 or less, and still more preferably an integer of 40 or less.

In the formula (d), A^dis-SO₃X^dor-COOX^d(X^dIs H, a metal atom, NR^5d ₄Imidazolium with or without substituents, pyridinium with or without substituents or phosphonium with or without substituents, R^5dIs H or an organic group, which may be the same or different). As R^5dThe organic group in (1) is preferably an alkyl group. As R^5dPreferably, H or an organic group having 1 to 10 carbon atoms, more preferably H or an organic group having 1 to 4 carbon atoms, and further preferably H or an alkyl group having 1 to 4 carbon atoms. Examples of the metal atom include alkali metals (group 1), alkaline earth metals (group 2), and the like, and Na, K, and Li are preferable. X ^dMay be a metal atom or NR^5d ₄(R^5dAs described above).

As X^dPreferably H, alkali metal (group 1), alkaline earth metal (group 2) or NR^5d ₄For reasons of easy solubility in water, H, Na, K, Li or NH are more preferred₄Further, Na, K or NH is preferable for the reason of being more soluble in water₄Particularly preferred is Na or NH₄For reasons of easy removal, NH is most preferred₄。X^dIs NH₄In the case of the surfactant, the surfactant has excellent solubility in an aqueous medium, and a metal component is not likely to remain in PTFE or a final product.

In the formula (d), L is a single bond, -CO₂-B-*、-OCO-B-*、-CONR^6d-B-*、-NR^6dCO-B-, or-CO- (excluding-CO)₂-B-、-OCO-B-、-CONR^6d-B-、-NR^6dA carbonyl group contained in CO-B-), B is a single bond or an alkylene group having 1 to 10 carbon atoms and having or not having a substituent, R^6dH or an alkyl group having 1 to 4 carbon atoms, which may have a substituent. The number of carbon atoms of the alkylene group is more preferably 1 to 5. In addition, the above R^6dMore preferably H or methyl. Is represented by A in the formula^dOne side of the bond.

L is preferably a single bond.

The above surfactant is in¹The integral value of all peak intensities observed in a region of chemical shift 2.0 to 5.0ppm in the H-NMR spectrum is preferably 10 or more.

The above surfactant is in¹The integral value of all peak intensities observed in a region of chemical shift 2.0 to 5.0ppm in the H-NMR spectrum is preferably within the above range. In this case, the surfactant preferably has a ketone structure in the molecule.

In the surfactant, the integrated value is more preferably 15 or more, preferably 95 or less, more preferably 80 or less, and still more preferably 70 or less.

The integral value was measured at room temperature using a heavy water solvent. The amount of heavy water was 4.79 ppm.

Examples of the surfactant (d) include

CH₃C(O)CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂COOK、

CH₃C(O)CH₂CH₂CH₂CH₂CH₂CH₂CH₂COONa、

CH₃C(O)CH₂CH₂CH₂CH₂CH₂CH₂COONa、

CH₃C(O)CH₂CH₂CH₂CH₂CH₂COONa、

CH₃C(O)CH₂CH₂CH₂CH₂COONa、

CH₃C(O)CH₂CH₂CH₂COONa、

CH₃C(O)CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂COONa、

CH₃C(O)CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂COONa、

(CH₃)₃CC(O)CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂COONa、

(CH₃)₂CHC(O)CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂COONa、

(CH₂)₅CHC(O)CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂COONa、

CH₃CH₂C(O)CH₂CH₂CH₂CH₂CH₂CH₂CH₂COONa、

CH₃CH₂CH₂C(O)CH₂CH₂CH₂CH₂CH₂CH₂COONa、

CH₃CH₂CH₂CH₂C(O)CH₂CH₂CH₂CH₂CH₂COONa、

CH₃CH₂CH₂CH₂CH₂C(O)CH₂CH₂CH₂CH₂COONa、

CH₃CH₂CH₂CH₂CH₂CH₂C(O)CH₂CH₂CH₂COONa、

CH₃CH₂CH₂CH₂CH₂CH₂CH₂C(O)CH₂CH₂COONa、

CH₃CH₂CH₂CH₂CH₂CH₂CH₂CH₂C(O)CH₂COONa、

CH₃C(O)CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂OCH₂CH₂COONa、

CH₃C(O)CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂C(O)NHCH₂COOK、

CH₃C(O)CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂NHC(O)CH₂COOK、

CH₃C(O)CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂C(O)OCH₂COONa、

CH₃C(O)CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂OC(O)CH₂COONa、

CH₃C(O)CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂C(O)COONa、

CH₃C(O)CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂C(O)COOH、

CH₃C(O)CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂C(O)COOLi、

CH₃C(O)CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂C(O)COONH₄、

CH₃C(O)CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂C(O)COONa、CH₃C(O)CH₂CH₂CH₂CH₂CH₂CH₂CH₂C(CH₃)₂COOK、

CH₃C(O)CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂SO₃Na、

CH₃C(O)CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂SO₃Na、

CH₃C(O)CH₂CH₂CH₂CH₂CH₂CH₂CH₂SO₃Na、

CH₃C(O)CH₂CH₂CH₂CH₂CH₂CH₂SO₃Na、

CH₃C(O)CH₂CH₂CH₂CH₂CH₂SO₃Na、

CH₃C(O)CH₂CH₂CH₂CH₂SO₃Na、

CH₃C(O)CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂SO₃Na、

CH₃C(O)CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂SO₃Na、

CH₃C(O)CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂SO₃Na、

(CH₃)₃CC(O)CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂SO₃Na、

(CH₃)₂CHC(O)CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂SO₃Na、

(CH₂)₅CHC(O)CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂SO₃Na、

CH₃C(O)CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂SO₃Na、

CH₃C(O)CH₂CH₂CH₂CH₂CH₂CH₂CH₂SO₃Na、

CH₃C(O)CH₂CH₂CH₂CH₂CH₂CH₂SO₃Na、

CH₃C(O)CH₂CH₂CH₂CH₂CH₂SO₃Na、

CH₃C(O)CH₂CH₂CH₂CH₂SO₃Na、

CH₃C(O)CH₂CH₂CH₂SO₃Na、

CH₃C(O)CH₂CH₂SO₃Na、

CH₃C(O)CH₂SO₃Na、

CH₃C(O)CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂OCH₂CH₂CH₂SO₃Na、

CH₃C(O)CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂C(O)NHCH₂SO₃Na、

CH₃C(O)CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂NHC(O)CH₂SO₃Na、

CH₃C(O)CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂C(O)SO₃Na、

CH₃C(O)CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂C(O)OCH₂SO₃Na、

CH₃C(O)CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂OC(O)CH₂SO₃Na、

CH₃C(O)CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂SO₃H、

CH₃C(O)CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂SO₃K、

CH₃C(O)CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂SO₃Li、

CH₃C(O)CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂SO₃NH₄、

CH₃C(O)CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂C(CH₃)₂SO₃Na and the like.

The surfactant (d) is a novel compound, and can be produced, for example, by the production method described below.

The surfactant (d) can be suitably produced by a production method comprising the step (11d) of,

the step (11d) is a step of reacting a compound represented by the formula:

[ solution 102]

(in the formula, R^1d、R^2dAnd n is as described above)

The compound (10d) represented is represented by the following formula:

[ solution 103]

(in the formula, R^3dAs described above. L is a single bond, -CO₂-B-*、-OCO-B-*、-CONR^6d-B-*、-NR^6dCO-B-, or-CO- (excluding-CO)₂-B-、-OCO-B-、-CONR^6d-B-、-NR^6dCarbonyl group contained in CO-B-), B being a single bond or having or not having substitutionAn alkylene group having 1 to 10 carbon atoms, R^6dH or an alkyl group having 1 to 4 carbon atoms, which may have a substituent. Means and in formula-S (═ O)₂-bonded side) to yield the following formula:

[ solution 104]

(in the formula, R^1d～R^3dN and X^dAs described above. L is a single bond, -CO₂-B-*、-OCO-B-*、-CONR^6d-B-*、-NR^6dCO-B-, or-CO- (excluding-CO)₂-B-、-OCO-B-、-CONR^6d-B-、-NR^6dA carbonyl group contained in CO-B-), B is a single bond or an alkylene group having 1 to 10 carbon atoms and having or not having a substituent, R ^6dH or an alkyl group having 1 to 4 carbon atoms, which may have a substituent. is-OSO in the formula₃X^dThe side to which the bond is bonded) of the compound (11 d).

The reaction in the step (11d) may be carried out in the presence of a base.

Examples of the base include sodium hydride, sodium hydroxide, potassium hydroxide, and triethylamine. The base may be used in an amount of 0.5 to 20 mol based on 1 mol of the compound (10 d).

The reaction in the step (11d) may be carried out in a solvent.

The solvent is preferably an organic solvent, and more preferably an aprotic polar solvent. Examples of the organic solvent include ethers, aromatic compounds, nitriles, halogenated hydrocarbons, and the like.

Examples of the ether include diethyl ether, tetrahydrofuran, dioxane, diethylene glycol diethyl ether, and the like, and among them, diethyl ether and tetrahydrofuran are preferable.

The aromatic compound includes benzene, toluene, xylene, etc., and among them, benzene is preferable.

The nitrile includes acetonitrile, propionitrile, butyronitrile, isobutyronitrile, benzonitrile and the like, and among them, acetonitrile is preferable.

Examples of the halogenated hydrocarbon include dichloromethane, dichloroethane, chloroform, chlorobenzene, and o-dichlorobenzene, and dichloromethane and chloroform are preferable among them.

The temperature of the reaction in the step (11d) is preferably-78 to 150 ℃, more preferably-20 to 100 ℃.

The pressure of the reaction in the step (11d) is preferably 0 to 10MPa, more preferably 0 to 1.0 MPa.

The reaction time in the step (11d) is preferably 0.1 to 72 hours, more preferably 0.1 to 48 hours.

The surfactant (d) can also be suitably produced by a production method comprising the step (21d) of, among others,

the step (21d) is a step of reacting a compound represented by the formula:

[ solution 105]

(in the formula, R^1d～R^4dN, p and q are as described above. L is a single bond, -CO₂-B-*、-OCO-B-*、-CONR^6d-B-*、-NR^6dCO-B-, or-CO- (excluding-CO)₂-B-、-OCO-B-、-CONR^6d-B-、-NR^6dA carbonyl group contained in CO-B-), B is a single bond or an alkylene group having 1 to 10 carbon atoms and having or not having a substituent, R^6dH or an alkyl group having 1 to 4 carbon atoms, which may have a substituent. is-CH in the formula₂One side of-OH bond)

Oxidation of the compound (20d) shown gives the following formula:

[ solution 106]

(in the formula, R^1d～R^4dN, p, q and X^dAs described above. L is a single bond, -CO₂-B-*、-OCO-B-*、-CONR^6d-B-*、-NR^6dCO-B-, or-CO- (excluding-CO)₂-B-、-OCO-B-、-CONR^6d-B-、-NR^6dA carbonyl group contained in CO-B-), B is a single bond or an alkylene group having 1 to 10 carbon atoms and having or not having a substituent, R^6dH or an alkyl group having 1 to 4 carbon atoms, which may have a substituent. is-CH in the formula ₂-COOX^dOne side of the bond)

A step of preparing the compound (21 d).

The oxidation in the step (21d) can be carried out by allowing a nitrosating agent to act on the compound (20 d).

As the nitrosating agent, sodium nitrite, nitrososulfuric acid, isoamylnitrite, and the like can be used.

The nitrosating agent may be used in an amount of 0.5 to 10 mol based on 1 mol of the compound (20 d).

The oxidation in the step (21d) may be carried out in a solvent. As the solvent, trifluoroacetic acid, acetonitrile, or the like can be used.

The temperature of the oxidation in the step (21d) is preferably-78 to 200 ℃, more preferably-20 to 100 ℃.

The pressure for the oxidation in the step (21d) is preferably 0 to 10MPa, more preferably 0 to 1.0 MPa.

The time for oxidation in the step (21d) is preferably 0.1 to 72 hours, more preferably 0.1 to 24 hours.

The compound (10d) and the compound (20d) can be produced by a production method comprising the step (101d) and the step (102d),

the step (101d) is a step of reacting a compound represented by the formula:

R^11d-CH＝CH-Y^1d-OH

(in the formula, R^11dThe substituent(s) is (are) H, a linear or branched alkyl group having 1 or more carbon atoms with or without a substituent, or a cyclic alkyl group having 3 or more carbon atoms with or without a substituent, and when the number of carbon atoms is 3 or more, the substituent(s) may include a heterocyclic ring having 1 or 2 valences, or may form a ring. Y is ^1dIs- (CR)^2d ₂)_n-or- (CR)^2d ₂)_n-(OR^3d)_p-(CR^4d ₂)_q-L-CH₂-(R^2d～R^4dN, p and q are as described above. L is a single bond, -CO₂-B-*、-OCO-B-*、-CONR^6d-B-*、-NR^6dCO-B-, or-CO- (excluding-CO)₂-B-、-OCO-B-、-CONR^6d-B-、-NR^6dA carbonyl group contained in CO-B-), B is a single bond or an alkylene group having 1 to 10 carbon atoms and having or not having a substituent, R^6dH or an alkyl group having 1 to 4 carbon atoms, which may have a substituent. is-CH in the formula₂-one side of the bond)) to obtain the following formula:

[ solution 107]

(in the formula, R^11dAnd Y^1dAs described above) of the compound (101d),

the step (102d) is to oxidize the compound (101d) to obtain the following formula:

[ solution 108]

(in the formula, R^11dAnd Y^1dAs described above) of the compound (102 d).

As R^11dThe above alkyl group of (a) preferably does not contain a carbonyl group.

As R^11dIn the above alkyl groups, 75% or less of the hydrogen atoms bonded to the carbon atoms may be substituted with a halogen atom, 50% or less may be substituted with a halogen atom, and 25% or less may be substituted with a halogen atom, but a non-halogenated alkyl group containing no halogen atom such as a fluorine atom or a chlorine atom is preferable.

The above alkyl group preferably does not have any substituent.

As R^11dThe alkyl group is preferably H, a linear or branched alkyl group having 1 to 9 carbon atoms with or without a substituent, or a cyclic alkyl group having 3 to 9 carbon atoms with or without a substituent, more preferably H, a linear or branched alkyl group having 1 to 9 carbon atoms which does not include a carbonyl group, or a cyclic alkyl group having 3 to 9 carbon atoms which does not include a carbonyl group, still more preferably H, or a linear or branched alkyl group having 1 to 9 carbon atoms which does not include a substituent, and still more preferably H or a methyl group (-CH) ₃) Or ethyl (-C)₂H₅) Particularly preferred is H or methyl (-CH)₃) Most preferably, H.

The hydroxylation in the step (101d) can be carried out, for example, by the following method: (1d) a method of allowing iron (II) phthalocyanine (fe (pc)) and sodium borohydride to act on the compound (100d) in an oxygen atmosphere; (2d) reacting isopinocampheylborane (IpcBH)₂) A method in which the compound (100d) is allowed to act thereon, and then the obtained intermediate (dialkylboron) is oxidized.

In the method (1d), the amount of the iron (II) phthalocyanine may be a catalyst amount, and may be used in an amount of 0.001 to 1.2 mol based on 1 mol of the compound (100 d).

In the method (1d), sodium borohydride may be used in an amount of 0.5 to 20 mol based on 1 mol of the compound (100 d).

The reaction of process (1d) may be carried out in a solvent. The solvent is preferably an organic solvent, and examples thereof include ethers, halogenated hydrocarbons, aromatic hydrocarbons, nitriles, nitrogen-containing polar organic compounds, and the like.

Examples of the ether include diethyl ether, tetrahydrofuran, dioxane, diethylene glycol diethyl ether, and the like, and among them, diethyl ether and tetrahydrofuran are preferable.

Examples of the halogenated hydrocarbon include dichloromethane, dichloroethane, chloroform, chlorobenzene, and o-dichlorobenzene, and dichloromethane and chloroform are preferable among them.

The aromatic hydrocarbon includes benzene, toluene, xylene, etc., and among them, benzene and toluene are preferable.

The nitrile includes acetonitrile, propionitrile, butyronitrile, isobutyronitrile, benzonitrile and the like, and among them, acetonitrile is preferable.

Examples of the nitrogen-containing polar organic compound include N, N-dimethylformamide, N-dimethylacetamide, N-methyl-2-pyrrolidone, 1, 3-dimethyl-2-imidazolidinone, and the like, and among them, N-dimethylformamide, N-dimethylacetamide, and N-methyl-2-pyrrolidone are preferable.

The reaction temperature in the method (1d) is preferably-78 to 200 ℃ and more preferably 0 to 150 ℃.

The pressure for the reaction in the process (1d) is preferably 0 to 5.0MPa, more preferably 0.1 to 1.0 MPa.

The reaction time in the method (1d) is preferably 0.1 to 72 hours, more preferably 0.1 to 48 hours.

In the method (2d), isopinocampheylborane may be used in an amount of 1.0 to 10.0 mol based on 1 mol of the compound (100 d).

The reaction of the compound (100d) with isopinocampheylborane may be carried out in a solvent. The solvent is preferably an organic solvent, and examples thereof include ethers, halogenated hydrocarbons, aromatic hydrocarbons, and the like.

Examples of the ether include diethyl ether, tetrahydrofuran, dioxane, diethylene glycol diethyl ether, and the like, and among them, diethyl ether and tetrahydrofuran are preferable.

Examples of the halogenated hydrocarbon include dichloromethane, dichloroethane, chloroform, chlorobenzene, and o-dichlorobenzene, and dichloromethane and chloroform are preferable among them.

The aromatic hydrocarbon includes benzene, toluene, xylene, etc., and among them, benzene and toluene are preferable.

The reaction temperature of the compound (100d) with isopinocampheylborane is preferably-78 to 200 ℃ and more preferably 0 to 150 ℃.

The pressure for the reaction of the compound (100d) with isopinocampheylborane is preferably 0 to 5.0MPa, more preferably 0.1 to 1.0 MPa.

The reaction time of the compound (100d) with isopinocampheylborane is preferably 0.1 to 72 hours, more preferably 0.1 to 48 hours.

The oxidation in the method (2d) may be carried out by allowing an oxidizing agent to act on the intermediate. Examples of the oxidizing agent include hydrogen peroxide. The oxidizing agent may be used in an amount of 0.7 to 10 mol based on 1 mol of the intermediate.

The oxidation in process (2d) may be carried out in a solvent. Examples of the solvent include water, methanol, and ethanol, and among them, water is preferable.

The temperature for the oxidation in the method (2d) is preferably 0 to 100 ℃ and more preferably 0 to 80 ℃.

The pressure for the oxidation in the process (2d) is preferably 0 to 5.0MPa, more preferably 0.1 to 1.0 MPa.

The time for the oxidation in the method (2d) is preferably 0.1 to 72 hours, more preferably 0.1 to 48 hours.

In the step (102d), examples of the method for oxidizing the compound (101d) include: (a) using Jones reagent (CrO)₃/H₂SO₄) Method (jones oxidation); (b) methods using dess-martin periodinane (DMP) (dess-martin oxidation); (c) a method using pyridinium chlorochromate (PCC); (d) in NiCl₂A method of allowing a bleaching agent (about 5 to 6% aqueous solution of NaOCl) to act in the presence of a nickel compound; (e) in Al (CH)₃)₃、Al[OCH(CH₃)₂]₃And a method of allowing a hydrogen acceptor such as an aldehyde or a ketone to act in the presence of an aluminum catalyst (W-type oxidation).

The oxidation in the step (102d) may be carried out in a solvent. The solvent is preferably water or an organic solvent, and examples thereof include water, ketones, ethers, halogenated hydrocarbons, aromatic hydrocarbons, and nitriles.

Examples of the ketone include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, diacetone alcohol, and the like, and among them, acetone is preferable.

Examples of the ether include diethyl ether, tetrahydrofuran, dioxane, diethylene glycol diethyl ether, and the like, and among them, diethyl ether and tetrahydrofuran are preferable.

Examples of the halogenated hydrocarbon include dichloromethane, dichloroethane, chloroform, chlorobenzene, and o-dichlorobenzene, and dichloromethane and chloroform are preferable among them.

The aromatic hydrocarbon includes benzene, toluene, xylene, etc., and among them, benzene and toluene are preferable.

The nitrile includes acetonitrile, propionitrile, butyronitrile, isobutyronitrile, benzonitrile and the like, and among them, acetonitrile is preferable.

The temperature of the oxidation in the step (102d) is preferably-78 to 200 ℃ and can be suitably selected depending on the method used.

The pressure for the oxidation in the step (102d) is preferably 0 to 5.0MPa, and can be suitably selected according to the method used.

The time for oxidation in the step (102d) is preferably 0.1 to 72 hours, and can be appropriately selected depending on the method used.

The compound (10d) and the compound (20d) can be produced by a production method comprising the step (201d) of,

the step (201d) is a step of reacting a compound represented by the formula:

[ solution 109]

(in the formula, R^1dAnd Y^1dAs described above. R^101dIs an organic group) to give the following formula:

[ solution 110]

(in the formula, R^1dAnd Y^1dAs described above) of the compound (201 d).

As R^101dPreferably, the alkyl group has 1 to 20 carbon atoms. 2R^101dMay be the same or different.

The ozonolysis in step (201d) can be carried out by subjecting the compound (200d) to ozone treatment and then to a post-treatment with a reducing agent.

Ozone can be generated by silent discharge in oxygen.

Examples of the reducing agent used in the above-mentioned post-treatment include zinc, dimethyl sulfide, thiourea, phosphines, etc., and among them, phosphines are preferable.

The ozonolysis in step (201d) may be carried out in a solvent. The solvent is preferably water or an organic solvent, and examples thereof include water, alcohols, carboxylic acids, ethers, halogenated hydrocarbons, and aromatic hydrocarbons.

Examples of the alcohol include methanol, ethanol, 1-propanol, and isopropanol. Among them, methanol and ethanol are preferable.

Examples of the carboxylic acids include acetic acid and propionic acid. Among them, acetic acid is preferred.

Examples of the ether include diethyl ether, tetrahydrofuran, dioxane, diethylene glycol diethyl ether, and the like, and among them, diethyl ether and tetrahydrofuran are preferable.

Examples of the halogenated hydrocarbon include dichloromethane, dichloroethane, chloroform, chlorobenzene, and o-dichlorobenzene, and dichloromethane and chloroform are preferable among them.

The aromatic hydrocarbon includes benzene, toluene, xylene, etc., and among them, benzene and toluene are preferable.

The temperature for the ozonolysis in the step (201d) is preferably-78 to 200 ℃, more preferably 0 to 150 ℃.

The pressure for ozonolysis in step (201d) is preferably 0 to 5.0MPa, more preferably 0.1 to 1.0 MPa.

The time for ozonolysis in step (201d) is preferably 0.1 to 72 hours, more preferably 0.1 to 48 hours.

The compound (10d) and the compound (20d) can be produced by a production method comprising the step (301d), the step (302d) and the step (303d),

the step (301d) is a step of reacting a compound represented by the formula:

R^21d-CH＝CH-Y^1d-OH

(in the formula, Y^1dAs described above. R^21dIs H, a linear or branched alkyl group having 1 or more carbon atoms with or without a substituent, or a cyclic alkyl group having 3 or more carbon atoms with or without a substituent, in which case the number of carbon atoms is 3 or moreThe following compound (300d) which may contain a heterocyclic ring having a valence of 1 or 2 or may form a ring) is epoxidized to obtain the following formula:

[ solution 111]

(in the formula, R^21dAnd Y^1dAs described above) of the compound (301d),

the step (302d) is to react the compound (301d) with R^22d ₂CuLi(R^22dA linear or branched alkyl group having 1 or more carbon atoms, which may have a substituent, or a cyclic alkyl group having 3 or more carbon atoms, which may have a substituent, and which may contain a heterocyclic ring having 1 or 2 valences or may form a ring when the number of carbon atoms is 3 or more), to obtain the following formula:

[ solution 112]

(in the formula, R^21d、R^22dAnd Y^1dAs described above) of the compound (302d),

step (303d) is to oxidize compound (302d) to obtain the following formula:

[ solution 113]

(in the formula, R^21d、R^22dAnd Y^1dAs described above) of the compound (303 d).

As R^21dThe above alkyl group of (a) preferably does not contain a carbonyl group.

As R^21dIn the above alkyl group, 75% or less of hydrogen atoms bonded to carbon atoms may be substituted with halogen atoms, 50% or less may be substituted with halogen atoms,The alkyl group may be substituted by 25% or less of halogen atoms, but is preferably a non-halogenated alkyl group containing no halogen atom such as a fluorine atom or chlorine atom.

The above alkyl group preferably does not have any substituent.

As R^21dThe alkyl group is preferably H, a linear or branched alkyl group having 1 to 8 carbon atoms with or without a substituent, or a cyclic alkyl group having 3 to 8 carbon atoms with or without a substituent, more preferably H, a linear or branched alkyl group having 1 to 8 carbon atoms which does not include a carbonyl group, or a cyclic alkyl group having 3 to 8 carbon atoms which does not include a carbonyl group, still more preferably H, or a linear or branched alkyl group having 1 to 8 carbon atoms which does not include a substituent, and particularly preferably H or a methyl group (-CH)₃) Most preferably, H.

As R^22dThe above alkyl group of (a) preferably does not contain a carbonyl group.

As R^22dIn the above alkyl groups, 75% or less of the hydrogen atoms bonded to the carbon atoms may be substituted with a halogen atom, 50% or less may be substituted with a halogen atom, and 25% or less may be substituted with a halogen atom, but a non-halogenated alkyl group containing no halogen atom such as a fluorine atom or a chlorine atom is preferable.

The above alkyl group preferably does not have any substituent.

As R^22dThe alkyl group is preferably a linear or branched alkyl group having 1 to 9 carbon atoms, which may or may not have a substituent, or a cyclic alkyl group having 3 to 9 carbon atoms, more preferably a linear or branched alkyl group having 1 to 9 carbon atoms, which may or may not include a carbonyl group, or a cyclic alkyl group having 3 to 9 carbon atoms, which may not include a carbonyl group, even more preferably a linear or branched alkyl group having 1 to 9 carbon atoms, which may not have a substituent, and particularly preferably a methyl group (-CH)₃) Or ethyl (-C)₂H₅) Most preferred is methyl (-CH)₃)。

2R^22dMay be the same or different.

R^21dAnd R^22dThe total number of carbon atoms of (A) is preferably 1 to 7, more preferably 1 to 2, and most preferably 1.

The epoxidation in the step (301d) can be carried out by allowing an epoxidizing agent to act on the compound (300 d).

Examples of the epoxidizing agent include m-chloroperbenzoic acid (m-CPBA), perbenzoic acid, peracids such as hydrogen peroxide and t-butyl hydroperoxide, dimethyldioxirane and methyltrifluoromethyldioxirane, among which peracids are preferred and m-chloroperbenzoic acid is more preferred.

The epoxidizing agent may be used in an amount of 0.5 to 10.0 mol based on 1 mol of the compound (300 d).

The epoxidation in the step (301d) may be carried out in a solvent. The solvent is preferably an organic solvent, and examples thereof include ketones, ethers, halogenated hydrocarbons, aromatic hydrocarbons, nitriles, pyridine, nitrogen-containing polar organic compounds, and dimethyl sulfoxide, and among them, dichloromethane is preferable.

Examples of the ketone include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, diacetone alcohol, and the like, and among them, acetone is preferable.

Examples of the ether include diethyl ether, tetrahydrofuran, dioxane, diethylene glycol diethyl ether, and the like, and among them, diethyl ether and tetrahydrofuran are preferable.

Examples of the halogenated hydrocarbon include dichloromethane, dichloroethane, chloroform, chlorobenzene, and o-dichlorobenzene, and dichloromethane and chloroform are preferable among them.

The aromatic hydrocarbon includes benzene, toluene, xylene, etc., and among them, benzene and toluene are preferable.

The nitrile includes acetonitrile, propionitrile, butyronitrile, isobutyronitrile, benzonitrile and the like, and among them, acetonitrile is preferable.

Examples of the nitrogen-containing polar organic compound include N, N-dimethylformamide, N-dimethylacetamide, N-methyl-2-pyrrolidone, 1, 3-dimethyl-2-imidazolidinone, and the like, and among them, N-dimethylformamide, N-dimethylacetamide, and N-methyl-2-pyrrolidone are preferable.

The temperature of epoxidation in the step (301d) is preferably-78 to 200 ℃, more preferably-40 to 150 ℃.

The pressure for epoxidation in the step (301d) is preferably 0 to 5.0MPa, more preferably 0.1 to 1.0 MPa.

The time for the epoxidation in the step (301d) is preferably 0.1 to 72 hours, more preferably 0.1 to 48 hours.

In the step (302d), the lithium dialkylcopper may be used in an amount of 0.5 to 10.0 mol based on 1 mol of the compound (301 d).

The reaction in the step (302d) may be carried out in a solvent. The solvent is preferably an organic solvent, and examples thereof include ethers, halogenated hydrocarbons, aromatic hydrocarbons, and the like.

Examples of the ether include diethyl ether, tetrahydrofuran, dioxane, diethylene glycol diethyl ether, and the like, and among them, diethyl ether and tetrahydrofuran are preferable.

Examples of the halogenated hydrocarbon include dichloromethane, dichloroethane, chloroform, chlorobenzene, and o-dichlorobenzene, and dichloromethane and chloroform are preferable among them.

The aromatic hydrocarbon includes benzene, toluene, xylene, etc., and among them, benzene and toluene are preferable.

The temperature of the reaction in the step (302d) is preferably-78 to 200 ℃ and more preferably-40 to 150 ℃.

The pressure of the reaction in the step (302d) is preferably 0 to 5.0MPa, more preferably 0.1 to 1.0 MPa.

The reaction time in the step (302d) is preferably 0.1 to 72 hours, more preferably 0.1 to 48 hours.

In the step (303d), examples of a method for oxidizing the compound (302d) include: (a) using Jones reagent (CrO)₃/H₂SO₄) Method (jones oxidation); (b) methods using dess-martin periodinane (DMP) (dess-martin oxidation); (c) a method using pyridinium chlorochromate (PCC); (d) in NiCl₂A method of allowing a bleaching agent (about 5 to 6% aqueous solution of NaOCl) to act in the presence of a nickel compound; (e) in Al (CH)₃)₃、Al[OCH(CH₃)₂]₃And a method of allowing a hydrogen acceptor such as an aldehyde or a ketone to act in the presence of an aluminum catalyst (W-type oxidation).

The oxidation in the step (303d) may be carried out in a solvent. The solvent is preferably water or an organic solvent, and examples thereof include water, ketones, alcohols, ethers, halogenated hydrocarbons, aromatic hydrocarbons, and nitriles.

Examples of the ketone include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, diacetone alcohol, and the like, and among them, acetone is preferable.

Examples of the alcohol include methanol, ethanol, 1-propanol, and isopropanol. Among them, methanol and ethanol are preferable.

Examples of the ether include diethyl ether, tetrahydrofuran, dioxane, diethylene glycol diethyl ether, and the like, and among them, diethyl ether and tetrahydrofuran are preferable.

Examples of the halogenated hydrocarbon include dichloromethane, dichloroethane, chloroform, chlorobenzene, and o-dichlorobenzene, and dichloromethane and chloroform are preferable among them.

The aromatic hydrocarbon includes benzene, toluene, xylene, etc., and among them, benzene and toluene are preferable.

The nitrile includes acetonitrile, propionitrile, butyronitrile, isobutyronitrile, benzonitrile and the like, and among them, acetonitrile is preferable.

The temperature of the oxidation in the step (303d) is preferably-78 to 200 ℃, and may be suitably selected depending on the method used.

The pressure for the oxidation in the step (303d) is preferably 0 to 5.0MPa, and can be appropriately selected depending on the method used.

The time for oxidation in the step (303d) is preferably 0.1 to 72 hours, and can be appropriately selected depending on the method used.

The compound (10d) and the compound (20d) can be produced by a production method comprising the step (401d) of,

the step (401d) is a step of reacting a compound represented by the formula:

R^11d-CH＝CH-Y^1d-OH

(in the formula, R^11dAnd Y^1dAs described above) to give the following formula:

[ chemical formula 114]

(in the formula, R^11dAnd Y^1dAs described above).

The oxidation in the step (401d) can be carried out by allowing an oxidizing agent to act on the compound (100d) in the presence of water and a palladium compound.

Examples of the oxidizing agent include monovalent or divalent copper salts such as copper chloride, copper acetate, copper cyanide and copper trifluoromethanesulfonate, iron salts such as iron chloride, iron acetate, iron cyanide, iron trifluoromethanesulfonate and iron hexacyanoferrate, benzoquinones such as 1, 4-benzoquinone, 2, 3-dichloro-5, 6-dicyano-1, 4-benzoquinone, tetrachloro-1, 2-benzoquinone and tetrachloro-1, 4-benzoquinone, H₂O₂、MnO₂、KMnO₄、RuO₄Meta-chloroperbenzoic acid, oxygen, etc. Among them, copper salts, iron salts and benzoquinones are preferable, and copper chloride, iron chloride and 1, 4-benzoquinone are more preferable.

The oxidizing agent may be used in an amount of 0.001 to 10 mol based on 1 mol of the compound (100 d).

The water may be used in an amount of 0.5 to 1000 mol based on 1 mol of the compound (100 d).

The palladium compound may be palladium dichloride. The amount of the palladium compound may be a catalyst amount, and may be used in an amount of 0.0001 to 1.0 mol based on 1 mol of the compound (100 d).

The oxidation in the step (401d) may be carried out in a solvent. Examples of the solvent include water, esters, aliphatic hydrocarbons, aromatic hydrocarbons, alcohols, carboxylic acids, ethers, halogenated hydrocarbons, nitrogen-containing polar organic compounds, nitriles, dimethyl sulfoxide, and sulfolane.

Examples of the ester include ethyl acetate, butyl acetate, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate (PGMEA; also known as 1-methoxy-2-acetoxypropane), and ethyl acetate is preferable.

Examples of the aliphatic hydrocarbon include hexane, cyclohexane, heptane, octane, nonane, decane, undecane, dodecane, mineral spirits, and the like, and cyclohexane and heptane are preferable among them.

The aromatic hydrocarbon includes benzene, toluene, xylene, etc., and among them, benzene and toluene are preferable.

Examples of the alcohol include methanol, ethanol, 1-propanol, and isopropanol.

Examples of the carboxylic acids include acetic acid and propionic acid. Among them, acetic acid is preferred.

Examples of the ether include diethyl ether, tetrahydrofuran, dioxane, diethylene glycol diethyl ether, and the like, and among them, diethyl ether and tetrahydrofuran are preferable.

Examples of the halogenated hydrocarbon include dichloromethane, dichloroethane, chloroform, chlorobenzene, and o-dichlorobenzene, and dichloromethane and chloroform are preferable among them.

Examples of the nitrogen-containing polar organic compound include N, N-dimethylformamide, N-dimethylacetamide, N-methyl-2-pyrrolidone, 1, 3-dimethyl-2-imidazolidinone, and the like, and among them, N-dimethylformamide, N-dimethylacetamide, and N-methyl-2-pyrrolidone are preferable.

The nitrile includes acetonitrile, propionitrile, butyronitrile, isobutyronitrile, benzonitrile and the like, and among them, acetonitrile is preferable.

The temperature of the oxidation in the step (401d) is preferably-78 to 200 ℃, more preferably-20 to 150 ℃.

The pressure for the oxidation in the step (401d) is preferably 0 to 10MPa, more preferably 0.1 to 5.0 MPa.

The time for oxidation in the step (401d) is preferably 0.1 to 72 hours, more preferably 0.1 to 48 hours.

The surfactant (d) can also be produced by a production method comprising the step (31d) of,

the step (31d) is a step of reacting a compound represented by the formula:

R^11d-CH＝CH-(CR^2d ₂)n-(OR^3d)_p-(CR^4d ₂)_q-L-COOX^d

(in the formula, R^2d～R^4d、R^11dN, p, q and X^dAs described above. L is a single bond, -CO₂-B-*、-OCO-B-*、-CONR^6d-B-*、-NR^6dCO-B-, or-CO- (excluding-CO)₂-B-、-OCO-B-、-CONR^6d-B-、-NR^6dA carbonyl group contained in CO-B-), B is a single bond or an alkylene group having 1 to 10 carbon atoms and having or not having a substituent, R^6dH or an alkyl group having 1 to 4 carbon atoms, which may have a substituent. The alkylene group preferably has 1 to 5 carbon atoms. In addition, the above R ^6dMore preferably H or methyl. is-COOX in the formula^dBonded side) to yield the following formula:

[ solution 115]

(R^2d～R^4d、L、R^11dN, p, q and X^dAs described above) of the compound (31 d).

The oxidation in the step (31d) can be carried out by allowing an oxidizing agent to act on the compound (30d) in the presence of water and a palladium compound, and the same conditions as those for the oxidation in the step (401d) can be employed.

In any of the above-mentioned production methods, after completion of each step, the purity of the obtained compound can be improved by removing the solvent by distillation, or by performing distillation, purification, or the like. In addition, the resulting compound is-SO₃H. X-COOH or the like^dIn the case of the compound of H, these groups can be converted into a salt form by contacting with a base such as sodium carbonate or ammonia.

The surfactant (e) will be explained.

In the formula (e), R^1e～R^5eRepresents H or a monovalent substituent, wherein R^1eAnd R^3eRepresents the general formula: -Y^e-R^6eA group shown, R^2eAnd R^5eRepresents the general formula: -X^e-A^eA group of the formula: -Y^e-R^6eThe groups shown. R^1e～R^5eAny two of which may be bonded to each other to form a ring.

With respect to as R^1eThe substituent which the alkyl group may have is preferably a halogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, a cyclic alkyl group having 3 to 10 carbon atoms or a hydroxyl group, and particularly preferably a methyl group or an ethyl group.

As R^1eThe above alkyl group of (a) preferably does not contain a carbonyl group.

In the above alkyl groups, 75% or less of hydrogen atoms bonded to carbon atoms may be substituted with a halogen atom, 50% or less may be substituted with a halogen atom, and 25% or less may be substituted with a halogen atom, but a non-halogenated alkyl group containing no halogen atom such as a fluorine atom or a chlorine atom is preferable.

The above alkyl group preferably does not have any substituent.

As R^1eThe alkyl group is preferably a linear or branched alkyl group having 1 to 10 carbon atoms, which may or may not have a substituent, or a cyclic alkyl group having 3 to 10 carbon atoms, more preferably a linear or branched alkyl group having 1 to 10 carbon atoms, which may or may not include a carbonyl group, or a cyclic alkyl group having 3 to 10 carbon atoms, which may not include a carbonyl group, further preferably a linear or branched alkyl group having 1 to 10 carbon atoms, which may not have a substituent, further more preferably a linear or branched alkyl group having 1 to 3 carbon atoms, which may not have a substituent, and particularly preferably a methyl group (-CH)₃) Or ethyl (-C)₂H₅) Most preferred is methyl (-CH)₃)。

As monovalent substituents, preference is given to those of the formula: -Y^e-R^6eA group represented by the general formula: -X^e-A^eA group represented by, -H, C with or without a substituent _1-20Alkyl, -NH of₂、-NHR^9e(R^9eIs an organic radical), -OH, -COOR^9e(R^9eIs an organic group) OR-OR^9e(R^9eIs an organic group). The number of carbon atoms of the alkyl group is preferably 1 to 10.

As R^9ePreferably C_1-10Alkyl or C_1-10Alkylcarbonyl of (a), more preferably C_1-4Alkyl or C_1-4An alkylcarbonyl group of (a).

In the formula, X^eIdentical or different at each occurrence and represents a 2-valent linking group or bond.

R^6eX does not contain any one of carbonyl group, ester group, amide group and sulfonyl group^ePreferred is a 2-valent linking group comprising at least one selected from the group consisting of a carbonyl group, an ester group, an amide group and a sulfonyl group.

As X^ePreferably comprising a compound selected from the group consisting of-CO-, -S (═ O)₂-、-O-、-COO-、-OCO-、-S(＝O)₂-O-、-O-S(＝O)₂-、-CONR^8e-and-NR^8eA 2-valent linking group of at least one bond of the group consisting of CO-, C_1-10Alkylene groups or a bond of (a). R^8eRepresents H or an organic group.

As R^8eThe organic group in (1) is preferably an alkyl group. As R^8ePreferably H or C_1-10More preferably H or C_1-4Further preferably H or C_1-4The alkyl group of (1) is more preferably H.

In the formula (e), A^eIdentical or different at each occurrence and denotes-COOM^e、-SO₃M^eor-OSO₃M^e(M^eIs H, a metal atom, NR^7e ₄Imidazolium with or without substituents, pyridinium with or without substituents or phosphonium with or without substituents, R ^7eIs H or an organic group. 4R^7eMay be the same or different). In the formula (e), A^eis-COOM^eIs one of the preferred modes.

As R^7eThe organic group in (1) is preferably an alkyl group. As R^7ePreferably H or C_1-10More preferably H or C_1-4Further preferably H or C_1-4Alkyl group of (1).

Examples of the metal atom include alkali metals (group 1), alkaline earth metals (group 2), and the like, and Na, K, and Li are preferable.

As M^ePreferably H, a metal atom or NR^7e ₄More preferably H, alkali metal (group 1), alkaline earth metal (group 2) or NR^7e ₄Further, H, Na, K, Li or NH is preferable₄Further more preferably Na, K or NH₄Particularly preferred is Na or NH₄Most preferably NH₄。

In the formula (e), Y^eIdentical or different at each occurrence and represents a residue selected from the group consisting of-S (═ O)₂-、-O-、-COO-、-OCO-、-CONR^8e-and-NR^8e2-valent linking groups or bonds in the group consisting of CO-, R^8eRepresents H or an organic group.

As Y^ePreferably a bond selected from the group consisting of-O-, -COO-, -OCO-, -CONR^8e-and-NR^8eA 2-valent linking group in the group consisting of CO-, more preferably a binding bond, a 2-valent linking group selected from the group consisting of-COO-and-OCO-.

As R^8eThe organic group in (1) is preferably an alkyl group. As R^8ePreferably H or C_1-10More preferably H or C _1-4Further preferably H or C_1-4The alkyl group of (1) is more preferably H.

In the formula (e), R^6eThe alkyl group having 2 or more carbon atoms, which may contain at least one group selected from the group consisting of a carbonyl group, an ester group, an amide group and a sulfonyl group, may be the same or different at each occurrence. R is as defined above^6eThe number of carbon atoms of the organic group(s) is preferably 2 to 20, more preferably 2 to 10.

R^6eThe alkyl group of (a) may contain 1 or 2 or more of at least one selected from the group consisting of a carbonyl group, an ester group, an amide group and a sulfonyl group between carbon-carbon atoms, but these groups are not contained at the terminal of the above alkyl group. R is as defined above^6eIn the alkyl group (b), 75% or less of hydrogen atoms bonded to carbon atoms may be substituted with a halogen atom, 50% or less may be substituted with a halogen atom, and 25% or less may be substituted with a halogen atom, but a non-halogenated alkyl group containing no halogen atom such as a fluorine atom or a chlorine atom is preferable.

AsR^6ePreference is given to

A compound of the general formula: -R^10e-CO-R^11eThe group shown,

A compound of the general formula: -R^10e-COO-R^11eThe group shown,

A compound of the general formula: -R^11eThe group shown,

A compound of the general formula: -R^10e-NR^8eCO-R^11eThe group shown, or

A compound of the general formula: -R^10e-CONR^8e-R^11eA group shown

(in the formula, R^8eRepresents H or an organic group. R^10eIs alkylene, R^11eAlkyl with or without substituents).

As R^6eMore preferred is the general formula: -R^10e-CO-R^11eThe groups shown.

As R^8eThe organic group in (1) is preferably an alkyl group. As R^8ePreferably H or C_1-10More preferably H or C_1-4Further preferably H or C_1-4The alkyl group of (1) is more preferably H.

R^10eThe number of carbon atoms of the alkylene group(s) is preferably 1 or more, more preferably 3 or more, preferably 20 or less, more preferably 12 or less, further preferably 10 or less, and particularly preferably 8 or less. In addition, R^10eThe alkylene group (B) preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and further preferably 3 to 10 carbon atoms.

R^11eThe alkyl group (C) may have 1 to 20 carbon atoms, preferably 1 to 15 carbon atoms, more preferably 1 to 12 carbon atoms, still more preferably 1 to 10 carbon atoms, yet more preferably 1 to 8 carbon atoms, particularly preferably 1 to 6 carbon atoms, yet more preferably 1 to 3 carbon atoms, particularly preferably 1 or 2 carbon atoms, and most preferably 1 carbon atom. In addition, the above R^11eThe alkyl group (b) preferably consists only of a primary carbon, a secondary carbon and a tertiary carbon, and particularly preferably consists only of a primary carbon and a secondary carbon. I.e. as R^11eMethyl, ethyl, n-propyl and isopropyl are preferred, and methyl is particularly preferred.

In the formula (e), R^2eAnd R^5eAt least one of which is of the general formula: -X^e-A^eThe group shown, and the A^eis-COOM^eIs also one of the preferred modes.

As the surfactant (e), a compound represented by the general formula (e-1), a compound represented by the general formula (e-2) or a compound represented by the general formula (e-3) is preferable, and a compound represented by the general formula (e-1) or a compound represented by the general formula (e-2) is more preferable.

General formula (e-1):

[ solution 116]

(in the formula, R^3e～R^6e、X^e、A^eAnd Y^eAs described above. )

General formula (e-2):

[ solution 117]

(in the formula, R^4e～R^6e、X^e、A^eAnd Y^eAs described above. )

General formula (e-3):

[ chemical formula 118]

(in the formula, R^2e、R^4e～R^6e、X^e、A^eAnd Y^eAs described above. )

As a general formula: -X^e-A^eThe radicals indicated are preferred

-COOM^e、

-R^12eCOOM^e、

-SO₃M^e、

-OSO₃M^e、

-R^12eSO₃M^e、

-R^12eOSO₃M^e、

-OCO-R^12e-COOM^e、

-OCO-R^12e-SO₃M^e、

-OCO-R^12e-OSO₃M^e、

-COO-R^12e-COOM^e、

-COO-R^12e-SO₃M^e、

-COO-R^12e-OSO₃M^e、

-CONR^8e-R^12e-COOM^e、

-CONR^8e-R^12e-SO₃M^e、

-CONR^8e-R^12e-OSO₃M^e、

-NR^8eCO-R^12e-COOM^e、

-NR^8eCO-R^12e-SO₃M^e、

-NR^8eCO-R^12e-OSO₃M^e、

-OS(＝O)₂-R^12e-COOM^e、

-OS(＝O)₂-R^12e-SO₃M^eOr is or

-OS(＝O)₂-R^12e-OSO₃M^e

(in the formula, R^8eAnd M^eAs described above. R^12eIs C_1-10Alkylene groups of (ii).

R is as defined above^12eThe alkylene group of (2) may have 75% or less of hydrogen atoms bonded to carbon atoms substituted with halogen atoms, 50% or less of hydrogen atoms substituted with halogen atoms, and 25% or less of hydrogen atoms substituted with halogen atoms, but is preferably a non-halogenated alkylene group containing no halogen atom such as a fluorine atom or chlorine atom.

As a general formula: -Y^e-R^6eShown inRadicals, preferably

A compound of the general formula: -R^10e-CO-R^11eThe group shown,

A compound of the general formula: -OCO-R^10e-CO-R^11eThe group shown,

A compound of the general formula: -COO-R^10e-CO-R^11eThe group shown,

A compound of the general formula: -OCO-R^10e-COO-R^11eThe group shown,

A compound of the general formula: -COO-R^11eA group shown by the group shown,

A compound of the general formula: -NR^8eCO-R^10e-CO-R^11eThe group shown, or

A compound of the general formula: -CONR^8e-R^10e-NR^8eCO-R^11eA group shown

(in the formula, R^8e、R^10eAnd R^11eAs described above).

In the formula, as R^4eAnd R^5ePreferably independently H or C_1-4Alkyl group of (1).

R is as defined above^4eAnd R^5eIn the alkyl group (b), 75% or less of hydrogen atoms bonded to carbon atoms may be substituted with a halogen atom, 50% or less may be substituted with a halogen atom, and 25% or less may be substituted with a halogen atom, but a non-halogenated alkyl group containing no halogen atom such as a fluorine atom or a chlorine atom is preferable.

As R in the general formula (e-1)^3ePreferably H or C with or without substituents_1-20More preferably H or C having no substituent_1-20The alkyl group of (3) is more preferably H.

R is as defined above^3eIn the alkyl group (b), 75% or less of hydrogen atoms bonded to carbon atoms may be substituted with a halogen atom, 50% or less may be substituted with a halogen atom, and 25% or less may be substituted with a halogen atom, but a non-halogenated alkyl group containing no halogen atom such as a fluorine atom or a chlorine atom is preferable.

As R in the general formula (e-3)^2ePreferably H, OH or C with or without substituents_1-20More preferably H, OH or C having no substituent_1-20Further, the alkyl group of (1) is preferably H or OH.

R is as defined above^2eIn the alkyl group (b), 75% or less of hydrogen atoms bonded to carbon atoms may be substituted with a halogen atom, 50% or less may be substituted with a halogen atom, and 25% or less may be substituted with a halogen atom, but a non-halogenated alkyl group containing no halogen atom such as a fluorine atom or a chlorine atom is preferable.

The surfactant (e) can be produced by a known production method.

The specific hydrocarbon surfactant is also preferably a carboxylic acid type hydrocarbon surfactant. The carboxylic acid type hydrocarbon surfactant is not limited as long as it has a carboxyl group (-COOH) or a group in which a hydrogen atom of the carboxyl group is substituted with an inorganic cation (for example, a metal atom, ammonium, or the like), and, for example, among the specific hydrocarbon surfactants, a hydrocarbon surfactant having a group in which a hydrogen atom of the carboxyl group or a group in which a hydrogen atom of the carboxyl group is substituted with an inorganic cation can be used.

The carboxylic acid type hydrocarbon surfactant is preferably at least one selected from the group consisting of the surfactant (c) represented by the formula (c) and the surfactant (d) represented by the formula (d), and has a group in which a carboxyl group (-COOH) or a hydrogen atom of the carboxyl group is substituted with an inorganic cation (for example, a metal atom, ammonium, or the like).

The PTFE of the present invention can be efficiently produced by using at least one of the above-mentioned specific hydrocarbon surfactants. The PTFE of the present invention can be produced by using 2 or more kinds of the specific hydrocarbon surfactants at the same time, and can be produced by using a compound having a surface-active ability other than the specific hydrocarbon surfactants as long as it is a volatile substance or a substance that may remain in a molded article or the like made of PTFE.

As the other compounds having surface-active ability, for example, those described in Japanese patent laid-open Nos. 2013-542308, 2013-542309 and 2013-542310 can be used.

Other compounds having surface-active ability may be surfactants having a hydrophilic part and a hydrophobic part on the same molecule, such as hydrocarbon-based surfactants. They may be cationic, nonionic or anionic.

Cationic surfactants generally have a positively charged hydrophilic moiety such as an alkylated ammonium halide, e.g., an alkylated ammonium bromide, and a hydrophobic moiety such as a long chain fatty acid.

Anionic surfactants generally have a hydrophilic portion such as carboxylate, sulfonate or sulfate, and a hydrophobic portion such as alkyl as a long-chain hydrocarbon portion.

Nonionic surfactants generally do not contain charged groups and have a hydrophobic portion that is a long chain hydrocarbon. The hydrophilic portion of the nonionic surfactant contains a water-soluble functional group such as a vinyl ether chain derived from polymerization with ethylene oxide.

Examples of nonionic surfactants:

polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, polyoxyethylene sorbitan alkyl esters, glycerol esters, and derivatives thereof.

Specific examples of polyoxyethylene alkyl ethers: polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene behenyl ether, and the like.

Specific examples of polyoxyethylene alkylphenyl ethers: polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether, and the like.

Specific examples of polyoxyethylene alkyl esters: polyethylene glycol monolaurate, polyethylene glycol monooleate, polyethylene glycol monostearate, and the like.

Specific examples of sorbitan alkyl esters: polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan monooleate, and the like.

Specific examples of polyoxyethylene sorbitan alkyl esters: polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, and the like.

Specific examples of glycerides: glyceryl monotetradecanoate, glyceryl monostearate, glyceryl monooleate, and the like.

Specific examples of the above derivatives: polyoxyethylene alkylamines, polyoxyethylene alkylphenyl-formaldehyde condensates, polyoxyethylene alkyl ether phosphates, and the like.

The ethers and esters may have an HLB value of 10 to 18.

Examples of the nonionic hydrocarbon surfactant include Triton (registered trademark), Triton (registered trademark) X series (X15, X45, X100, etc.), Tergitol (registered trademark) 15-S series, Tergitol (registered trademark) TMN series (TMN-6, TMN-10, TMN-100, etc.), Tergitol (registered trademark) L series, Pluronic (registered trademark) R series (31R1, 17R2, 10R5, 25R4(m to 22, n to 23), and Iconol (registered trademark) TDA series (TDA-6, TDA-9, TDA-10) manufactured by Dow Chemical Company.

Examples of the anionic hydrocarbon surfactant include Versatic (registered trademark) 10 manufactured by Resolution Performance Products, and Avanel S series (S-70, S-74, etc.) manufactured by BASF.

Examples of the other compounds having surface-active ability include compounds represented by the formula R-L-M (wherein R represents a linear or branched alkyl group having 1 or more carbon atoms with or without a substituent or a cyclic alkyl group having 3 or more carbon atoms with or without a substituent, and when the number of carbon atoms is 3 or more, a heterocyclic ring having 1 or 2 valences may be included or a ring may be formed; L represents-ArSO₃ ^-、-SO₃ ^-、-SO₄-、-PO₃ ^-or-COO^-M is H, a metal atom, NR ⁵ ₄(R⁵Which may be the same or different, is H or an organic group), an imidazolium with or without a substituent, a pyridinium with or without a substituent, or a phosphonium with or without a substituent. -ArSO₃ ^-Aryl sulfonate) as a surfactant. R⁵Preferably H or an organic group having 1 to 10 carbon atoms, and more preferably H or an organic group having 1 to 4 carbon atoms.

Specifically, there may be mentioned CH represented by lauric acid₃-(CH₂)_nL-M (wherein n is an integer of 6 to 17, and L and M are the same as described above).

A mixture of a substance in which R is an alkyl group having 12 to 16 carbon atoms and L-M is a sulfate or Sodium Dodecyl Sulfate (SDS) may also be used.

As other compounds having surface-active ability, there may be mentioned compounds represented by the formula R⁶(-L-M)₂(in the formula, R⁶The alkylene group may be a linear or branched alkylene group having 1 or more carbon atoms, which may have a substituent, or a cyclic alkylene group having 3 or more carbon atoms, which may have a substituent, and may contain a heterocyclic ring having 1 or 2 valences when the number of carbon atoms is 3 or more, or may form a ring. L is-ArSO₃ ^-、-SO₃ ^-、-SO₄-、-PO₃ ^-or-COO^-M is H, a metal atom, NR⁵ ₄Imidazolium with or without substituents, pyridinium with or without substituents or phosphonium with or without substituents, R ⁵Is H or an organic radical, -ArSO₃ ^-Aryl sulfonate) as a surfactant.

As other compounds having surface-active ability, there may be mentioned compounds represented by the formula R⁷(-L-M)₃(in the formula, R⁷The alkylene group may be a linear or branched alkylene group having 1 or more carbon atoms, which may have a substituent, or a cyclic alkylene group having 3 or more carbon atoms, which may have a substituent, and may contain a heterocyclic ring having 1 or 2 valences or may form a ring when the number of carbon atoms is 3 or more. L is-ArSO₃ ^-、-SO₃ ^-、-SO₄ ^-、-PO₃ ^-or-COO^-M is H, a metal atom, NR⁵ ₄Imidazolium with or without substituents, pyridinium with or without substituents or phosphonium with or without substituents, R⁵Is H or an organic group. -ArSO₃ ^-Aryl sulfonates) are listed as anionic surfactantsA surfactant.

Examples of the siloxane hydrocarbon surfactant include those described in Silicone Surfactants, R.M. Hill, Marcel Dekker, Inc., ISBN: 0-8247-00104. The structure of siloxane surfactants contains well-defined hydrophobic and hydrophilic portions. The hydrophobic moiety comprises 1 or more dihydrocarbylsiloxane units, where the substituents on the silicon atoms are entirely hydrocarbons.

These siloxane surfactants can also be considered as hydrocarbon surfactants in the sense that, in the case where the carbon atom of the hydrocarbon group can be substituted with a halogen such as fluorine, it is completely substituted with a hydrogen atom, i.e., the monovalent substituent on the carbon atom of the hydrocarbon group is hydrogen.

The hydrophilic moiety of the siloxane hydrocarbon surfactant may include 1 or more polar moieties containing ionic groups, such as sulfate ester, sulfonate ester, phosphonate ester, phosphate ester, carboxylate ester, carbonate ester, sulfosuccinate ester, taurate (in the form of free acid, salt, or ester), phosphine oxide, betaine polyol, and quaternary ammonium salt. The ionic hydrophobic moiety may also comprise ionically functionalized siloxane grafts.

Examples of such silicone hydrocarbon surfactants include polydimethylsiloxane-graft- (meth) acrylate, polydimethylsiloxane-graft-polyacrylate, and polydimethylsiloxane-grafted quaternary amine.

The polar portion of the hydrophilic portion of the siloxane surfactant may comprise: polyethers such as Polyoxyethylene (PEO) and mixed polyoxyethylene/oxypropylene polyethers (PEO/PPO); monosaccharides and disaccharides; and a nonionic group formed from a water-soluble heterocyclic ring such as pyrrolidone. The ratio of ethylene oxide to propylene oxide (EO/PO) can be varied in the mixed polyoxyethylene/oxypropylene polyethers.

The hydrophilic portion of the siloxane hydrocarbon surfactant may also comprise a combination of ionic and nonionic moieties. Examples of such moieties include polyethers or polyols functionalized with ionic ends or randomly. Preferred in the practice of the present invention are silicones having a nonionic moiety, i.e., nonionic silicone hydrocarbon-based surfactants.

The arrangement of the hydrophobic and hydrophilic portions of the structure of the silicone hydrocarbon surfactant may take the form of a diblock polymer (AB), a triblock polymer (ABA) (here, "B" represents the siloxane portion of the molecule), or a multiblock polymer. Alternatively, the siloxane hydrocarbon-based surfactant may comprise a graft polymer.

Siloxane hydrocarbon surfactants are also disclosed in U.S. Pat. No. 6,841,616.

Examples of the anionic hydrocarbon surfactant for the siloxane matrix include Noveon (registered trademark) manufactured by Lubrizol Advanced Materials, Inc., and SilSense available from Consumer Specialties^TMPE-100Silicone、SilSense^TMCA-1Silicone, and the like.

Examples of the anionic hydrocarbon surfactant include a sulfosuccinate surfactant Lankropol (registered trademark) K8300 manufactured by Akzo Nobel Surface Chemistry LLC.

Examples of the sulfosuccinate surfactant include diisodecyl sulfosuccinate Na salt, (Emulsogen (registered trademark) SB10 manufactured by Clariant corporation), diisotridecyl sulfosuccinate Na salt (Polirol (registered trademark) TR/LNA manufactured by Cesapini Chemicals, Inc.), and the like.

Other compounds having surface-active ability include a polyFox (registered trademark) surfactant (PolyFox) manufactured by Omnova Solutions, Inc^TMPF-156A、PolyFox^TMPF-136A, etc.).

As the other compound having a surface-active ability, an anionic hydrocarbon surfactant is preferable. As the anionic hydrocarbon surfactant, the above-mentioned compounds can be used, and for example, the following hydrocarbon surfactants can be suitably used.

Examples of the anionic hydrocarbon surfactant include the following formula (α):

R¹⁰⁰-COOM (α)

(in the formula, R¹⁰⁰To comprise1-valent organic group of 1 or more carbon atoms. M is H, a metal atom, NR¹⁰¹ ₄Imidazolium with or without substituents, pyridinium with or without substituents or phosphonium with or without substituents, R¹⁰¹H or an organic group, which may be the same or different). As R ¹⁰¹The organic group of (2) is preferably an alkyl group. As R¹⁰¹Preferably, H or an organic group having 1 to 10 carbon atoms, more preferably H or an organic group having 1 to 4 carbon atoms, and further preferably H or an alkyl group having 1 to 4 carbon atoms.

From the aspect of surface-active ability, R¹⁰⁰The number of carbon atoms of (b) is preferably 2 or more, more preferably 3 or more. In addition, from the aspect of water solubility, R¹⁰⁰The number of carbon atoms of (b) is preferably 29 or less, more preferably 23 or less.

Examples of the metal atom of M include alkali metals (group 1), alkaline earth metals (group 2), and the like, and Na, K, and Li are preferable. M is preferably H, a metal atom or NR¹⁰¹ ₄More preferably H, alkali metal (group 1), alkaline earth metal (group 2) or NR¹⁰¹ ₄Further, H, Na, K, Li or NH is preferable₄Further more preferably Na, K or NH₄Particularly preferred is Na or NH₄Most preferably NH₄。

The compound (. alpha.) may be represented by R¹⁰²-COOM (wherein R¹⁰²The alkyl group may be a linear or branched alkyl, alkenyl, alkylene or alkenylene group having 1 or more carbon atoms which may have a substituent, or a cyclic alkyl, alkenyl, alkylene or alkenylene group having 3 or more carbon atoms which may have a substituent, and may contain an ether bond. When the number of carbon atoms is 3 or more, a heterocyclic ring having a valence of 1 or 2 may be included, or a ring may be formed. M is the same as above).

Specifically, the group consisting of CH₃-(CH₂)_n-COOM (wherein n is an integer of 2 to 28, and M is the same as above).

From the viewpoint of emulsion stability, the compound (α) may contain no carbonyl group (excluding a carbonyl group in a carboxyl group).

As the hydrocarbon-containing surfactant not containing a carbonyl group, for example, the following formula (B) can be preferably exemplified:

R¹⁰³-COO-M (B)

(in the formula, R¹⁰³Is an alkyl group, alkenyl group, alkylene group or alkenylene group having 6 to 17 carbon atoms, which may contain an ether bond. M is H, a metal atom, NR¹⁰¹ ₄An imidazolium with or without a substituent, a pyridinium with or without a substituent, or a phosphonium with or without a substituent. R¹⁰¹Identical or different, is H or an organic group).

In the above formula (B), R¹⁰³Preferably an alkyl or alkenyl group (which may contain ether groups). R is as defined above¹⁰³The alkyl group or alkenyl group in (1) may be linear or branched. R is as defined above¹⁰³The number of carbon atoms of (2) is not limited, and is, for example, 2 to 29.

When the alkyl group is linear, R¹⁰³The number of carbon atoms of (A) is preferably 3 to 29, more preferably 5 to 23. When the alkyl group is branched, R¹⁰³The number of carbon atoms of (A) is preferably 5 to 35, more preferably 11 to 23.

When the alkenyl group is linear, R¹⁰³The number of carbon atoms of (A) is preferably 2 to 29, more preferably 9 to 23. When the alkenyl group is branched, R¹⁰³The number of carbon atoms of (A) is preferably 2 to 29, more preferably 9 to 23.

Examples of the alkyl group and the alkenyl group include a methyl group, an ethyl group, an isobutyl group, a tert-butyl group, and a vinyl group.

Examples of other compounds having surface-active ability include butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, lauric acid, myristic acid, pentadecanoic acid, palmitic acid, palmitoleic acid, heptadecanoic acid, stearic acid, oleic acid, vaccenic acid, linoleic acid, (9,12,15) -linolenic acid, (6,9,12) linolenic acid, elaeostearic acid, arachidic acid, 8, 11-eicosadienoic acid, eicosatrienoic acid, arachidonic acid, behenic acid, lignoceric acid, nervonic acid, cerotic acid, montanic acid, melissic acid, crotonic acid, myristoleic acid, palmitoleic acid, cis-6-hexadecenoic acid, oleic acid, elaidic acid, vaccenic acid, gadoleic acid, eicosenoic acid, erucic acid, nervonic acid, linoleic acid, eicosadienoic acid, docosenoic acid, pinolenic acid, Beta-eleostearic acid, eicosatrienoic acid, dihomo-gamma-linolenic acid, eicosatrienoic acid, stearidonic acid, arachidonic acid, eicosatetraenoic acid, docosatetraenoic acid, octadecapentaenoic acid, eicosapentaenoic acid, docosapentaenoic acid, sardine acid, tetracosapentaenoic acid, docosahexaenoic acid, herring acid, and salts thereof.

Particularly, at least one selected from the group consisting of lauric acid, capric acid, myristic acid, pentadecanoic acid, palmitic acid, and salts thereof is preferable.

Examples of the salt include a metal atom having a carboxyl group and a hydrogen atom of the formula M, NR¹¹ ₄The salt of imidazolium, pyridinium, or phosphonium is not particularly limited.

Examples of the anionic hydrocarbon surfactant include the following formula (1-0A):

[ solution 119]

(in the formula, R^1A～R^5AIs H, a 1-valent hydrocarbyl group that may contain an ester group between carbon-carbon atoms, or a compound of the formula: -X^A-A is a group represented by. However, R^2AAnd R^5ARepresents the general formula: -X^A-A is a group represented by.

X^AIdentical or different at each occurrence and is a 2-valent hydrocarbyl group or a bond;

a is identical or different on each occurrence and is-COOM (M is H, a metal atom, NR)⁷ ₄Imidazolium with or without substituents, with or without substituentsOr a substituted or unsubstituted phosphonium of (A), R⁷Is H or an organic group);

R^1A～R^5Aany two of which may be bonded to each other to form a ring), and the like.

In the general formula (1-0A), in R^1A～R^5AIn the above formula, the number of carbon atoms of the 1-valent hydrocarbon group which may contain an ester group between carbon-carbon atoms is preferably 1 to 50, more preferably 5 to 20. R^1A～R^5AAny two of which may be bonded to each other to form a ring. The 1-valent hydrocarbon group which may contain an ester group between carbon and carbon atoms is preferably an alkyl group.

In the formula, X^AIn the (2) -valent hydrocarbon group, the number of carbon atoms is preferably 1 to 50, more preferably 5 to 20. Examples of the 2-valent hydrocarbon group include an alkylene group and an alkanediyl group, and an alkylene group is preferable.

In the general formula (1-0A), R^2AAnd R^5AAny of the above is preferably of the general formula: -X^AA group represented by-A, more preferably R^2AIs represented by the general formula: -X^A-A is a group represented by.

In the general formula (1-0A), R is a preferable embodiment^2AIs represented by the general formula: -X^AA group represented by-A, R^1A、R^3A、R^4AAnd R^5AIn the form of H. In this case, X^APreferably a bond or an alkylene group having 1 to 5 carbon atoms.

In the general formula (1-0A), the following is also preferable: r^2AIs represented by the general formula: -X^AA group represented by-A, R^1AAnd R^3Ais-Y^A-R⁶A group shown, Y^AIs the same or different at each occurrence and is-COO-, -OCO-, or a bond, R⁶Each occurrence of the alkyl group is the same or different and is an alkyl group having 2 or more carbon atoms. In this case, R ^4AAnd R^5APreferably H.

Examples of the hydrocarbon-based surfactant represented by the general formula (1-0A) include glutaric acid or a salt thereof, adipic acid or a salt thereof, pimelic acid or a salt thereof, suberic acid or a salt thereof, azelaic acid or a salt thereof, sebacic acid or a salt thereof, and the like.

The aliphatic carboxylic acid type hydrocarbon surfactant represented by the general formula (1-0A) may be a double-chain double hydrophilic group type synthetic surfactant, and examples of the Gemini type surfactant include Gemini Surf (kyoto fat and oil co., ltd.), gemmurf α 142 (c 12 lauryl), gemmurf α 102 (c 10), and gemmurf α 182 (c 14).

Even when the specific hydrocarbon surfactant is not used, the PTFE of the present invention can be obtained by a production method including the following polymerization step: in the presence of a hydrocarbon surfactant and a polymerization initiator, tetrafluoroethylene alone or tetrafluoroethylene and a modifying monomer copolymerizable with the tetrafluoroethylene are polymerized in an aqueous medium having a pH of 4.0 or more to obtain PTFE.

Conventionally, since a polymerization initiator exhibiting acidity is used in a polymerization step for producing PTFE, the pH of an aqueous medium used for polymerization is less than 4.0. As a result of intensive studies, the present inventors have unexpectedly found that when the pH of an aqueous medium used in polymerization is 4.0 or more, the stability of polymerization is improved and PTFE having a high molecular weight can be produced.

In the above production method, tetrafluoroethylene alone or tetrafluoroethylene and a modifying monomer copolymerizable with the tetrafluoroethylene are polymerized in an aqueous medium having a pH of 4.0 or more. The pH may be 4.0 or more, preferably more than 4.0, more preferably 4.5 or more, further preferably 5.0 or more, further preferably 5.5 or more, particularly preferably 6.0 or more, particularly preferably 6.5 or more, particularly preferably 7.0 or more, particularly preferably 7.5 or more, and particularly preferably 8.0 or more. The upper limit of the pH is not particularly limited, and may be, for example, 13.0 or less. From the viewpoint of corrosion of the polymerization reactor, it is preferably 12.0 or less, more preferably 11.5 or less, and still more preferably 11.0 or less.

The pH can be measured by a pH meter.

In the above-mentioned production method, the method for adjusting the pH of the aqueous medium to 4.0 or more is not particularly limited, and for example, an alkaline aqueous solution, an aqueous dispersion exhibiting alkalinity, or a pH adjuster may be used to adjust the pH to 4.0 or more.

In addition, even when a polymerization initiator that exhibits acidity when dissolved in an aqueous medium is used, the pH can be adjusted to 4.0 or more by further adding an alkali compound such as sodium hydroxide. The alkali compound is any compound which is soluble in water and ionized to generate OH ^-Examples of the compound (4) include hydroxides of alkali metals such as sodium hydroxide and potassium hydroxide; hydroxides of alkaline earth metals; ammonia; amines, etc., are not particularly limited. The polymerization step may include a step of adding an alkali compound to the aqueous medium.

The above-mentioned production method may be such that the pH of the aqueous medium is 4.0 or more throughout the polymerization step. The pH may be set to 4.0 or more in the middle of the polymerization step, or may be set to 4.0 or more in the latter half of the polymerization step. In addition, the pH may be set to 4.0 or more in the middle stage and the latter half of the polymerization step.

For example, in the polymerization step, the pH of the aqueous medium is preferably 4.0 or more at a polymer solid content concentration of 3 mass% or more. In other words, the production method includes a polymerization step of polymerizing tetrafluoroethylene alone or tetrafluoroethylene and a modifying monomer copolymerizable with tetrafluoroethylene in an aqueous medium in the presence of a hydrocarbon surfactant and a polymerization initiator to obtain PTFE, and the aqueous medium preferably has a pH of 4.0 or more at a polymer solid content concentration of 3 mass% or more. The aqueous medium preferably has a pH of 4.0 or more at a polymer solid content concentration of 5% by mass or more, more preferably has a pH of 4.0 or more at a polymer solid content concentration of 8% by mass or more, even more preferably has a pH of 4.0 or more at a polymer solid content concentration of 10% by mass or more, particularly preferably has a pH of 4.0 or more at a polymer solid content concentration of 15% by mass or more, particularly preferably has a pH of 4.0 or more at a polymer solid content concentration of 18% by mass or more, more preferably has a pH of 4.0 or more at 20% by mass or more, and even more preferably has a pH of 4.0 or more at 25% by mass or more.

In the polymerization step, the pH of the aqueous medium is preferably maintained at 4.0 or more from the time when the polymer solid content concentration is 25% by mass to the end of polymerization, more preferably at 4.0 or more from the time when the polymer solid content concentration reaches 20% by mass to the end of polymerization, still more preferably at 4.0 or more from the time when the polymer solid content reaches 18% by mass to the end of polymerization, yet more preferably at 4.0 or more from the time when the polymer solid content reaches 15% by mass to the end of polymerization, particularly preferably at 4.0 or more from the time when the polymer solid content reaches 10% by mass to the end of polymerization, particularly preferably at 4.0 or more from the time when the polymer solid content reaches 8% by mass to the end of polymerization, more preferably at 4.0 or more from the time when the polymer solid content reaches 5% by mass to the end of polymerization, further preferably, the pH of the aqueous medium is maintained at 4.0 or more from the time when the pH reaches 3 mass% to the end of polymerization.

In addition, in the polymerization step, it is preferable that the pH of the aqueous medium is 4.0 or more when the polymer solid content concentration is less than 15% by mass. In the polymerization step, the pH of the aqueous medium is more preferably 4.0 or more at a polymer solid content concentration of 3 mass% or more and less than 15 mass%, more preferably 4.0 or more at a polymer solid content concentration of 5 mass% or more and less than 15 mass%, still more preferably 4.0 or more at a polymer solid content concentration of 8 mass% or more and less than 15 mass%, and yet still more preferably 4.0 or more at a polymer solid content concentration of 10 mass% or more and less than 15 mass%.

In the polymerization step, the pH of the aqueous medium is preferably maintained at 4.0 or more, more preferably at 4.0 or more, even more preferably at 5% by mass or more and 15% by mass, and even more preferably at 4.0 or more, at a polymer solid content concentration of 10% by mass or more and 15% by mass.

The pH of the aqueous medium is preferably more than 4.0, more preferably 4.5 or more, further preferably 5.0 or more, further preferably 5.5 or more, particularly preferably 6.0 or more, particularly preferably 6.5 or more, more preferably 7.0 or more, further preferably 7.5 or more, and further preferably 8.0 or more in any case.

In the polymerization step, the pH of the aqueous medium is preferably 4.0 or more during 60% or more (preferably 70% or more, more preferably 80% or more, more preferably 90% or more, even more preferably 95% or more, still more preferably 99% or more, and particularly preferably 100%) from the time when the polymerization starts to the time when the polymer solid content concentration is 3% by mass (preferably 5% by mass, more preferably 8% by mass, even more preferably 10% by mass, even more preferably 15% by mass, still even more preferably 18% by mass, still even more preferably 20% by mass, and particularly preferably 25% by mass).

In the polymerization step, the pH of the aqueous medium is preferably 4.0 or more during 60% or more (preferably 70% or more, more preferably 80% or more, further preferably 90% or more, further preferably 95% or more, further preferably 99% or more, and particularly preferably 100%) from the time when the polymer solid content concentration is 10% by mass (preferably 8% by mass, more preferably 5% by mass, further preferably 3% by mass, and even more preferably the start of polymerization) to the time when the polymer solid content concentration is 15% by mass.

In the polymerization step, the pH of the aqueous medium is preferably 4.0 or more during 60% or more (preferably 70% or more, more preferably 80% or more, further preferably 90% or more, further preferably 95% or more, still further preferably 99% or more, and particularly preferably 100%) from the time when the polymer solid content concentration is 15% by mass to the time when the polymer solid content concentration is 18% by mass (preferably 20% by mass, and more preferably 25% by mass).

In the polymerization step, the pH of the aqueous medium is preferably 4.0 or more during a period from a time point when the polymer solid content concentration is 25 mass% (preferably 20 mass, more preferably 18 mass%, further preferably 15 mass%, further preferably 10 mass%, still further preferably 8 mass%, particularly preferably 5 mass%, further preferably 3 mass%, further preferably polymerization start) to 60% or more (preferably 70% or more, more preferably 80% or more, further preferably 90% or more, further preferably 95% or more, more preferably 99% or more, particularly preferably 100%) before the polymerization termination time.

The pH of the aqueous medium is preferably more than 4.0, more preferably 4.5 or more, further preferably 5.0 or more, further preferably 5.5 or more, particularly preferably 6.0 or more, particularly preferably 6.5 or more, more preferably 7.0 or more, further preferably 7.5 or more, and further preferably 8.0 or more in any case.

In the above production method, the hydrocarbon surfactant is preferably an anionic hydrocarbon surfactant, and more preferably a carboxylic acid type hydrocarbon surfactant. The anionic hydrocarbon surfactant and the carboxylic acid type hydrocarbon surfactant are not particularly limited, and for example, the compound (α) exemplified in the above-mentioned other compounds having surface-active ability, and the like can be suitably used.

Even when the specific hydrocarbon surfactant is not used, the PTFE of the present invention comprises the following polymerization step: PTFE is obtained by polymerizing tetrafluoroethylene alone or tetrafluoroethylene and a modifying monomer copolymerizable with the tetrafluoroethylene in an aqueous medium in the presence of an anionic hydrocarbon surfactant containing a salt of the hydrocarbon surfactant and a polymerization initiator. In other words, at least a part of the anionic hydrocarbon surfactant in the polymerization step is in the form of a salt.

As a result of intensive studies, the present inventors have unexpectedly found that when an anionic hydrocarbon surfactant is contained in a salt of an anionic hydrocarbon surfactant, the stability of polymerization is improved and PTFE having a large molecular weight can be produced.

The anionic hydrocarbon surfactant is as described below.

It can be confirmed by measuring the electrical conductivity that the anionic hydrocarbon surfactant contains a salt of the hydrocarbon surfactant.

In the above production method, the concentration of the salt of the anionic hydrocarbon surfactant in the anionic hydrocarbon surfactant is preferably 50% by mass or more, more preferably 60% by mass or more, further preferably 70% by mass or more, further preferably 80% by mass or more, particularly preferably 90% by mass or more, and particularly preferably 95% by mass or more, based on the total mass of the anionic hydrocarbon surfactant.

The ratio of the above salts can be determined by the solution concentration and the conductivity.

In the above production method, the hydrocarbon surfactant is more preferably a carboxylic acid type hydrocarbon surfactant.

In the salt of the anionic hydrocarbon surfactant, the cation (excluding hydrogen atom) replacing the hydrogen atom of the acid is, for example, a metal atom, NR ^y ₄(R^yEach of which may be the same or different, is H or an organic group), an imidazolium with or without a substituent, a pyridinium with or without a substituent, or a phosphonium with or without a substituent. R is as defined above^yPreferably H or an alkyl group, more preferably H or an alkyl group having 1 to 10 carbon atoms, and still more preferably H or an alkyl group having 1 to 4 carbon atoms.

As the cation in the salt of an anionic hydrocarbon surfactant, a metal atom or NR is preferable^y ₄More preferably NR^y ₄Further, NH is preferable₄。

Since the conductivity greatly changes due to the influence of temperature, the sample liquid temperature was kept at 25 ℃ using a constant temperature bath, and the conductivity was measured similarly to the temperature of the cell of the pH meter.

In the above production method, the polymerization step is preferably carried out in the absence of the hydrocarbon surfactant substantially in the form of an organic acid. By carrying out the polymerization in the absence of the above-mentioned hydrocarbon surfactant in the form of a substantially organic acid, the stability of the polymerization is further improved, and a high molecular weight PTFE can be obtained.

The hydrocarbon surfactant substantially in the form of an organic acid is not present, and means that the concentration of the organic acid is preferably 1.0% by mass or less, more preferably 0.5% by mass or less, further preferably 0.1% by mass or less, particularly preferably 0.05% by mass or less, and particularly preferably 0.01% by mass or less, based on the mass of the aqueous dispersion obtained.

In the present specification, "organic acid" refers to an organic compound exhibiting acidity. Examples of the organic acid include a carboxylic acid having a-COOH group and a carboxylic acid having a-SO group₃The H-group sulfonic acid is preferably a carboxylic acid because it facilitates adjustment of the pH of an aqueous solution containing an organic acid.

The term "organic acid form" means an acidic group (for example, -COOH group, -SO) contained in an organic acid₃H group, etc.) in the form of the free H.

In the above production method, the hydrocarbon surfactant is an anionic hydrocarbon surfactant.

In the polymerization step, the amount of the hydrocarbon surfactant at the start of polymerization is preferably more than 50ppm with respect to the aqueous medium. The amount of the hydrocarbon surfactant at the start of polymerization is preferably 60ppm or more, more preferably 70ppm or more, further preferably 80ppm or more, and further preferably 100ppm or more. The upper limit is not particularly limited, but is preferably 10000ppm, more preferably 5000ppm, for example. When the amount of the hydrocarbon surfactant at the start of polymerization is in the above range, an aqueous dispersion having a smaller average primary particle diameter and more excellent stability can be obtained.

The polymerization may be started when the gas TFE in the reactor becomes PTFE and the pressure in the reactor is reduced. U.S. Pat. No. 3,391,099 (Punderson) discloses a dispersion polymerization of tetrafluoroethylene in an aqueous medium, which includes 2 different stages of the polymerization process, first the formation of polymer nuclei as nucleation sites, and second the growth stage of the polymerization, which contains the established particles. Note that the polymerization is usually started when both the monomer to be polymerized and the polymerization initiator are charged into the reactor. In the present invention, an additive involved in the formation of a nucleation site is used as a nucleating agent.

The polymerization step preferably includes an addition step of adding a composition containing a hydrocarbon surfactant after the start of polymerization. By the above addition step, the stability of polymerization is further improved, and PTFE having a higher molecular weight can be obtained.

The hydrocarbon surfactant may be in the form of a solid (for example, a powder of a hydrocarbon surfactant) or a liquid, for example.

The composition may be composed of only the hydrocarbon surfactant as long as it contains the hydrocarbon surfactant, or may be a solution or dispersion of the hydrocarbon surfactant containing the hydrocarbon surfactant and a liquid medium. Therefore, the above-mentioned addition step may be referred to as a step of adding a single substance of a hydrocarbon surfactant or a composition containing a hydrocarbon surfactant after the start of polymerization.

The hydrocarbon surfactant is not limited to one kind, and may be a mixture of 2 or more kinds.

The liquid medium may be either an aqueous medium or an organic solvent, or a combination of an aqueous medium and an organic solvent may be used.

Specific examples of the composition include an aqueous solution in which a hydrocarbon surfactant is dissolved in an aqueous medium, and an aqueous dispersion in which a hydrocarbon surfactant is dispersed in an aqueous medium.

The hydrocarbon surfactant added in the adding step is preferably 0.0001 to 10% by mass with respect to the aqueous medium. The content is more preferably 0.001% by mass or more, still more preferably 0.01% by mass or more, and particularly preferably 0.05% by mass or more relative to the aqueous medium. Further, the content is more preferably 5% by mass or less, still more preferably 3% by mass or less, and particularly preferably 1% by mass or less with respect to the aqueous medium.

Since the stability of polymerization is improved and PTFE having a higher molecular weight can be obtained, the composition is preferably an aqueous solution containing a hydrocarbon surfactant and having a pH of 5.0 or more. The pH of the aqueous solution is more preferably 6.0 or more, further preferably 6.5 or more, further preferably 7.0 or more, particularly preferably 7.5 or more, and particularly preferably 8.0 or more. The upper limit of the pH is not particularly limited, and may be 12.0 or less, or may be 11.0 or less.

The hydrocarbon surfactant in the addition step is preferably an anionic hydrocarbon surfactant, and more preferably a carboxylic acid type hydrocarbon surfactant.

The anionic hydrocarbon surfactant and the carboxylic acid type hydrocarbon surfactant are not particularly limited, and for example, the compound (α) exemplified in the above-mentioned other compounds having surface-active ability, and the like can be suitably used.

The carboxylic acid type hydrocarbon surfactant used in the polymerization step and the addition step is preferably selected from the group consisting of the surfactant (e) and the formula: r⁶(-L-M)₂An anionic surfactant of the formula and the formula: r⁷(-L-M)₃The anionic surfactant described above includes at least one member selected from the group consisting of a surfactant having a carboxyl group (-COOH) or a group in which a hydrogen atom of a carboxyl group is substituted with an inorganic cation (for example, a metal atom, ammonium, or the like), the compound (α) described above, the surfactant (1-0A), and a surfactant obtained by subjecting the above surfactants to radical treatment or oxidation treatment. The carboxylic acid type hydrocarbon surfactant may be used in a mixture of 1 species or 2 or more species.

The above compound (α) includes not only the above formula: r¹⁰²-COOM (wherein R¹⁰²And M is the same as described above), and an anionic hydrocarbon surfactant (preferably a compound represented by the formula (B) further comprising the formula: and anionic surfactants represented by R-L-M (wherein R, L and M are the same as those described above), surfactants (c) and (d) having a carboxyl group (-COOH) or a group in which a hydrogen atom of a carboxyl group is substituted with an inorganic cation (for example, a metal atom, ammonium, etc.), and the like.

The carboxylic acid type hydrocarbon surfactant is preferably the compound (. alpha.), more preferably a compound selected from the group consisting of the compounds represented by the formula (B) and A in the formula (c)^cis-COOX^cA in the above formula (d)^dis-COOX^dA in the above formula (e)^eis-COOM^eAt least one member selected from the group consisting of compounds wherein A in the formula (1-0A) is-COOM and compounds obtained by subjecting these compounds to radical treatment or oxidation treatment, andin the one step, at least one selected from the group consisting of the compound represented by the above formula (a) and a compound obtained by subjecting the compound to radical treatment or oxidation treatment is preferable.

Particularly, at least one selected from the group consisting of lauric acid, capric acid, myristic acid, pentadecanoic acid, palmitic acid, and salts thereof, and compounds obtained by subjecting these compounds to radical treatment or oxidation treatment is preferable. Examples of the salt include a metal atom having a carboxyl group and a hydrogen atom of the formula M, NR¹⁰¹ ₄The salt of imidazolium, pyridinium, or phosphonium is not particularly limited.

The above-mentioned production method preferably comprises polymerizing tetrafluoroethylene in the substantial absence of a fluorine-containing surfactant.

The phrase "substantially in the absence of a fluorosurfactant" in the above production method means that the fluorosurfactant is 10ppm or less, preferably 1ppm or less, more preferably 100ppb or less, further preferably 10ppb or less, and further more preferably 1ppb or less with respect to the aqueous medium.

Examples of the fluorinated surfactant include anionic fluorinated surfactants.

The anionic fluorosurfactant may be a surfactant containing fluorine atoms, for example, in which the total carbon number of the portion excluding the anionic groups is 20 or less.

The fluorine-containing surfactant may be a surfactant containing fluorine having an anionic moiety and a molecular weight of 800 or less.

The "anionic moiety" refers to a moiety of the above-mentioned fluorosurfactant other than cations. For example, F (CF) represented by the following formula (I)₂)_n1COOM is "F (CF)₂)_n1COO'.

The above-mentioned fluorosurfactant includes a fluorosurfactant having a LogPOW of 3.5 or less. The LogPOW is a partition coefficient between 1-octanol and water and is represented by LogP [ where P represents a ratio of a concentration of a fluorosurfactant in octanol/a concentration of the fluorosurfactant in water when a mixed solution of octanol/water (1: 1) containing the fluorosurfactant is phase-separated ].

The LogPOW is calculated as follows: in the column: TOSOH ODS-120T columnManufactured by tokyo corporation), eluent: acetonitrile/0.6 mass% HClO4 water 1/1 (vol/vol%), flow rate: 1.0 ml/min, sample size: 300. mu.L, column temperature: detection at 40 ℃ light: HPLC was performed under UV210nm conditions on standard substances (heptanoic acid, octanoic acid, nonanoic acid, and decanoic acid) having known octanol/water partition coefficients, calibration curves were prepared for each elution time and the known octanol/water partition coefficients, and the elution time of HPLC in the sample solution was calculated based on the calibration curves.

Specific examples of the above-mentioned fluorosurfactant include U.S. patent application publication No. 2007/0015864, U.S. patent application publication No. 2007/0015865, U.S. patent application publication No. 2007/0015866, U.S. patent application publication No. 2007/0276103, U.S. patent application publication No. 2007/0117914, U.S. patent application publication No. 2007/142541, U.S. patent application publication No. 2008/0015319, U.S. patent application publication No. 3250808, U.S. patent application publication No. 3271341, Japanese patent laid-open No. 2003-119204, International publication No. 2005/042593, International publication No. 2008/060461, International publication No. 2007/046377, International publication No. 2007/119526, International publication No. 2007/046482, International publication No. 2007/046345, And fluorosurfactants described in U.S. patent application publication No. 2014/0228531, international publication No. 2013/189824, and international publication No. 2013/189826.

Examples of the anionic fluorosurfactant include those represented by the following general formula (N)⁰)：

Xⁿ⁰-Rfⁿ⁰-Y⁰ (N⁰)

(in the formula, Xⁿ⁰H, Cl or F. Rfⁿ⁰The alkylene group may contain 1 or more ether bonds and may have 3 to 20 carbon atoms in a chain, branched or cyclic manner, wherein part or all of H is substituted by F, and part of H may be substituted by Cl. Y is⁰Is an anionic group).

Y⁰The anionic group of (A) may be-COOM, -SO₂M or-SO₃M, may also be-COOM or-SO₃M。

M is H, a metal atom, NR⁷ ₄Imidazolium with or without substituents, pyridinium with or without substituents or phosphonium with or without substituents, R⁷Is H or an organic group.

Examples of the metal atom include alkali metals (group 1), alkaline earth metals (group 2), and the like, and examples thereof include Na, K, and Li.

As R⁷May be H or C_1-10May also be H or C_1-4May also be H or C_1-4Alkyl group of (1).

M may be H, a metal atom or NR⁷ ₄It may be H, an alkali metal (group 1), an alkaline earth metal (group 2) or NR⁷ ₄And may also be H, Na, K, Li or NH₄。

Rf aboveⁿ⁰In (b), 50% or more of H may be substituted by fluorine.

As the above general formula (N)⁰) Examples of the compound include:

The following general formula (N)¹)：

Xⁿ⁰-(CF₂)_m1-Y⁰ (N¹)

(in the formula, Xⁿ⁰H, Cl and F, m1 is an integer of 3-15, Y⁰Is a substance defined above); the following general formula (N)²)：

Rfⁿ¹-O-(CF(CF₃)CF₂O)_m2CFXⁿ¹-Y⁰ (N²)

(wherein Rfⁿ¹Is a perfluoroalkyl group having 1 to 5 carbon atoms, and m2 is 0 to 3Number, Xⁿ¹Is F or CF₃，Y⁰Is a substance defined above); the following general formula (N)³)：

Rfⁿ²(CH₂)_m3-(Rfⁿ³)_q-Y⁰ (N³)

(wherein Rfⁿ²Is a partially or fully fluorinated alkyl group having 1 to 13 carbon atoms and containing an ether bond, m3 is an integer of 1 to 3, and Rfⁿ³Is a linear or branched perfluoroalkylene group having 1 to 3 carbon atoms, q is 0 or 1, Y⁰Is a substance defined above); the following general formula (N)⁴)：

Rfⁿ⁴-O-(CYⁿ¹Yⁿ²)_pCF₂-Y⁰ (N⁴)

(wherein Rfⁿ⁴Is a linear or branched partially or fully fluorinated alkyl group having 1 to 12 carbon atoms and containing an ether bond, Yⁿ¹And Yⁿ²Identical or different, is H or F, p is 0 or 1, Y⁰Is a substance defined above); and the following general formula (N)⁵)：

The following general formula (N)⁵)：

[ chemical formula 120]

(in the formula, Xⁿ²、Xⁿ³And Xⁿ⁴H, F or a linear or branched partially or fully fluorinated alkyl group having 1 to 6 carbon atoms and optionally containing an ether bond. Rfⁿ⁵Is a linear or branched partially or fully fluorinated alkylene group having 1 to 3 carbon atoms and containing an ether bond, L is a linking group, Y is ⁰Are defined above. Wherein, Xⁿ²、Xⁿ³、Xⁿ⁴And Rfⁿ⁵The total number of carbon atoms of (2) is 18 or less).

As the above general formula (N)⁰) The compounds shown, more specifically,examples thereof include a perfluorocarboxylic acid (I) represented by the following general formula (I), an ω -H perfluorocarboxylic acid (II) represented by the following general formula (II), a perfluoropolyether carboxylic acid (III) represented by the following general formula (III), a perfluoroalkylalkylalkylene carboxylic acid (IV) represented by the following general formula (IV), a perfluoroalkoxy fluorocarboxylic acid (V) represented by the following general formula (V), a perfluoroalkylsulfonic acid (VI) represented by the following general formula (VI), an ω -H perfluorosulfonic acid (VII) represented by the following general formula (VII), a perfluoroalkylalkylalkylene sulfonic acid (VIII) represented by the following general formula (VIII), an alkylalkylalkylene carboxylic acid (IX) represented by the following general formula (IX), a fluorocarboxylic acid (X) represented by the following general formula (X), an alkoxy fluorocarbonic acid (XI) represented by the following general formula (XI), and a compound (XII) represented by the.

The above-mentioned perfluorocarboxylic acid (I) is represented by the following general formula (I)

F(CF₂)_n1COOM (I)

(wherein n1 is an integer of 3 to 14, M is H, a metal atom, NR⁷ ₄Imidazolium with or without substituents, pyridinium with or without substituents or phosphonium with or without substituents, R⁷Is H or an organic group).

The above-mentioned omega-H perfluorocarboxylic acid (II) is represented by the following general formula (II)

H(CF₂)_n2COOM (II)

(wherein n2 is an integer of 4 to 15, and M is as defined above).

The above perfluoropolyether carboxylic acid (III) is represented by the following general formula (III)

Rf¹-O-(CF(CF₃)CF₂O)_n3CF(CF₃)COOM (III)

(wherein Rf¹A perfluoroalkyl group having 1 to 5 carbon atoms, n3 is an integer of 0 to 3, and M is as defined above).

The above perfluoroalkyl alkylene carboxylic acid (IV) is represented by the following general formula (IV)

Rf²(CH₂)_n4Rf³COOM (IV)

(wherein Rf²Is a perfluoroalkyl group having 1 to 5 carbon atoms, Rf³Is straight-chain or branchedA perfluoroalkylene group having 1 to 3 carbon atoms, n4 is an integer of 1 to 3, and M is as defined above).

The alkoxy fluorocarboxylic acid (V) is represented by the following general formula (V)

Rf⁴-O-CY¹Y²CF₂-COOM (V)

(wherein Rf⁴Is a linear or branched partially or fully fluorinated alkyl group having 1 to 12 carbon atoms and containing an ether bond, Y¹And Y²Identical or different, H or F, M being a substance as defined above).

The above perfluoroalkylsulfonic acid (VI) is represented by the following general formula (VI)

F(CF₂)_n5SO₃M (VI)

(wherein n5 is an integer of 3 to 14, and M is as defined above).

The omega-H perfluorosulfonic acid (VII) is represented by the following general formula (VII)

H(CF₂)_n6SO₃M (VII)

(wherein n6 is an integer of 4 to 14, and M is as defined above).

The above perfluoroalkyl alkylene sulfonic acid (VIII) is represented by the following general formula (VIII)

Rf⁵(CH₂)_n7SO₃M (VIII)

(wherein Rf⁵A perfluoroalkyl group having 1 to 13 carbon atoms, n7 is an integer of 1 to 3, and M is defined as above).

The above-mentioned alkyl alkylene carboxylic acid (IX) is represented by the following general formula (IX)

Rf⁶(CH₂)_n8COOM (IX)

(wherein Rf⁶A linear or branched partially or fully fluorinated alkyl group having 1 to 13 carbon atoms and containing an ether bond, n8 is an integer of 1 to 3, and M is defined as above).

The fluorocarboxylic acid (X) is represented by the following general formula (X)

Rf⁷-O-Rf⁸-O-CF₂-COOM (X)

(wherein Rf⁷Is a linear or branched partially or fully fluorinated alkyl group having 1 to 6 carbon atoms and containing an ether bond, and Rf⁸A linear or branched partially or fully fluorinated alkyl group having 1 to 6 carbon atoms, wherein M is as defined above).

The above alkoxy fluorosulfonic acid (XI) is represented by the following general formula (XI)

Rf⁹-O-CY¹Y²CF₂-SO₃M (XI)

(wherein Rf⁹Is a linear or branched C1-12 alkyl group which may contain an ether bond and may be partially or fully fluorinated and may contain chlorine, and Y is¹And Y²Identical or different, H or F, M being a substance as defined above).

The above compound (XII) is represented by the following general formula (XII):

[ solution 121]

In the formula, X¹、X²And X³H, F and a linear or branched partially or fully fluorinated alkyl group having 1 to 6 carbon atoms and containing an ether bond, and Rf ¹⁰Is a C1-3 perfluoroalkylene group, L is a linking group, Y⁰Anionic group).

Y⁰Can be-COOM, -SO₂M or-SO₃M, may also be-SO₃M or COOM (wherein M is defined above).

Examples of L include a single bond, a partially or fully fluorinated alkylene group having 1 to 10 carbon atoms and containing an ether bond.

As described above, examples of the anionic fluorosurfactant include a carboxylic acid surfactant and a sulfonic acid surfactant.

The PTFE of the present invention can be suitably produced by a production method including an addition step of adding at least one selected from the group consisting of a radical scavenger and a decomposition agent for a polymerization initiator. The addition step is performed in a step of performing the emulsion polymerization in an aqueous medium. The radical concentration during polymerization can be adjusted by adding a radical scavenger or a decomposition agent for the polymerization initiator. From the viewpoint of reducing the radical concentration, a radical scavenger is preferable.

As the radical scavenger, a compound which is added to a radical in a polymerization system or does not have a re-initiation ability after chain transfer is used. Specifically, a compound having the following functions is used: the chain transfer reaction with the primary radical or the growing radical is likely to occur, and then a stable radical which does not react with the monomer is generated, or the addition reaction with the primary radical or the growing radical is likely to occur, and a stable radical is generated.

The activity of a substance commonly referred to as a chain transfer agent is characterized by a chain transfer constant and a reinitiation efficiency, and among chain transfer agents, a substance having a reinitiation efficiency of substantially 0% is referred to as a radical scavenger.

The radical scavenger is, for example, a compound having a chain transfer constant with TFE higher than the polymerization rate constant at the polymerization temperature and having a reinitiation efficiency of substantially zero%. "the reinitiation efficiency is substantially zero%" means that the radical scavenger is a stable radical by the generated radical.

The compound is preferably a compound having a chain transfer constant (Cs) (═ chain transfer rate constant (kc)/polymerization rate constant (kp)) with TFE of more than 0.1 at the polymerization temperature, and the chain transfer constant (Cs) of the compound is more preferably 0.5 or more, still more preferably 1.0 or more, further more preferably 5.0 or more, and particularly preferably 10 or more.

The radical scavenger in the present invention is preferably selected from the group consisting of aromatic hydroxy compounds, aromatic amines, N-diethylhydroxylamine, quinone compounds, terpenes, thiocyanates, and copper chloride (CuCl)₂) At least one of the group consisting of.

Examples of the aromatic hydroxy compound include unsubstituted phenol, polyhydric phenol, salicylic acid, m-or p-salicylic acid, gallic acid, naphthol, and the like.

Examples of the unsubstituted phenol include o-nitrophenol, m-nitrophenol, p-nitrophenol, o-aminophenol, m-aminophenol, p-aminophenol, and p-nitrosophenol. Examples of the polyhydric phenol include catechol, resorcinol, hydroquinone, pyrogallol, phloroglucinol, and naphthol resorcinol.

Examples of the aromatic amines include o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, and benzidine.

Examples of the quinone compound include o-benzoquinone, m-benzoquinone, p-benzoquinone, 1, 4-naphthoquinone, alizarin, and the like.

The thiocyanate may be ammonium thiocyanate (NH)₄SCN), potassium thiocyanate (KSCN), sodium thiocyanate (NaSCN), and the like.

Among these, aromatic hydroxy compounds are preferable, unsubstituted phenols or polyhydric phenols are more preferable, and hydroquinone is further preferable.

The amount of the radical scavenger added is preferably an amount corresponding to 3 to 500% (on a molar basis) of the concentration of the polymerization initiator, from the viewpoint of reducing the standard specific gravity. The lower limit is more preferably 5% (on a molar basis), still more preferably 8% (on a molar basis), still more preferably 10% (on a molar basis), still more preferably 15% (on a molar basis), still more preferably 20% (on a molar basis), particularly preferably 25% (on a molar basis), particularly preferably 30% (on a molar basis), and particularly preferably 35% (on a molar basis). The upper limit is more preferably 400% (molar basis), still more preferably 300% (molar basis), still more preferably 200% (molar basis), and yet more preferably 100% (molar basis).

The decomposition agent of the polymerization initiator may be any compound that can decompose the polymerization initiator used, and is preferably at least one selected from the group consisting of sulfite, bisulfite, bromate, diimine salt, oxalic acid, oxalate, copper salt, and iron salt, for example. Examples of the sulfite include sodium sulfite and ammonium sulfite. Copper salt may be copper sulfate (II), and iron salt may be iron sulfate (II).

The amount of the decomposition agent of the polymerization initiator is 25 to 300 mass% based on the amount of the oxidizing agent combined as the polymerization initiator (redox initiator described later). Preferably 25 to 150 mass%, and more preferably 50 to 100 mass%.

The amount of the above-mentioned decomposition agent for the polymerization initiator is preferably an amount corresponding to 3 to 500% (on a molar basis) of the concentration of the polymerization initiator, from the viewpoint of reducing the standard specific gravity. The lower limit is more preferably 5% (by mol), still more preferably 8% (by mol), still more preferably 10% (by mol), still more preferably 13% (by mol), and yet more preferably 15% (by mol). The upper limit is more preferably 400% (molar basis), still more preferably 300% (molar basis), still more preferably 200% (molar basis), and yet more preferably 100% (molar basis).

At least one selected from the group consisting of radical scavengers and decomposers of polymerization initiators is preferably added when the concentration of PTFE formed in the aqueous medium is 5 mass% or more. More preferably 10% by mass or more.

Further, it is preferably added when the concentration of PTFE formed in the aqueous medium is 40% by mass or less. More preferably 35% by mass or less, and still more preferably 30% by mass or less.

The addition step may be a step of continuously adding at least one selected from the group consisting of a radical scavenger and a decomposition agent for a polymerization initiator.

The continuous addition of at least one selected from the group consisting of the radical scavenger and the decomposition agent for the polymerization initiator means, for example, that at least one selected from the group consisting of the radical scavenger and the decomposition agent for the polymerization initiator is not added all at once but added over time and without interruption or in portions.

The polymerization step may further comprise polymerizing tetrafluoroethylene in the presence of a nucleating agent.

The nucleating agent is preferably at least one selected from the group consisting of fluoropolyethers, nonionic surfactants, and chain transfer agents.

In this case, the polymerization step is preferably a step of polymerizing tetrafluoroethylene in an aqueous medium in the presence of a hydrocarbon surfactant and the nucleating agent to obtain PTFE.

The fluoropolyether is preferably a perfluoropolyether.

The fluoropolyether preferably has repeating units represented by the formulae (1a) to (1 d).

(-CFCF₃-CF₂-O-)_n (1a)

(-CF₂-CF₂-CF₂-O-)_n (1b)

(-CF₂-CF₂-O-)n-(-CF₂-O-)_m (1c)

(-CF₂-CFCF₃-O-)n-(-CF₂-O-)_m (1d)

(in the formulae (1a) to (1d), m and n are integers of 1 or more.)

The fluoropolyether is preferably a fluoropolyether acid or a salt thereof, and the fluoropolyether acid is preferably a carboxylic acid, a sulfonic acid, a sulfonamide, or a phosphonic acid, and more preferably a carboxylic acid. Among fluoropolyether acids or salts thereof, preferred are salts of fluoropolyether acids, more preferred are ammonium salts of fluoropolyether acids, and still more preferred are ammonium salts of fluoropolyether carboxylic acids.

The fluoropolyether acid or salt thereof may have: an arbitrary chain structure in which oxygen atoms in the main chain of the molecule are separated by saturated carbon fluoride groups having 1 to 3 carbon atoms. More than 2 carbon fluoride groups may be present in the molecule.

The fluoropolyether acid or salt thereof is preferably represented by the formula:

CF₃-CF₂-CF₂-O(-CFCF₃-CF₂-O-)_nCFCF₃-COOH、

CF₃-CF₂-CF₂-O(-CF₂-CF₂-CF₂-O-)_n-CF₂-CF₂COOH, or

HOOC-CF₂-O(-CF₂-CF₂-O-)n-(-CF₂-O-)_mCF₂COOH

(wherein m and n are the same as described above.)

The compounds shown or their salts.

These structures were studied by Kasai in j.appl.polymer sci.57,797 (1995). Such fluoropolyethers may have a carboxylic acid group or salt thereof at one or both ends, as disclosed herein. Likewise, such fluoropolyethers may have sulfonic or phosphonic acid groups or salts thereof at one or both ends. In addition to this, fluoropolyethers having acid functional groups at both ends may have different groups at each end. With regard to monofunctional fluoropolyethers, the other end of the molecule is typically perfluorinated and may also contain a hydrogen or chlorine atom.

The fluoropolyether having an acid group at one or both ends has at least 2 ether oxygens, preferably at least 4 ether oxygens, and even more preferably at least 6 ether oxygens. Preferably at least one of the carbon fluoride groups spaced apart from the ether oxygen, more preferably at least two of such carbon fluoride groups, has 2 or 3 carbon atoms. Even more preferably at least 50% of the carbon fluoride groups separating the ether oxygen have 2 or 3 carbon atoms. In addition, it is preferred that the fluoropolyethers have at least 15 carbon atoms in total, e.g., a preferred minimum value of n or n + m in the above repeating unit structure is at least 5. More than 2 fluoropolyethers having acid groups at one or both ends may be used in the process of the present invention. Typically, in the manufacture of a single species of a particular fluoropolyether compound, unless otherwise noted, the fluoropolyether can contain two or more compounds in various proportions within the molecular weight range relative to the average molecular weight.

The fluoropolyether preferably has a number average molecular weight of 800g/mol or more. The fluoropolyether acid or salt thereof preferably has a number average molecular weight of less than 6000g/mol, since dispersion in aqueous media can be difficult. The number average molecular weight of the fluoropolyether acid or salt thereof is more preferably 800 to 3500g/mol, still more preferably 1000 to 2500 g/mol.

The amount of the fluoropolyether is preferably 5 to 3000ppm, more preferably 5 to 2000ppm, further preferably 10ppm at the lower limit, and further preferably 100ppm at the upper limit, based on the aqueous medium.

The nonionic surfactant of the nucleating agent may be the nonionic surfactant described above, and preferably a nonionic surfactant containing no fluorine. For example, the nonionic surfactant may be represented by the following general formula (i)

R³-O-A¹-H (i)

(in the formula, R³Is a linear or branched primary or secondary alkyl group having 8 to 18 carbon atoms, A¹Is a polyoxyalkylene chain).

R³The number of carbon atoms of (A) is preferably 10 to 16, more preferably 12 to 16. If R is³When the number of carbon atoms of (2) is 18 or less, good dispersion stability of the aqueous dispersion can be easily obtained. In addition if R³If the number of carbon atoms exceeds 18, the flow temperature is high, and therefore, handling is difficult. If R is³When the number of carbon atoms of (2) is less than 8, the surface tension of the aqueous dispersion increases, and the permeability and wettability tend to decrease.

The polyoxyalkylene chain may be composed of ethylene oxide and propylene oxide. Is a polyoxyalkylene chain having 5 to 20 average repeating numbers of oxyethylene groups and 0 to 2 average repeating numbers of oxypropylene groups, and is a hydrophilic group. The ethylene oxide unit number may comprise any of a broad or narrow monomodal distribution, as typically provided, or a broader or bimodal distribution obtained by blending. When the average repeating number of the oxypropylene group exceeds 0, the oxyethylene group and the oxypropylene group in the polyoxyalkylene chain may be arranged in a block form or in a random form.

From the viewpoint of viscosity and stability of the aqueous dispersion, a polyoxyalkylene chain comprising an average repeating number of oxyethylene groups of 7 to 12 and an average repeating number of oxypropylene groups of 0 to 2 is preferred. Especially if A¹It is preferable that the acrylic resin composition has an oxypropylene group of 0.5 to 1.5 on average because low foaming property is good.

More preferably R³Is (R ') (R') HC-, wherein R 'and R' are the same or different linear, branched or cyclic alkyl groups, and the total number of carbon atoms is at least 5, preferably 7 to 17. Preferably R' orAt least one of R' is a branched or cyclic hydrocarbon group.

Specific examples of the polyoxyethylene alkyl ether include C₁₃H₂₇-O-(C₂H₄O)₁₀-H、C₁₂H₂₅-O-(C₂H₄O)₁₀-H、C₁₀H₂₁CH(CH₃)CH₂-O-(C₂H₄O)₉-H、C₁₃H₂₇-O-(C₂H₄O)₉-(CH(CH₃)CH₂O)-H、C₁₆H₃₃-O-(C₂H₄O)₁₀-H、HC(C₅H₁₁)(C₇H₁₅)-O-(C₂H₄O)₉-H, etc. Examples of commercially available products of the polyoxyethylene alkyl ether include Genapol X080 (product name, manufactured by Clariant), Noigen TDS series (first Industrial pharmaceutical Co., Ltd.) such as Noigen TDS-80 (trade name), Leocol TD series (LION Co., Ltd.) such as Leocol TD-90 (trade name), LIONOL (registered trademark) TD series (LION Co., Ltd.), T-DetA series (Harcross Chemicals Co., Ltd.) such as T-DetA138 (trade name), and TERGITOL (registered trademark) 15S series (manufactured by Tao Co., Ltd.).

The above nonionic surfactants are also preferably ethoxylates of 2,6, 8-trimethyl-4-nonanol having an average of about 4 to about 18 ethylene oxide units, ethoxylates of 2,6, 8-trimethyl-4-nonanol having an average of about 6 to about 12 ethylene oxide units, or mixtures thereof. Nonionic surfactants of this type are also commercially available, for example, as TERGITOL TMN-6, TERGITOL TMN-10, and TERGITOL TMN-100X (both product names, manufactured by the Dow chemical company).

In addition, the hydrophobic group of the nonionic surfactant may be any of an alkylphenol group, a straight-chain alkyl group, and a branched-chain alkyl group.

For example, examples of the polyoxyethylene alkylphenyl ether nonionic compound include those represented by the following general formula (ii)

R⁴-C₆H₄-O-A²-H (ii)

(in the formula, R⁴Is a linear or branched primary or secondary alkyl group having 4 to 12 carbon atoms, A²Is a polyoxyalkylene chain). Specific examples of the polyoxyethylene alkylphenyl ether nonionic compound include TRITONX-100 (trade name, manufactured by Dow Chemical Co., Ltd.).

Examples of the nonionic surfactant include polyhydric alcohol compounds. Specifically, there are polyol compounds described in international publication No. 2011/014715, and the like.

As a typical example of the polyol compound, a compound having 1 or more sugar units as a polyol unit can be cited. The saccharide units may be modified to contain at least 1 long chain. Examples of suitable polyol compounds containing at least 1 long chain moiety include alkyl glycosides, modified alkyl glycosides, sugar esters, and combinations thereof. Examples of the saccharide include, but are not limited to, monosaccharides, oligosaccharides, and sorbitan. Examples of the monosaccharide include a five-carbon sugar and a six-carbon sugar. Typical examples of the monosaccharide include ribose, glucose, galactose, mannose, fructose, arabinose, and xylose. The oligosaccharide may be an oligomer of 2 to 10 identical or different monosaccharides. Examples of the oligosaccharide include, but are not limited to, sucrose, maltose, lactose, raffinose, and isomaltose.

Typically, as the sugar suitable for use as the polyol compound, there may be mentioned a five-membered ring cyclic compound containing 4 carbon atoms and 1 hetero atom (typically oxygen or sulfur, preferably oxygen atom), or a six-membered ring cyclic compound containing 5 carbon atoms and the above-mentioned 1 hetero atom, preferably oxygen atom. They further contain at least 2 or at least 3 hydroxyl groups (-OH groups) bonded to carbon ring atoms. Typically, to make ether or ester linkages between long chain residues and sugar moieties, sugars are modified in the following ways: more than 1 of the hydrogen atoms of the hydroxyl (and/or hydroxyalkyl) groups bonded to carbon ring atoms are substituted with long chain residues.

The sugar-based polyol may contain 1 sugar unit or 2 or more sugar units. 1 sugar unit or 2 or more sugar units may be modified with the above-mentioned long chain moiety. Specific examples of the sugar-based polyol compound include glycosides, sugar esters, sorbitan esters, and mixtures and combinations thereof.

A preferred class of polyol compounds is alkyl or modified alkyl glucosides. These classes of surfactants contain at least 1 glucose moiety. Can give

[ chemical formula 122]

(wherein x represents 0, 1, 2, 3, 4, or 5, R¹And R²Independently represents H or a long chain unit containing at least 6 carbon atoms, wherein R¹And R²At least 1 of which is not H). As R¹And R²As a typical example of (A), an aliphatic alcohol residue can be mentioned. Examples of the aliphatic alcohol include hexanol, heptanol, octanol, nonanol, decanol, undecanol, dodecanol (lauryl alcohol), tetradecanol, hexadecanol (cetyl alcohol), heptadecanol, octadecanol (stearyl alcohol), eicosanoic acid, and combinations thereof.

The above formula shows a specific example of an alkylpolyglucoside of glucose representing the pyranose form, but it will be appreciated that other sugars or sugars which are the same sugar but different mirror image isomers or diastereoisomers may also be used.

The alkyl glucosides can be obtained, for example, by acid-catalyzed reaction of glucose, starch, or n-butyl glucoside with an aliphatic alcohol, in the typical case a mixture of various alkyl glucosides being obtained (Alkylpolyglycylcoside, Rompp, Lexikon Chemie, Version 2.0, Stuttgart/New York, Georg Thieme Verlag, 1999). Examples of the aliphatic alcohol include hexanol, heptanol, octanol, nonanol, decanol, undecanol, dodecanol (lauryl alcohol), tetradecanol, hexadecanol (cetyl alcohol), heptadecanol, octadecanol (stearyl alcohol), eicosanoic acid, and combinations thereof. In addition, alkyl glucosides are commercially available from Dusseldorf Cognis GmbH, Germany under the trade name GLUCOPON or DISPONIL.

Other nonionic surfactants include bifunctional block copolymers supplied by BASF as Pluronic (registered trademark) R series, tridecanol alkoxylates supplied by BASF as Iconol (registered trademark) TDA series, hydrocarbon-containing siloxane surfactants, preferably hydrocarbon surfactants, wherein the hydrocarbon group is completely substituted with a hydrogen atom when the hydrocarbon group can be substituted with a halogen such as fluorine, and these siloxane surfactants can also be considered as hydrocarbon surfactants, i.e., monovalent substituents on the hydrocarbon group are hydrogen.

In addition, in the above production method, in addition to the specific hydrocarbon surfactant and other compounds having a surface-active ability to be used as desired, an additive for stabilizing each compound may be used. Examples of the additives include a buffer, a pH adjuster, a stabilizing aid, and a dispersion stabilizer.

The stabilizing aid is preferably paraffin, a fluorine-based oil, a fluorine-based solvent, silicone oil, or the like. The stabilizing aids may be used singly or in combination of 1 or more. As the stabilizing aid, paraffin wax is more preferable. The paraffin wax may be liquid, semisolid, or solid at room temperature, but is preferably a saturated hydrocarbon having 12 or more carbon atoms. The melting point of the paraffin wax is preferably 40 to 65 ℃ and more preferably 50 to 65 ℃.

The amount of the stabilizing aid used is preferably 0.1 to 12% by mass, more preferably 0.1 to 8% by mass, based on the mass of the aqueous medium used. The stabilizing aid is preferably sufficiently hydrophobic to be completely separated from the aqueous PTFE emulsion after emulsion polymerization of TFE and not to become a contaminating component.

In the above production method, the emulsion polymerization is carried out as follows: the emulsion polymerization is carried out by charging an aqueous medium, the above-mentioned hydrocarbon-based surfactant, a monomer and, if necessary, other additives into a polymerization reactor, stirring the contents of the reactor, maintaining the reactor at a predetermined polymerization temperature, and then adding a predetermined amount of a polymerization initiator to initiate the polymerization reaction. After the polymerization reaction is started, a monomer, a polymerization initiator, a chain transfer agent, the surfactant, and the like may be added thereto according to the purpose. The hydrocarbon surfactant may be added after the polymerization reaction is started.

In the emulsion polymerization, the polymerization temperature and polymerization pressure are appropriately determined depending on the kind of the monomer to be used, the molecular weight of the target PTFE, and the reaction rate. The polymerization temperature is usually 5 to 150 ℃, preferably 10 ℃ or higher, more preferably 30 ℃ or higher, and still more preferably 50 ℃ or higher. Further, it is more preferably 120 ℃ or lower, and still more preferably 100 ℃ or lower.

The polymerization pressure is 0.05 to 10 MPaG. The polymerization pressure is more preferably 0.3MPaG or more, and still more preferably 0.5MPaG or more. Further, it is more preferably 5.0MPaG or less, and still more preferably 3.0MPaG or less.

In particular, from the viewpoint of increasing the yield, it is preferably 1.0MPaG or more, more preferably 1.2MPaG or more, further preferably 1.5MPaG or more, further preferably 1.8MPaG or more, and particularly preferably 2.0MPaG or more.

In the emulsion polymerization, the hydrocarbon surfactant is preferably added when the concentration of PTFE formed in the aqueous medium is less than 0.60 mass%. The concentration is more preferably 0.50% by mass or less, still more preferably 0.36% by mass or less, still more preferably 0.30% by mass or less, still more preferably 0.20% by mass or less, particularly preferably 0.10% by mass or less, and most preferably added at the same time as the start of polymerization. The concentration is a concentration based on the total of the aqueous medium and PTFE.

In the emulsion polymerization, the amount of the hydrocarbon surfactant at the start of the polymerization is preferably 1ppm or more with respect to the aqueous medium. The amount of the hydrocarbon surfactant at the start of polymerization is preferably 10ppm or more, more preferably 50ppm or more, further preferably 100ppm or more, and further preferably 200ppm or more. The upper limit is not particularly limited, but is preferably 100000ppm, more preferably 50000ppm, for example. When the amount of the hydrocarbon surfactant at the start of polymerization is in the above range, an aqueous dispersion having a smaller average primary particle diameter and more excellent stability can be obtained.

The polymerization initiator is not particularly limited as long as it can generate radicals in the above polymerization temperature range, and known oil-soluble and/or water-soluble polymerization initiators can be used. Further, the polymerization may be initiated in a redox form in combination with a reducing agent or the like. The concentration of the polymerization initiator is appropriately determined depending on the kind of the monomer, the molecular weight of the target PTFE, and the reaction rate.

As the polymerization initiator, an oil-soluble radical polymerization initiator or a water-soluble radical polymerization initiator can be used.

The oil-soluble radical polymerization initiator may be a known oil-soluble peroxide, and examples thereof include the following peroxides as representative: dialkyl peroxycarbonates such as diisopropyl peroxydicarbonate and di-sec-butyl peroxydicarbonate; peroxyesters such as tert-butyl peroxyisobutyrate and tert-butyl peroxypivalate; dialkyl peroxides such as di-tert-butyl peroxide; and di (omega-hydro-dodecafluoroheptanoyl) peroxide, di (omega-hydro-tetradecafluoroheptanoyl) peroxide, di (omega-hydro-hexadecafluorononoyl) peroxide, di (perfluorobutanoyl) peroxide, di (perfluoropentanoyl) peroxide, di (perfluorohexanoyl) peroxide, di (perfluoroheptanoyl) peroxide, di (perfluorooctanoyl) peroxide, di (perfluorononanoyl) peroxide, di (omega-chloro-hexafluorobutanoyl) peroxide, di (omega-chloro-decafluorohexanoyl) peroxide, di (omega-chloro-tetradecafluorooctanoyl) peroxide, omega-hydro-dodecafluoroheptanoyl-omega-hydroxyhexadecafluorononoyl-peroxide, omega-chloro-hexafluorobutanoyl-omega-chloro-decafluorohexanoyl-peroxide, di (omega-chloro-tetradecafluorooctanoyl) peroxide, omega-hydro-dodecafluoroheptanoyl-omega-hydroxyhexadecafluorononyl-peroxide, omega-chloro-decafluorohexanoyl, Di [ perfluoro (or fluorochloro) acyl ] peroxides such as ω -hydroxydodecafluoroheptanoyl-perfluorobutanoyl-peroxide, di (dichloropentafluorobutanoyl) peroxide, di (trichlorooctafluorohexanoyl) peroxide, di (tetrachloroundecanooctanoyl) peroxide, di (pentachlorotridecanoyl) peroxide, and di (undecanoyl-triacontadoxodidodecanoyl) peroxide; and so on.

The water-soluble radical polymerization initiator may be a known water-soluble peroxide, and examples thereof include ammonium salts, potassium salts, sodium salts, t-butyl peroxymaleate, t-butyl hydroperoxide, and the like of persulfuric acid, perboric acid, perchloric acid, perphosphoric acid, percarbonic acid, and the like. The reducing agent may be a reducing agent such as sulfite or sulfite, and the amount of the reducing agent to be used may be 0.1 to 20 times that of the peroxide.

For example, when the polymerization is carried out at a low temperature of 30 ℃ or lower, a redox initiator in which an oxidizing agent and a reducing agent are combined is preferably used as the polymerization initiator. Examples of the oxidizing agent include persulfates, organic peroxides, potassium permanganate, manganese triacetate, cerium ammonium nitrate, bromates, and the like. Examples of the reducing agent include sulfite, bisulfite, bromate, diimine, oxalic acid, and the like. Examples of the persulfate include ammonium persulfate and potassium persulfate. Examples of the sulfite include sodium sulfite and ammonium sulfite. In order to increase the decomposition rate of the initiator, it is also preferable to add a copper salt or an iron salt to the combination of the redox initiators. Copper salt may be copper (II) sulfate, and iron salt may be iron (II) sulfate.

The redox initiator is preferably permanganate or a salt thereof, persulfate, manganese triacetate, cerium (IV) salt, or bromic acid or a salt thereof as the oxidizing agent, or dicarboxylic acid or a salt thereof as the reducing agent, or diimine.

More preferably, the oxidizing agent is permanganic acid or a salt thereof, the persulfate, or bromic acid or a salt thereof, and the reducing agent is dicarboxylic acid or a salt thereof.

Examples of the redox initiator include potassium permanganate/oxalic acid, potassium permanganate/ammonium oxalate, manganese triacetate/oxalic acid, manganese triacetate/ammonium oxalate, cerium ammonium nitrate/oxalic acid, cerium ammonium nitrate/ammonium oxalate, and the like in combination.

In the case of using a redox initiator, either an oxidizing agent or a reducing agent may be charged into a polymerization vessel in advance, and then the other may be continuously or intermittently added to initiate polymerization. For example, in the case of using potassium permanganate/ammonium oxalate, it is preferable to charge ammonium oxalate into the polymerization vessel and continuously add potassium permanganate thereto.

In the redox initiator of the present specification, the term "potassium permanganate/ammonium oxalate" refers to a combination of potassium permanganate and ammonium oxalate. The same applies to the other compounds.

As the redox initiator, an oxidizing agent or a reducing agent capable of adjusting the pH of the redox initiator aqueous solution to 4.0 or more is preferably used. The redox initiator aqueous solution refers to a 0.50 mass% aqueous solution of an oxidizing agent or a 0.50 mass% aqueous solution of a reducing agent.

That is, at least one of the 0.50 mass% aqueous solution of the oxidizing agent and the 0.50 mass% aqueous solution of the reducing agent may have a pH of 4.0 or more, and preferably both the 0.50 mass% aqueous solution of the oxidizing agent and the 0.50 mass% aqueous solution of the reducing agent have a pH of 4.0 or more.

The pH of the redox initiator aqueous solution (0.50 mass% aqueous solution of the oxidizing agent or 0.50 mass% aqueous solution of the reducing agent) is more preferably 5.0 or more, still more preferably 5.5 or more, and particularly preferably 6.0 or more, respectively.

The redox initiator is particularly preferably a combination of an oxidizing agent as a salt and a reducing agent as a salt.

For example, the oxidizing agent as the salt is more preferably at least one selected from the group consisting of a persulfate, a permanganate, a cerium (IV) salt, and a bromate, and is further preferably a permanganate, and is particularly preferably potassium permanganate.

The reducing agent as the salt is more preferably at least one selected from the group consisting of an oxalate, a malonate, a succinate, a glutarate and a bromate, and is further preferably an oxalate, and particularly preferably ammonium oxalate.

Specifically, the redox initiator is preferably at least one selected from the group consisting of potassium permanganate/ammonium oxalate, potassium bromate/ammonium sulfite, manganese triacetate/ammonium oxalate, and cerium ammonium nitrate/ammonium oxalate, and preferably at least one selected from the group consisting of potassium permanganate/ammonium oxalate, potassium bromate/ammonium sulfite, and cerium ammonium nitrate/ammonium oxalate.

By using a redox initiator in the polymerization step, the molecular weight of the obtained PTFE can be increased. Therefore, SSG can be reduced and stretching can be performed.

Further, the number of particles of PTFE produced in the aqueous dispersion can be increased by using a redox initiator in the polymerization step. In addition, the yield of PTFE can be increased.

In the case of using a redox initiator, the oxidizing agent and the reducing agent may be added all at once in the initial stage of polymerization, the reducing agent may be added all at once and the oxidizing agent may be continuously added in the initial stage of polymerization, the oxidizing agent may be added all at once and the reducing agent may be continuously added in the initial stage of polymerization, or both the oxidizing agent and the reducing agent may be continuously added.

When a redox initiator is used as the polymerization initiator, the amount of the oxidizing agent added is preferably 5 to 10000ppm, more preferably 10 to 1000ppm, and the amount of the reducing agent added is preferably 5 to 10000ppm, more preferably 10 to 1000ppm, relative to the aqueous medium.

When a redox initiator is used in the polymerization step, the polymerization temperature is preferably 100 ℃ or lower, more preferably 95 ℃ or lower, and still more preferably 90 ℃ or lower. Further, it is preferably 10 ℃ or higher, more preferably 20 ℃ or higher, and still more preferably 30 ℃ or higher.

The amount of the polymerization initiator to be added is not particularly limited, and may be added at once, or sequentially, or continuously in the initial stage of polymerization in an amount (for example, several ppm with respect to the concentration of water) or more to such an extent that the polymerization rate does not significantly decrease. The upper limit is a range in which the heat of polymerization reaction can be removed from the apparatus surface and the reaction temperature can be increased, and the more preferable upper limit is a range in which the heat of polymerization reaction can be removed from the apparatus surface. More specifically, for example, the concentration is preferably 1ppm or more, more preferably 10ppm or more, and further preferably 50ppm or more, relative to the aqueous medium. Further, it is preferably 100000ppm or less, more preferably 10000ppm or less, and further preferably 5000ppm or less.

The aqueous medium is a reaction medium for carrying out the polymerization and is a liquid containing water. The aqueous medium is not particularly limited as long as it contains water, and may contain water and a non-fluorine-containing organic solvent such as an alcohol, an ether, or a ketone and/or a fluorine-containing organic solvent having a boiling point of 40 ℃ or lower.

In the emulsion polymerization, a known chain transfer agent may be further added according to the purpose to adjust the polymerization rate and the molecular weight.

Examples of the chain transfer agent include esters such as dimethyl malonate, diethyl malonate, methyl acetate, ethyl acetate, butyl acetate, and dimethyl succinate, and halogenated hydrocarbons such as isopentane, methane, ethane, propane, isobutane, methanol, ethanol, isopropanol, acetone, various mercaptans, and carbon tetrachloride, and cyclohexane.

As the chain transfer agent, a bromine compound or an iodine compound can be used. Examples of the polymerization method using a bromine compound or an iodine compound include a method of polymerizing a fluorine-containing monomer in an aqueous medium in the substantial absence of oxygen in the presence of a bromine compound or an iodine compound (iodine transfer polymerization method). Representative examples of the bromine compound or iodine compound to be used include compounds represented by the general formula:

R^aI_xBr_y

(wherein x and y are each an integer of 0 to 2 and satisfy 1. ltoreq. x + y. ltoreq.2, R^aIs a saturated or unsaturated fluorocarbon group or chlorofluorocarbon group having 1 to 16 carbon atoms or a hydrocarbon group having 1 to 3 carbon atoms, wherein R is^aWith or without an oxygen atom). By using a bromine compound or an iodine compound, iodine or bromine is introduced into the polymer to function as a crosslinking point.

Examples of the iodine compound include 1, 3-diiodoperfluoropropane, 2-iodoperfluoropropane, 1, 3-diiodo-2-chloroperfluoropropane, 1, 4-diiodoperfluorobutane, 1, 5-diiodo-2, 4-dichloroperfluoropentane, 1, 6-diiodoperfluorohexane, 1, 8-diiodoperfluorooctane, 1, 12-diiodoperfluorododecane, 1, 16-diiodoperfluorohexadecane, diiodomethane, 1, 2-diiodoethane, 1, 3-diiodon-propane, CF ₂Br₂、BrCF₂CF₂Br、CF₃CFBrCF₂Br、CFClBr₂、BrCF₂CFClBr、CFBrClCFClBr、BrCF₂CF₂CF₂Br、BrCF₂CFBrOCF₃1-bromo-2-iodoperfluoroethane, 1-bromo-3-iodoperfluoropropane, 1-bromo-4-iodoperfluorobutane, 2-bromo-3-iodoperfluorobutane, 3-bromo-4-iodoperfluoro-1-butene, 2-bromo-4-iodoperfluoro-1-butene, monoiodomonobromo substituents of benzene, diiodomonobromo substituents, and (2-iodoethyl) and (2-bromoethyl) substituents, and the like, which may be used alone or in combination with each other.

Among these, 1, 4-diiodoperfluorobutane, 1, 6-diiodoperfluorohexane and 2-iodoperfluoropropane are preferably used from the viewpoints of polymerization reactivity, crosslinking reactivity, availability and the like.

The amount of the chain transfer agent is usually 1 to 50,000ppm, preferably 1 to 20,000ppm, based on the total amount of the fluorine-containing monomer to be supplied.

The chain transfer agent may be added to the reaction vessel at a time before the start of polymerization, may be added at a time after the start of polymerization, may be added in several portions during polymerization, or may be continuously added during polymerization.

The aqueous PTFE dispersion can be obtained by the above-described production method. The aqueous PTFE dispersion generally contains the PTFE of the present invention and an aqueous medium. The solid content concentration of the aqueous PTFE dispersion is not limited, and may be, for example, 1.0 to 70 mass%. The solid content concentration is preferably 8.0% by mass or more, more preferably 10.0% by mass or more, and is preferably 60.0% by mass or less, more preferably 50.0% by mass or less.

In the above production method, the amount of adhesion is preferably 3.0% by mass or less, more preferably 2.0% by mass or less, more preferably 1.0% by mass or less, further preferably 0.8% by mass or less, further more preferably 0.7% by mass or less, and particularly preferably 0.6% by mass or less, relative to the finally obtained PTFE.

The use of the PTFE aqueous dispersion is not particularly limited, and examples of direct application in the form of an aqueous dispersion include: a coating layer formed by coating on a substrate, drying, and then baking as needed; impregnation by impregnating a porous support such as a nonwoven fabric or a resin molded article with the resin, drying the impregnated support, and then preferably firing the dried support; examples of the coating film include a cast film formed by coating a substrate such as glass on the substrate, drying the substrate, immersing the substrate in water as needed, and peeling the substrate to obtain a thin film.

The aqueous PTFE dispersion preferably contains substantially no fluorosurfactant. In the aqueous dispersion liquid of the present specification, "the fluorosurfactant is not substantially contained" means that the fluorosurfactant is 10ppm or less with respect to polytetrafluoroethylene. The content of the fluorinated surfactant is preferably 1ppm or less, more preferably 100ppb or less, still more preferably 10ppb or less, still more preferably 1ppb or less, and particularly preferably the detection limit or less of the fluorinated surfactant obtained by measurement by liquid chromatography-mass spectrometry (LC/MS).

The amount of the above-mentioned fluorosurfactant can be determined by a known method. For example, quantification can be performed by LC/MS/MS analysis. First, the obtained aqueous dispersion was extracted into an organic solvent of methanol, and molecular weight information was extracted from the extract by LC/MS spectroscopy to confirm that the molecular weight information agrees with the structural formula of a candidate surfactant.

Then, an aqueous solution having a concentration of 5 levels or more was prepared for the confirmed surfactant, and LC/MS analysis was performed for each concentration to prepare a calibration curve with respect to the area of the region.

The aqueous dispersion obtained was subjected to soxhlet extraction with methanol, and the extract was subjected to LC/MS analysis, whereby quantitative measurement was possible.

The fluorinated surfactant is the same as the fluorinated surfactant exemplified above in the production method of the present invention. For example, the surfactant may contain a fluorine atom having a total carbon number of a portion other than the anionic group of 20 or less, may contain a fluorine atom having a molecular weight of 800 or less in the anionic portion, or may contain a fluorine-containing surfactant having a LogPOW of 3.5 or less.

Examples of the anionic fluorosurfactant include those represented by the general formula (N) ⁰) Specific examples of the compound include compounds represented by the general formula (N)¹) A compound represented by the general formula (N)²) A compound represented by the general formula (N)³) A compound represented by the general formula (N)⁴) A compound represented by the formula (N)⁵) The compound shown in the specification. More specifically, there may be mentioned perfluorocarboxylic acid (I) represented by general formula (I), ω -H perfluorocarboxylic acid (II) represented by general formula (II), perfluoropolyether carboxylic acid (III) represented by general formula (III), perfluoroalkylalkylalkylene carboxylic acid (IV) represented by general formula (IV), perfluoroalkoxy fluorocarboxylic acid (V) represented by general formula (V), perfluoroalkylsulfonic acid (VI) represented by general formula (VI), ω -H perfluorosulfonic acid (VII) represented by general formula (VII), perfluoroalkylalkylalkylene sulfonic acid (VIII) represented by general formula (VIII), alkylalkylalkylene carboxylic acid (IX) represented by general formula (IX), fluorocarboxylic acid (X) represented by general formula (X), alkoxyfluorosulfonic acid (XI) represented by general formula (XI), and compound (XII) represented by general formula (XII).

The aqueous PTFE dispersion may be any of an aqueous dispersion obtained by the polymerization, a dispersion obtained by concentrating or performing dispersion stabilization treatment on the aqueous dispersion, and an aqueous dispersion obtained by dispersing a powder composed of PTFE in an aqueous medium in the presence of the surfactant.

As a method for producing the aqueous PTFE dispersion, a purified aqueous dispersion may be produced by subjecting an aqueous dispersion obtained by the polymerization to the following steps: a step (I) of contacting the resulting product with an anion exchange resin or a mixed bed comprising an anion exchange resin and a cation exchange resin in the presence of a nonionic surfactant; and/or a step (II) of concentrating the aqueous dispersion so that the solid content concentration is 30 to 70% by mass relative to 100% by mass of the aqueous dispersion.

The nonionic surfactant is not particularly limited, and those described later can be used. The anion exchange resin is not particularly limited, and a known one can be used. In addition, the above-mentioned method of contacting with the anion exchange resin may employ a known method.

As a method for producing the aqueous PTFE dispersion, a purified aqueous dispersion can be produced by subjecting the aqueous dispersion obtained by the polymerization to the step (I) and subjecting the aqueous dispersion obtained by the step (I) to the step (II). Alternatively, the purified aqueous dispersion may be produced by performing the step (II) without performing the step (I). The steps (I) and (II) may be repeated, or may be combined.

Examples of the anion exchange resin include resins having a functional group of-N⁺X^-(CH₃)₃Strongly basic anion exchange resin of group (X represents Cl or OH), having-N⁺X^-(CH₃)₃(C₂H₄OH) group (X is the same as above). Specifically, examples thereof include those described in International publication No. 99/62858, International publication No. 03/020836, International publication No. 2004/078836, International publication No. 2013/027850 and International publication No. 2014/084399.

The cation exchange resin is not particularly limited, and examples thereof include those having a functional group of-SO₃ ^-Strongly acidic cation exchange resin having-COO as a functional group^-Among them, a strongly acidic cation exchange resin is preferable, and H is more preferable from the viewpoint of removal efficiency⁺Strong acid cation exchange resins of the type.

The "mixed bed containing a cation exchange resin and an anion exchange resin" is not particularly limited, and includes a case where both are packed in the same column, a case where both are packed in different columns, a case where both are dispersed in an aqueous dispersion, and the like.

As the above concentration method, a known method is used. Specifically, there are methods described in International publication No. 2007/046482 and International publication No. 2014/084399.

Examples thereof include phase separation, centrifugal sedimentation, cloud point concentration, electric concentration, electrophoresis, filtration treatment using ultrafiltration, filtration treatment using a reverse osmosis membrane (RO membrane), nanofiltration treatment, and the like. The concentration may be such that the concentration of PTFE is 30 to 70% by mass depending on the use. The stability of the dispersion may be impaired by concentration, but in this case a dispersion stabilizer may be further added.

The dispersion stabilizer may be added with the nonionic surfactant or various other surfactants.

As the nonionic surfactant, for example, the compounds exemplified as the nucleating agent can be suitably used.

The cloud point of a nonionic surfactant is a measure of the solubility of the surfactant in water. The surfactant used in the aqueous dispersion of the present invention has a cloud point of from about 30 ℃ to about 90 ℃, preferably from about 35 ℃ to about 85 ℃.

The total amount of the dispersion stabilizer is 0.5-20 mass% of the solid content of the dispersion. If less than 0.5 mass%, dispersion stability may be deteriorated; if the amount exceeds 20% by mass, the dispersion effect is not obtained in accordance with the amount of the polymer, and the method is not practical. A more preferable lower limit of the dispersion stabilizer is 2% by mass, and a more preferable upper limit is 12% by mass.

The surfactant can be removed by the above-mentioned concentration operation.

The aqueous dispersion obtained by the above polymerization may be subjected to dispersion stabilization treatment without concentration according to the use, and an aqueous dispersion having a long shelf life may be prepared. The dispersion stabilizer used may be the same as described above.

The use of the aqueous PTFE dispersion is not particularly limited, and examples of direct application in the form of an aqueous dispersion include: a coating layer formed by coating on a substrate, drying, and then baking as needed; impregnation by impregnating a porous support such as a nonwoven fabric or a resin molded article with the resin, drying the impregnated support, and then preferably firing the dried support; examples of the coating film include a cast film formed by coating a substrate such as glass on the substrate, drying the substrate, immersing the substrate in water as needed, and peeling the substrate to obtain a thin film.

The aqueous PTFE dispersion can be used as a coating aqueous coating material by mixing a known compounding agent such as a pigment, a thickener, a dispersant, a defoaming agent, an antifreezing agent, and a film-forming aid, or further compounding with another polymer compound.

In addition, the additives can be used for adhesives, and compounds such as anti-dripping agents, which inhibit the fall-off of the active material of the electrode.

In order to adjust the viscosity of the aqueous PTFE dispersion or to improve the miscibility of a pigment, a filler, and the like, an anionic surfactant may be preferably contained. The anionic surfactant may be appropriately added within a range that causes no problem in terms of economy and environment.

Examples of the anionic surfactant include a non-fluorinated anionic surfactant and a fluorine-containing anionic surfactant, and a non-fluorinated anionic surfactant containing no fluorine, that is, a hydrocarbon anionic surfactant is preferable.

For the purpose of adjusting the viscosity, the type of the anionic surfactant is not particularly limited as long as it is known, and for example, the anionic surfactants described in international publication No. 2013/146950 and international publication No. 2013/146947 can be used. Examples thereof include anionic surfactants having a saturated or unsaturated aliphatic chain having 6 to 40 carbon atoms, preferably 8 to 20 carbon atoms, and more preferably 9 to 13 carbon atoms. The saturated or unsaturated aliphatic chain may be either a straight chain or a branched chain, or may have a cyclic structure. The hydrocarbon may be aromatic or may have an aromatic group. The hydrocarbon may have a hetero atom such as oxygen, nitrogen, or sulfur.

Examples of the anionic surfactant include alkylsulfonates, alkylsulfates, alkylarylsulfates, and salts thereof; aliphatic (carboxylic) acids and salts thereof; alkyl phosphates, alkyl aryl phosphates, or salts thereof; and the like, among which alkyl sulfonates, alkyl sulfates, aliphatic carboxylic acids or salts thereof are preferred.

The alkyl sulfate or a salt thereof is preferably ammonium lauryl sulfate, sodium lauryl sulfate or the like.

As the aliphatic carboxylic acid or a salt thereof, succinic acid, capric acid, undecanoic acid, undecylenic acid, lauric acid, hydrogenated dodecanoic acid, or a salt thereof is preferable.

The amount of the anionic surfactant to be added depends on the kind of the anionic surfactant or other compounding agent, and is preferably 10ppm to 5000ppm based on the solid content of PTFE.

The lower limit of the amount of the anionic surfactant to be added is more preferably 50ppm or more, and still more preferably 100ppm or more. If the amount of addition is too small, the viscosity adjusting effect is poor.

The upper limit of the amount of the anionic surfactant to be added is more preferably 3000ppm or less, and still more preferably 2000ppm or less. If the amount is too large, the mechanical stability and storage stability of the aqueous dispersion may be impaired.

For the purpose of adjusting the viscosity of the aqueous PTFE dispersion, for example, methylcellulose, alumina sol, polyvinyl alcohol, carboxylated vinyl polymer, and the like may be blended in addition to the anionic surfactant.

For the purpose of adjusting the pH of the aqueous dispersion, a pH adjuster such as ammonia water may be added.

The aqueous PTFE dispersion may contain other water-soluble polymer compounds as necessary within a range not impairing the characteristics of the aqueous dispersion.

The other water-soluble polymer compound is not particularly limited, and examples thereof include polyethylene oxide (dispersion stabilizer), polyethylene glycol (dispersion stabilizer), polyvinylpyrrolidone (dispersion stabilizer), phenol resin, urea resin, epoxy resin, melamine resin, polyester resin, polyether resin, acrylic silicone resin, silicone polyester resin, and polyurethane resin.

In addition, preservatives such as isothiazolone, azole, bronopol, chlorothalonil, methylsulfonyltetrachloropyridine, carbendazim, 2- [ (dichlorofluoromethyl) -thio ] -1H-isoindole-1, 3- (2H) -dione (Fluor Folpet), sodium diacetate, diiodomethyl-p-tolylsulfone and the like may be contained.

The PTFE of the present invention can further be suitably obtained by a production method comprising at least 1 of the following steps:

a step of recovering the aqueous PTFE dispersion obtained by the above-mentioned method;

a step of coagulating PTFE in the aqueous PTFE dispersion;

a step of recovering the coagulated PTFE; and

drying the recovered PTFE at 100 to 300 ℃.

The upper limit of the drying temperature is preferably 250 ℃.

The powder can be produced by agglomerating PTFE contained in the aqueous dispersion. The PTFE of the present invention may be a powder. The aqueous dispersion of PTFE can be coagulated, washed, and dried to prepare a powder for various uses. When the aqueous dispersion of PTFE is coagulated, an aqueous dispersion obtained by polymerization such as a polymer emulsion is usually diluted with water to a polymer concentration of 10 to 20 mass%, and in some cases, after adjusting the pH to neutral or alkaline, the aqueous dispersion is stirred in a vessel with a stirrer more vigorously than the stirring during the reaction. In the coagulation, a water-soluble organic compound such as methanol or acetone, an inorganic salt such as potassium nitrate or ammonium carbonate, an inorganic acid such as hydrochloric acid, sulfuric acid or nitric acid, or the like may be added as a precipitating agent and stirred simultaneously. The coagulation can also be continuously carried out using a line mixer or the like.

Before or during the coagulation, a pigment for coloring or various fillers for improving mechanical properties are added to obtain a pigment-or filler-containing PTFE powder in which a pigment or a filler is uniformly mixed.

The wet powder obtained by coagulating the PTFE is usually dried by vacuum, high frequency, hot air, or other means while keeping the wet powder in a state in which it hardly flows, preferably in a state in which it is left standing. Friction between powders, particularly at high temperatures, often adversely affects PTFE in the fine powder form. This is because such particles composed of PTFE have a property that they simply fibrillate even when subjected to a small shear force, losing the state of the original stable particle structure. The drying may be carried out at a drying temperature of 10 to 300 ℃, preferably 100 to 300 ℃. The upper limit of the drying temperature is preferably 250 ℃.

When the PTFE of the present invention is a powder, the average particle diameter (average secondary particle diameter) of the powder is preferably 100 to 2000 μm. The lower limit of the average secondary particle size is more preferably 200 μm or more, and still more preferably 300 μm or more. The upper limit of the average secondary particle size is preferably 1000 μm or less, more preferably 800 μm or less, and particularly preferably 700 μm or less. The average particle diameter is a value measured in accordance with JIS K6891.

The powder preferably contains substantially no fluorosurfactant. In the powder of the present specification, "the fluorosurfactant is not substantially contained" means that the fluorosurfactant is 10ppm or less with respect to polytetrafluoroethylene. The content of the fluorinated surfactant is preferably 1ppm or less, more preferably 100ppb or less, still more preferably 10ppb or less, still more preferably 1ppb or less, and particularly preferably the detection limit or less of the fluorinated surfactant obtained by measurement by liquid chromatography-mass spectrometry (LC/MS).

The amount of the above-mentioned fluorosurfactant can be determined by a known method. For example, quantification can be performed by LC/MS/MS analysis. First, the obtained powder was extracted into an organic solvent of methanol, and molecular weight information was extracted from the extract by LC/MS spectroscopy to confirm that the molecular weight information agrees with the structural formula of a candidate surfactant.

Then, an aqueous solution having a concentration of 5 levels or more was prepared for the confirmed surfactant, and LC/MS analysis was performed for each concentration to prepare a calibration curve with respect to the area of the region.

The obtained powder was subjected to soxhlet extraction with methanol, and the extract was subjected to LC/MS analysis, whereby quantitative measurement was possible.

The above-mentioned fluorosurfactant is the same as that exemplified in the above-mentioned production method. For example, the surfactant may contain a fluorine atom having a total carbon number of a portion other than the anionic group of 20 or less, may contain a fluorine atom having a molecular weight of 800 or less in the anionic portion, or may contain a fluorine-containing surfactant having a LogPOW of 3.5 or less.

Examples of the anionic fluorosurfactant include those represented by the general formula (N)⁰) Specific examples of the compound include compounds represented by the general formula (N)¹) A compound represented by the general formula (N)²) A compound represented by the general formula (N)³) A compound represented by the general formula (N)⁴) A compound represented by the formula (N)⁵) The compound shown in the specification. More specifically, there may be mentioned perfluorocarboxylic acid (I) represented by general formula (I), ω -H perfluorocarboxylic acid (II) represented by general formula (II), perfluoropolyether carboxylic acid (III) represented by general formula (III), perfluoroalkylalkylalkylene carboxylic acid (IV) represented by general formula (IV), perfluoroalkoxy fluorocarboxylic acid (V) represented by general formula (V), perfluoroalkylsulfonic acid (VI) represented by general formula (VI), ω -H perfluorosulfonic acid (VII) represented by general formula (VII), perfluoroalkylalkylalkylene sulfonic acid (VIII) represented by general formula (VIII), alkylalkylalkylene carboxylic acid (IX) represented by general formula (IX), fluorocarboxylic acid (X) represented by general formula (X), alkoxyfluorosulfonic acid (XI) represented by general formula (XI), and compound (XII) represented by general formula (XII).

The PTFE of the present invention has stretchability and non-melt processability, and is also useful as a raw material for stretched products (porous bodies). The PTFE of the present invention can be stretched to obtain a stretched product having excellent breaking strength and stress relaxation time. For example, a stretched body can be obtained by paste-extruding a powder of the PTFE of the present invention mixed with an extrusion aid, rolling the paste as necessary, drying the paste to remove the extrusion aid, and stretching the paste in at least 1 direction. By stretching, the PTFE of the present invention is easily fibrillated to form a stretched body composed of nodules and fibers. The stretched body may be a porous body having a high porosity.

The present invention also relates to a stretched body containing the PTFE.

The stretched body of the present invention can be produced as follows: the above PTFE is paste extruded and rolled, and then is unfired or semi-fired, and stretched in at least 1 direction (preferably, roll stretched in the rolling direction, and then stretched in the width direction by a tenter). The stretching conditions are preferably a speed of 5 to 1000%/sec and a stretching ratio of 500% or more. By stretching, PTFE is easily fibrillated to form a stretched body composed of nodules and fibers. The porosity of the stretched product is not particularly limited, but is preferably in the range of 50 to 99%. The stretched body of the present invention may contain only PTFE, or may contain PTFE and the above-described pigment and filler, but preferably contains only PTFE.

The peak temperature of the stretched body of the present invention is preferably 325 to 350 ℃. In addition, the peak temperature of the stretched body of the present invention is preferably between 325 ℃ to 350 ℃ and 360 ℃ to 390 ℃. The peak temperature is a temperature corresponding to the maximum value in the heat of fusion curve when the temperature of the stretched material is raised at a rate of 10 ℃/min using a differential scanning calorimeter [ DSC ].

The tensile body of the present invention has a breaking strength of more preferably 13.0N or more, further preferably 16.0N or more, further preferably 19.0N or more, further preferably 22.0N or more, further preferably 23.0N or more, further preferably 25.0N or more, further preferably 28.0N or more, further preferably 29.0N or more, further preferably 30.0N or more, further preferably 32.0N or more, further preferably 35.0N or more, further preferably 37.0N or more, further preferably 40.0N or more. The higher the breaking strength, the better, the breaking strength may be 100N or less, 80.0N or less, or 50.0N or less.

The breaking strength of the above-mentioned tensile member was determined by holding the tensile member between movable jaws each having a gauge length of 5.0cm, and performing a tensile test at a speed of 300 mm/min at 25 ℃.

The stress relaxation time of the stretched body of the present invention is preferably 50 seconds or more, more preferably 80 seconds or more, further preferably 100 seconds or more, may be 120 seconds or more, may be 150 seconds or more, may be 190 seconds or more, may be 200 seconds or more, may be 220 seconds or more, may be 240 seconds or more, and may be 300 seconds or more. The stress relaxation time is a value measured by the following method.

Regarding the stress relaxation time of the above-described tensile body, both ends of the tensile body were attached to fixing tools, a sample of a total length of 8 inches (20cm) was made to be tensioned, the oven was maintained at 390 ℃, and the fixing tools were inserted into the oven through slits located at the sides (covered) of the oven. The time required from the time of insertion into the oven until the sample broke was taken as the stress relaxation time.

The porosity of the stretched product of the present invention is preferably in the range of 30% to 99%. The porosity is preferably 60% or more, more preferably 70% or more. If the proportion of PTFE in the stretched product is too small, the strength of the stretched product may be insufficient, and therefore the porosity is preferably 98% or less, preferably 95% or less, and more preferably 90% or less.

The porosity of the stretched body can be calculated from the following equation using the apparent density ρ.

Porosity (%) [ (2.2- ρ)/2.2] × 100

In the above formula, 2.2 is the true density (g/cm) of PTFE³)。

In the case where the stretched body is a film or a sheet, the density ρ of the stretched body is calculated from the mass and the film thickness of the sample measured by measuring the mass of the sample cut into a specific size with a precision balance.

ρ＝M/(4.0×12.0×t)

ρ ═ density (film density) (g/cm)³)

Mass (g)

thickness (cm) of film

The above measurement and calculation were performed for three sites, and the average value thereof was taken as the film density.

The film thickness was measured by using a film thickness meter, and the total film thickness was measured by overlapping 5 stretched materials, and the value obtained was divided by 5 to obtain a film thickness of 1 sheet.

When the stretched body is cylindrical, the mass of a sample cut to a predetermined length is measured with a precision balance with respect to the density ρ of the stretched body, and the density of the sample is calculated from the mass and the outer diameter of the measured sample by the following equation.

ρ＝M/(r×r×π)×L

Rho ═ density (g/cm)³)

Mass (g)

radius (cm)

Length (cm)

Pi-circumference ratio

The outer diameter of the stretched body was measured using a laser displacement sensor. The radius is a value obtained by dividing the value by 2.

The above measurement and calculation were performed for three sites, and the average value of these was taken as the density.

The stretched body of the present invention preferably contains substantially no fluorosurfactant. In the stretched product of the present specification, "the fluorinated surfactant is not substantially contained" means that the fluorinated surfactant is 10ppm or less with respect to polytetrafluoroethylene. The content of the fluorinated surfactant is preferably 1ppm or less, more preferably 100ppb or less, still more preferably 10ppb or less, still more preferably 1ppb or less, and particularly preferably the detection limit or less of the fluorinated surfactant obtained by measurement by liquid chromatography-mass spectrometry (LC/MS).

The amount of the above-mentioned fluorosurfactant can be determined by a known method. For example, quantification can be performed by LC/MS/MS analysis. First, the obtained fine stretched product was extracted into an organic solvent of methanol, and molecular weight information was extracted from the extract by LC/MS spectroscopy to confirm that the molecular weight information agrees with the structural formula of a candidate surfactant.

Then, an aqueous solution having a concentration of 5 levels or more was prepared for the confirmed surfactant, and LC/MS analysis was performed for each concentration to prepare a calibration curve with respect to the area of the region.

The obtained fine stretched product was subjected to soxhlet extraction with methanol, and the extract solution was subjected to LC/MS analysis, whereby quantitative measurement was possible.

The fluorinated surfactant is the same as the fluorinated surfactant exemplified above in the production method of the present invention. For example, the surfactant may contain a fluorine atom having a total carbon number of a portion other than the anionic group of 20 or less, may contain a fluorine atom having a molecular weight of 800 or less in the anionic portion, or may contain a fluorine-containing surfactant having a LogPOW of 3.5 or less.

Examples of the anionic fluorosurfactant include those represented by the general formula (N)⁰) Specific examples of the compound include compounds represented by the general formula (N)¹) A compound represented by the general formula (N)²) A compound represented by the general formula (N)³) A compound represented by the general formula (N)⁴) A compound represented by the formula (N)⁵) The compound shown in the specification. More specifically, there may be mentioned perfluorocarboxylic acid (I) represented by general formula (I), ω -H perfluorocarboxylic acid (II) represented by general formula (II), perfluoropolyether carboxylic acid (III) represented by general formula (III), perfluoroalkylalkylalkylene carboxylic acid (IV) represented by general formula (IV), perfluoroalkoxy fluorocarboxylic acid (V) represented by general formula (V), perfluoroalkylsulfonic acid (VI) represented by general formula (VI), ω -H perfluorosulfonic acid (VII) represented by general formula (VII), perfluoroalkylalkylalkylene sulfonic acid (VIII) represented by general formula (VIII), alkylalkylalkylene carboxylic acid (IX) represented by general formula (IX), fluorocarboxylic acid (X) represented by general formula (X), alkoxyfluorosulfonic acid (XI) represented by general formula (XI), and compound (XII) represented by general formula (XII).

The stretched body of the present invention is also preferably in the form of a film, a tube, a fiber, or a rod.

When the stretched product of the present invention is a film (stretched film or porous film), stretching can be performed by a known PTFE stretching method.

Preferably, the uniaxially stretched film can be obtained by roll-stretching the paste extrudate in a sheet or rod shape in the extrusion direction.

Further, a biaxially stretched film can also be obtained by stretching in the width direction with a tenter or the like.

It is also preferable to perform a semi-firing treatment before stretching.

The stretched body of the present invention is a porous body having a high porosity, and can be suitably used as a filter medium for various precision filtration filters such as air filters and reagent filters, a support material for polymer electrolyte membranes, and the like.

Further, the resin composition is also useful as a material for products used in the fields of fibers, medical treatment, electrochemistry, sealing materials, air filtration, ventilation/internal pressure control, liquid filtration, general consumables, and the like.

Specific applications are exemplified below.

Field of electrochemistry

Dielectric prepreg, EMI shielding material, heat transfer material, and the like. More specifically, a printed circuit board, an electromagnetic shielding material, an insulating heat transfer material, an insulating material, and the like.

Field of sealing materials

Gaskets, pump diaphragms, pump pipes, aircraft seals, and the like.

The field of air filtration

ULPA filters (for semiconductor manufacturing), HEPA filters (for hospital and semiconductor manufacturing), cylindrical cartridge filters (for industrial use), bag filters (for industrial use), heat-resistant bag filters (for exhaust gas treatment), heat-resistant pleated filters (for exhaust gas treatment), SINBRAN filters (for industrial use), catalytic filters (for exhaust gas treatment), filters with adsorbents (for HDD assembly), breather filters (for HDD assembly and the like), filters for vacuum cleaners (for vacuum cleaners), general-purpose multilayer felt materials, cartridge filters for GT (for GT compatible interchange), cooling filters (for electronic equipment housings), and the like.

Ventilation/internal pressure regulation field

A material for freeze drying such as a freeze drying container, a ventilation material for automobiles suitable for an electronic circuit or a lamp, a container suitable for container use such as a container cover, a protective ventilation use suitable for electronic equipment including a small terminal such as a tablet terminal or a mobile phone terminal, a medical ventilation use, and the like.

Field of liquid filtration

A semiconductor liquid filtration filter (for semiconductor production), a hydrophilic PTFE filter (for semiconductor production), a filter suitable for chemicals (for reagent treatment), a filter for a pure water production line (for pure water production), a backwashing type liquid filtration filter (for industrial wastewater treatment), and the like.

General field of consumable materials

Clothing, cable guide tubes (suitable for movable wires for motorcycles), clothing for motorcycles, cast pads (medical protectors), dust collector filters, horns (musical instruments), cables (signal cables for guitars, etc.), strings (for string instruments), etc.

Field of fiber

PTFE fibers (fibrous materials), sewing threads (fabrics), knitting threads (fabrics), ropes, and the like.

Medical field

In vivo implants (stretchings), artificial blood vessels, catheters, general surgery (tissue augmentation materials), head and neck articles (dura mater substitutes), oral health (tissue regeneration medicine), plastic surgery (taping), and the like.

Examples

The present invention will be described with reference to examples, but the present invention is not limited to the examples.

In the examples, the measurement of each physical property was performed by the following method.

(1) Standard Specific Gravity (SSG)

The measurement was carried out by the underwater substitution method according to ASTM D-792 using a sample molded according to ASTM D4895-89.

(2) Thermal Instability Index (TII)

Measured according to ASTM D4895-89.

(3) Polymer solid content

1g of the aqueous PTFE dispersion was dried in a forced air dryer at 150 ℃ for 60 minutes, and a value representing the ratio of the mass of the heating residue to the mass (1g) of the aqueous dispersion in percent was used.

(4) Average primary particle diameter

The aqueous PTFE dispersion was diluted with water to a solid content concentration of 0.15 mass%, and the transmittance of 550nm projection light per unit length of the resulting diluted emulsion and the number-based length-average particle diameter determined by measuring the orientation diameter from a transmission electron micrograph were measured to prepare a calibration curve. Using this calibration curve, the average primary particle size was determined from the measured transmittance of 550nm projected light for each sample.

(5) Determination of the extrusion pressure

21.7g of a lubricant (trade name: Isopar H (registered trademark), manufactured by Exxon corporation) was added to 100g of the fine powder, and the mixture was mixed in a glass bottle at room temperature for 3 minutes. Next, the glass bottle was left at room temperature (25 ℃ C.) for at least 1 hour before extrusion to obtain a lubricating resin. Lubricating resin was passed through a hole (diameter 2.5mm, land length 11mm, lead-in angle 30 °) at room temperature at a rate of 100: a uniform bead (extrusion molded article) was obtained by paste extrusion at a reduction ratio of 1. The extrusion speed, i.e., the ram speed, was set to 20 inches/minute (51 cm/minute). The extrusion pressure is a value obtained as follows: the extrusion pressure is determined as a value obtained by measuring the load at which the extrusion load reaches an equilibrium state in paste extrusion, and dividing the load by the cross-sectional area of the cylinder used for paste extrusion.

(6) Tensile test

The beads obtained by the above paste extrusion were heated at 230 ℃ for 30 minutes, whereby the lubricant was removed from the beads. Next, the beads (extrusion molded articles) were cut into appropriate lengths, each end was fixed to a chuck at a chuck interval of 1.5 inches (38mm), and heated to 300 ℃ in an air circulating furnace. Next, the chucks are separated at a desired speed (elongation speed) to a separation distance corresponding to a desired elongation (total elongation), and an elongation test is performed. The elongation process is essentially as disclosed in U.S. Pat. No. 4,576,869, except that the extrusion rate (51 cm/min, not 84 cm/min) is different. "elongation" refers to an increase in length caused by stretching, and is usually expressed in relation to the original length. In the above production method, the elongation rate is 1000%/second, and the total elongation is 2400%.

(7-1) breaking Strength A

The tensile beads (prepared by elongating beads) obtained in the above tensile test were held and fixed by a movable jaw having a gauge length of 5.0cm, and a tensile test was performed at a speed of 300 mm/min at 25 ℃.

(7-2) breaking Strength B

Tensile beads were obtained in the same manner as in the above tensile test except that the collet spacing was changed to 2.0 inches (51mm) and the elongation rate was changed to 100%/second, and the obtained tensile beads were subjected to a tensile test at 25 ℃ and at a rate of 300 mm/min, and the strength at break was measured as the break strength B.

(7-3) breaking Strength C

The obtained wet PTFE powder was dried at 285 ℃ for 18 hours to obtain PTFE powder. The obtained PTFE powder was extruded by the same method as the method for measuring the extrusion pressure to obtain beads. The obtained beads were subjected to the same method as in the tensile test described above to obtain tensile beads. The obtained stretched beads were subjected to a tensile test at a rate of 300 mm/min at 25 ℃ and the strength at break was measured as break strength C.

(7-4) breaking Strength D

The obtained wet PTFE powder was dried at 285 ℃ for 18 hours to obtain PTFE powder. The obtained PTFE powder was extruded by the same method as the method for measuring the extrusion pressure to obtain beads. Tensile beads were obtained in the same manner as in the measurement of the breaking strength C described above, except that the collet spacing was changed to 2.0 inches (51mm) and the elongation rate was changed to 100%/second in the tensile test. The obtained stretched beads were subjected to a tensile test at a rate of 300 mm/min at 25 ℃ and the strength at break was measured as the breaking strength D.

(8) Stress relaxation time

Both ends of the stretched beads obtained in the above-described tensile test were attached to a fixing tool to prepare a bead sample of a total length of 8 inches (20cm) which was pulled tight. The oven was held at 390 ℃ and the fixture was inserted into the oven through a slit located in the side of the oven (covered). The time required from the moment of insertion into the oven until the bead sample broke was determined as the stress relaxation time.

(9) Appearance of stretched article

The appearance of the stretched beads (produced by stretching the beads) obtained in the above-described tensile test was visually observed.

(10) 0.1% weight loss temperature

About 10mg of powder which had not been heated to a temperature of 300 ℃ or higher was precisely weighed, and the powder was stored in a dedicated aluminum pan to measure TG. DTA (differential thermal/thermogravimetric simultaneous measurement apparatus). With respect to the 0.1% weight loss temperature, the aluminum plate was heated at 10 ℃/min in a temperature range of 25 ℃ to 600 ℃ under an atmospheric atmosphere, and the temperature corresponding to the point at which the weight was reduced by 0.1 mass% was defined as the 0.1% weight loss temperature.

(11) 1.0% weight loss temperature

About 10mg of powder which had not been heated to a temperature of 300 ℃ or higher was precisely weighed, and the powder was stored in a dedicated aluminum pan to measure TG. DTA (differential thermal/thermogravimetric simultaneous measurement apparatus). With respect to the 1.0% weight loss temperature, the aluminum plate was heated at 10 ℃/min in the temperature range of 25 ℃ to 600 ℃ under the atmospheric atmosphere, and the temperature corresponding to the point at which the weight was reduced by 0.1 mass% was defined as the 0.1% weight loss temperature.

(12) Brightness (L)

210g of the powder was filled into a mold having an inner diameter of 50mm, and it took about 30 seconds to apply pressure until the final pressure reached about 200kg/cm²Then, the pressure was maintained for 5 minutes to prepare a preform. The preform was taken out from the mold, heat-treated in a hot air circulating electric furnace at 100 ℃ for 2 hours, 200 ℃ for 4 hours, and 370 ℃ for 5 hours, and then cooled to room temperature at a rate of 50 ℃/hour to obtain a cylindrical fired body. The fired body was cut along the side surfaces to produce a tape-shaped sheet having a thickness of 0.5 mm. The test piece was cut into a size of 100mm × 50mm from the strip, and the luminance (L;) of the strip was measured by a color difference meter (CR-400, manufactured by konica minolta optical corporation).

(13) Thermal shrinkage rate

210g of the powder was filled into a mold having an inner diameter of 50mm, and it took about 30 seconds to apply pressure until the final pressure reached about 200kg/cm²Then, the pressure was maintained for 5 minutes to prepare a preform. The preform was taken out of the mold, and the diameter (a) of the preform was measured. Thereafter, the preform is placed inAfter heat treatment at 100 ℃ for 2 hours, 200 ℃ for 4 hours, and 370 ℃ for 5 hours in a hot air circulation electric furnace, the temperature was lowered at a rate of 50 ℃/hour to room temperature to obtain a cylindrical fired body. The diameter (B) of the obtained fired body was measured, and the thermal shrinkage was calculated from the following equation.

Heat shrinkage ratio ((a) - (B))/(a) × 100

(14) Contact angle

210g of the powder was filled into a mold having an inner diameter of 50mm, and it took about 30 seconds to apply pressure until the final pressure reached about 200kg/cm²Then, the pressure was maintained for 5 minutes to prepare a preform. The preform was taken out from the mold, heat-treated in a hot air circulating electric furnace at 100 ℃ for 2 hours, 200 ℃ for 4 hours, and 370 ℃ for 5 hours, and then cooled to room temperature at a rate of 50 ℃/hour to obtain a cylindrical fired body. The fired body was cut along the side surfaces to produce a tape-shaped sheet having a thickness of 0.5 mm. The test piece was cut into a size of 50mm × 50mm from the strip, and the contact angle of the surface corresponding to the inner side of the strip was measured by a portable contact goniometer (PCA-1, manufactured by Kyowa interface chemical Co., Ltd.). The contact angle was calculated as follows: a water droplet is dropped onto a test piece, the shape of the droplet is introduced in a pattern by a CCD camera, the radius (r) and the height (h) of the droplet image are obtained by image processing, and the contact angle is calculated by substituting the following equation. (theta/2 method)

θ＝2arctan(h/r)

(15) Peak temperature

About 10mg of powder which had not been heated to a temperature of 300 ℃ or higher was precisely weighed, and the powder was stored in a dedicated aluminum pan to measure TG. DTA (differential thermal/thermogravimetric simultaneous measurement apparatus). As for the peak temperature, the temperature of the aluminum plate was raised in the temperature range of 25 ℃ to 600 ℃ at 10 ℃/min under the atmospheric atmosphere, and the temperature corresponding to the minimum value of the Differential Thermal (DTA) curve was taken as the peak temperature.

(16) Melting Point

About 10mg of powder which had not been heated to a temperature of 300 ℃ or higher was precisely weighed, and the powder was stored in a dedicated aluminum pan to measure TG. DTA (differential thermal/thermogravimetric simultaneous measurement apparatus). The melting point was determined by raising the temperature of the aluminum plate at 10 ℃/min in the temperature range of 25 ℃ to 600 ℃ in the atmospheric atmosphere and setting the temperature corresponding to the minimum value of the differential thermal energy (DTA) curve as the melting point.

Synthesis example 1

10-undecen-1-ol (16g), 1, 4-benzoquinone (10.2g), DMF (160mL), water (16mL) and PdCl₂(0.34g) the mixture was heated and stirred at 90 ℃ for 12 hours.

After that, the solvent was distilled off under reduced pressure. The resulting residue was purified by liquid separation and column chromatography to give 11-hydroxyundecan-2-one (15.4 g).

The spectral data of the 11-hydroxyundecan-2-one obtained are shown below.

1H-NMR(CDCl3)δppm：1.29-1.49(m,14H)、2.08(s,3H)、2.45(J＝7.6,t,2H)、3.51(J＝6.5,t,2H)

A mixture of 11-hydroxyundecan-2-one (13g), sulfur trioxide triethylamine complex (13.9g), and tetrahydrofuran (140mL) was stirred at 50 ℃ for 12 hours. To the reaction solution was added dropwise a solution of sodium methoxide (3.8g) in methanol (12 mL).

The precipitated solid was filtered under reduced pressure and washed with ethyl acetate to give sodium 10-oxoundecylsulfate (15.5g) (hereinafter referred to as surfactant A). The spectral data of the resulting sodium 10-oxoundecyl sulfate are shown below.

1H-NMR(CDCl3)δppm：1.08(J＝6.8,m,10H)、1.32(m,2H)、1.45(m,2H)、1.98(s,3H)、2.33(J＝7.6,t,2H)、3.83(J＝6.5,t,2H)

Synthesis example 2

A glass reactor having an internal volume of 1L and equipped with a stirrer was charged with 588.6g of deionized water and 70.0g of surfactant A, the reactor was sealed, and the inside of the system was replaced with nitrogen gas to remove oxygen. The reactor was warmed to 90 ℃ and pressurized to 0.4MPa with nitrogen. 41.4g of Ammonium Persulfate (APS) was charged and stirred for 3 hours. Stopping stirring, removing pressure until the reactor reaches atmospheric pressure, and cooling to obtain surfactant aqueous solution B.

Example 1

3600g of deionized and deaerated water, 180g of paraffin wax and 0.540g of a surfactant A were charged into a SUS reactor having an internal volume of 6L and equipped with a stirrer, the reactor was sealed, and the system was purged with nitrogen gas to remove oxygen. The reactor was heated to 70 ℃ and TFE was charged into the reactor to make the reactor 2.70 MPa. As a polymerization initiator, 0.620g of Ammonium Persulfate (APS) and 1.488g of succinyl peroxide (DSP) were charged. TFE was fed so that the reaction pressure was fixed at 2.70 MPa. The surfactant aqueous solution B was continuously started to be fed simultaneously with the start of feeding TFE. When 1400g of TFE was charged, the stirring was stopped, and the pressure was released until the reactor reached atmospheric pressure. 103g of an aqueous surfactant solution B was charged until the reaction was terminated. The contents were taken out of the reactor, cooled, and paraffin was separated to obtain an aqueous PTFE dispersion.

The solid content of the obtained PTFE aqueous dispersion was 28.0 mass%, and the average primary particle diameter was 322 nm.

The obtained PTFE aqueous dispersion was diluted with deionized water to a solid content of about 10 mass%, and was coagulated with high-speed stirring. The solidified wet powder was dried at 210 ℃ for 18 hours. The obtained PTFE powder was measured for various physical properties. The results are shown in tables 1 and 2.

The melting point was 339 ℃ which was the same as the peak temperature.

Example 2

An aqueous PTFE dispersion was obtained in the same manner as in example 1 except that 20g of deionized and degassed water containing 0.76g of hydroquinone dissolved therein was added to 540g of TFE, and stirring was stopped at the time of charging 1200g of TFE.

The solid content of the obtained PTFE aqueous dispersion was 25.9 mass%, and the average primary particle diameter was 290 nm.

The physical properties of the obtained PTFE powder were measured in the same manner as in example 1. The results are shown in tables 1 and 2.

The melting point was 344 ℃ which was the same as the peak temperature.

Example 3

3480g of deionized water, 100g of paraffin wax and 0.122g of surfactant A were charged into a SUS reactor having an internal volume of 6L and equipped with a stirrer, the reactor was sealed, and the system was purged with nitrogen to remove oxygen. Next, the contents of the reactor were warmed to 60 ℃ and further replaced with TFE. TFE was added to the reactor to a pressure of 0.73 MPa. 420mg of Ammonium Persulfate (APS) initiator and 700mg of succinyl peroxide (DSP) dissolved in 20g of deionized water were injected into the reactor to a pressure of 0.78 MPa. After the initiator was injected, a decrease in pressure occurred and polymerization was observed to start. TFE was charged so that the reaction pressure was constant at 0.78 MPa. Immediately after the polymerization started, the aqueous surfactant solution B was continuously added to the reactor. TFE monomer was charged into the reactor under pressure, and the stirring was stopped when 740g of TFE had been charged, to terminate the reaction. 36.8g of the aqueous surfactant solution B was charged until the reaction was terminated. Thereafter, the pressure in the reactor was vented to normal pressure, and the contents were taken out of the reactor and cooled. After cooling, the paraffin wax was removed from the aqueous PTFE dispersion.

The solid content of the obtained PTFE aqueous dispersion was 17.5 mass%, and the average primary particle diameter was 317 nm.

The obtained PTFE aqueous dispersion was diluted with deionized water to a solid content of about 10 mass%, coagulated under high-speed stirring, and separated into coagulated wet powder and precipitation drainage. The solidified wet powder was dried at 210 ℃ for 18 hours. The obtained PTFE powder was measured for various physical properties. The results are shown in tables 1 and 2.

The melting point was 344 ℃ which was the same as the peak temperature.

Preparation example 1

To 16g of deionized water was added 0.273g of lauric acid, and while stirring, 2.77g of a 2.8% ammonia aqueous solution was slowly added to obtain an aqueous solution C.

Preparation example 2

To 100g of deionized water was added 10g of lauric acid, and while stirring, 25g of a 10% ammonia aqueous solution was slowly added to obtain an aqueous solution D. The pH at this point was 9.6.

Example 4

1748g of deionized water, 90g of paraffin wax, aqueous solution C and 0.5g of ammonium oxalate were charged into a 3L SUS-made reactor equipped with a stirrer. The pH of the aqueous dispersion at this time was 9.0. The reactor was sealed, and the inside of the system was replaced with nitrogen gas to remove oxygen. The reactor was heated to 70 ℃ and 2.0g of HFP was added, and the pressure was increased by TFE to 2.70 MPa. As a polymerization initiator, 0.5 mass% of an aqueous potassium permanganate solution was continuously fed into the reactor to carry out the reaction. TFE was charged so that the reaction pressure was constant at 2.70 MPa. Stirring was stopped when 80g of TFE was charged, and the pressure was released until the reaction pressure reached atmospheric pressure. Immediately, TFE was charged into the reactor to make the reaction pressure 2.70MPa, and the reaction was continued with restarting stirring.

The continuous feeding of the aqueous solution D into the reactor was immediately started. When 590g of TFE were charged, the stirring was stopped, and the pressure was released until the reactor reached atmospheric pressure. 72.4g of aqueous potassium permanganate solution and 30g of aqueous solution D were introduced until the end of the reaction. The aqueous dispersion was taken out of the reactor, cooled, and paraffin was separated to obtain an aqueous PTFE dispersion. The pH of the obtained PTFE aqueous dispersion was 8.3.

The obtained PTFE aqueous dispersion was diluted with water to a concentration of 10%, and then coagulated under high-speed stirring and separated from water to obtain wet PTFE powder. The resulting wet PTFE powder was dried at 240 ℃ for 18 hours. The physical properties of the obtained PTFE powder are shown in tables 2 to 4 below.

Example 5

The reaction was carried out in the same manner as in example 4, and the stirring was stopped when 680g of TFE were charged. 56.0g of aqueous potassium permanganate solution and 26.2g of aqueous solution D were introduced until the end of the reaction. The pH of the resulting aqueous PTFE dispersion was 8.8.

Coagulation and drying were carried out in the same manner as in example 4. The physical properties of the obtained PTFE powder are shown in tables 2 to 4 below.

Preparation example 3

To 100g of deionized water was added 9.9g of lauric acid, and 14g of a 10% ammonia aqueous solution was poured while stirring to obtain an aqueous solution E. The pH at this point was 9.5.

Example 6

The reaction vessel was charged with the same operation as in example 4 except that 0.273g of lauric acid was used instead of the aqueous solution C. The pH of the aqueous dispersion at this time was 6.7.

Thereafter, the reaction was carried out in the same manner as in example 4. The reaction was continued in the same manner as above except that the aqueous solution E was continuously fed into the reactor in place of the aqueous solution D during the reaction. Stirring was stopped when 800g of TFE was charged, and the same operation as in example 4 was performed. 52.2g of aqueous potassium permanganate solution and 25.5g of aqueous solution E were added to the reactor until the end of the reaction.

The pH of the resulting aqueous PTFE dispersion was 8.2. Coagulation and drying were carried out in the same manner as in example 4. The physical properties of the obtained PTFE powder are shown in tables 2 to 4 below.