阅读说明：本技术 拒水拒油剂组合物、拒水拒油处理方法和拒水拒油性纤维 (Water-and oil-repellent agent composition, water-and oil-repellent treatment method, and water-and oil-repellent fiber ) 是由 村田直树 中川康宏 于 2020-11-04 设计创作，主要内容包括：本发明提供基材吸附性高、并且能够赋予基材高拒油性和拒水性的拒水拒油剂组合物.拒水拒油性纤维。拒水拒油剂组合物,含有共聚物(A)、阳离子性表面活性剂(B)、水性介质(C)和聚醚改性聚二甲基硅氧烷(D),水性介质(C)中分散存在有含有共聚物(A)的粒子,共聚物(A)含有由单体a1所产生的结构单元和由单体a2所产生的结构单元,单体a1由(甲基)丙烯酰氧基以外的部分为烃结构的(甲基)丙烯酸烷基酯组成,单体a2由具有烯属不饱和基和酰胺基的化合物组成,聚醚改性聚二甲基硅氧烷(D)是聚二甲基硅氧烷的甲基的氢原子的一部分或全部被聚醚链取代而成的化合物。(The invention provides a water-and oil-repellent agent composition which has high substrate adsorbability and can endow a substrate with high oil repellency and water repellency. A water/oil repellent composition comprising a copolymer (A), a cationic surfactant (B), an aqueous medium (C) and a polyether-modified polydimethylsiloxane (D), wherein particles comprising the copolymer (A) are dispersed in the aqueous medium (C), the copolymer (A) comprises a structural unit derived from a monomer a1 and a structural unit derived from a monomer a2, the monomer a1 is composed of an alkyl (meth) acrylate in which a portion other than a (meth) acryloyloxy group is a hydrocarbon structure, the monomer a2 is composed of a compound having an ethylenically unsaturated group and an amide group, and the polyether-modified polydimethylsiloxane (D) is a compound in which a part or all of hydrogen atoms of methyl groups of the polydimethylsiloxane are substituted by polyether chains.)

1. A water-and oil-repellent agent composition characterized by comprising a copolymer (A), a cationic surfactant (B), an aqueous medium (C) and a polyether-modified polydimethylsiloxane (D),

particles containing the copolymer (A) are dispersed in the aqueous medium (C),

the copolymer (A) contains a structural unit derived from a monomer a1 and a structural unit derived from a monomer a2, the monomer a1 is composed of an alkyl (meth) acrylate in which a portion other than a (meth) acryloyloxy group is a hydrocarbon structure, the monomer a2 is composed of a compound having an ethylenically unsaturated group and an amide group,

the polyether-modified polydimethylsiloxane (D) is a compound in which a part or all of hydrogen atoms of methyl groups of polydimethylsiloxane are substituted with polyether chains.

2. The water-and oil-repellent agent composition according to claim 1, wherein the content of the cationic surfactant (B) is 0.10 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the copolymer (A),

the content of the polyether-modified polydimethylsiloxane (D) is 0.10 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the copolymer (a).

3. The water-and oil-repellent agent composition according to claim 1 or 2, wherein a content of a structural unit derived from the monomer a1 in the copolymer (a) is 80% by mass or more and 99% by mass or less, and a content of a structural unit derived from the monomer a2 in the copolymer (a) is 0.10% by mass or more and 20% by mass or less.

4. The water-and oil-repellent agent composition according to any one of claims 1 to 3, wherein the cationic surfactant (B) contains a quaternary ammonium salt.

5. The water-and oil-repellent agent composition according to any one of claims 1 to 4, wherein the polyether-modified polydimethylsiloxane (D) has at least one of an alkoxy group and a hydroxyl group at a terminal of a polyether chain.

6. The water-and oil-repellent agent composition according to any one of claims 1 to 5, wherein the monomer a1 contains an alkyl (meth) acrylate in which the number of carbon atoms of a hydrocarbon structure of a portion other than the (meth) acryloyloxy group is 1 or more and 8 or less.

7. The water-and oil-repellent agent composition according to claim 6, wherein a content of a structural unit derived from an alkyl (meth) acrylate in which a carbon number of a hydrocarbon structure of a portion other than the (meth) acryloyloxy group is 1 or more and 8 or less in the copolymer (A) is 50% by mass or more and 99% by mass or less.

8. The water-and oil-repellent composition according to any one of claims 1 to 7, wherein the monomer a1 contains an alkyl (meth) acrylate having a chain hydrocarbon structure of 9 or more carbon atoms as a hydrocarbon structure other than the (meth) acryloyloxy group.

9. The water-and oil-repellent agent composition according to any one of claims 1 to 8, the monomer a2 comprising at least any one of acrylamide and methacrylamide.

10. The water-and oil-repellent agent composition according to any one of claims 1 to 9, the copolymer (A) containing a structural unit derived from a monomer a3 composed of a compound having a structure represented by formula (1),

in the formula (1), R¹Represents a hydrogen atom or a methyl group, R²Represents a C1-6 valent aliphatic group which may contain an ether bond, R³Represents an aliphatic group having 1 to 30 carbon atoms, an aromatic group having 1 to 30 carbon atoms, or a hydroxyl group, h represents any one of 0, 1, and 2, and j represents an integer of 0 to 500.

11. A fiber treatment agent comprising the water-and oil-repellent agent composition according to any one of claims 1 to 10.

12. A paper treating agent comprising the water-and oil-repellent composition according to any one of claims 1 to 10.

13. A coating agent comprising the water-and oil-repellent composition according to any one of claims 1 to 10.

14. A water-and oil-repellent treatment method comprising a step of applying the water-and oil-repellent composition according to any one of claims 1 to 10 to a substrate, and a step of drying the substrate applied with the water-and oil-repellent composition.

15. A water-and oil-repellent fiber wherein the copolymer (A), the cationic surfactant (B) and the polyether-modified polydimethylsiloxane (D) contained in the water-and oil-repellent composition according to any one of claims 1 to 10 are adhered to a fiber as a substrate.

Technical Field

The present invention relates to a water-and oil-repellent agent composition, a water-and oil-repellent treatment method, and a water-and oil-repellent fiber, and further relates to a fiber treatment agent, a paper treatment agent, and a coating agent containing the water-and oil-repellent agent composition.

The present application claims priority based on application No. 2019-232795 filed in japan on 24.12.2019, the contents of which are incorporated herein by reference.

Background

Conventionally, as a method for imparting oil repellency to a substrate such as fiber or paper, an oil repellent treatment has been performed using a water-and oil-repellent composition. As the water-and oil-repellent agent composition, there is a water-and oil-repellent agent composition containing a compound having a perfluoroalkyl group having 8 or more carbon atoms.

However, a compound containing a perfluoroalkyl group having 8 or more carbon atoms may be decomposed or metabolized to generate perfluorooctanoic acid (hereinafter, may be abbreviated as "PFOA"). The environmental protection agency in the united states requires a reduction in the amount of perfluorooctanoic acid produced. Therefore, a water and oil repellent composition having a compound having a perfluoroalkyl group with a short carbon chain has been proposed.

For example, patent document 1 describes a water and oil repellent composition containing: an aqueous dispersion of a pyrazole blocked hydrophobic polyisocyanate containing a pyrazole blocked hydrophobic polyisocyanate and a nonionic surfactant, and a water-and oil-repellent component having a perfluoroalkyl group having 6 or less carbon atoms.

Patent document 2 describes a water/oil repellent composition containing: the fluorine-containing polymer composition comprises a fluorine-containing polymer having a C1-6 polyfluoroalkyl group, a fluorine-containing polymer having a fluoroolefin-based structural unit, and an aqueous medium.

In recent years, compounds in which the use of perfluoroalkyl groups containing short carbon chains is to be reduced have also been studied. Therefore, a water/oil repellent composition containing no fluorine-containing compound has been proposed.

For example, patent document 3 describes a water/oil repellent composition for fiber treatment containing no fluorine-containing compound. Patent document 4 discloses a cationic silicone-acrylic resin.

Documents of the prior art

Patent document

Patent document 1: japanese patent laid-open No. 2012 and 031285

Patent document 2: international publication No. 2012/020806

Patent document 3: international publication No. 2018/163911

Patent document 4: japanese patent laid-open publication No. 2016-102272

Disclosure of Invention

Problems to be solved by the invention

However, conventional water-and oil-repellent compositions containing no fluorine-containing compound sometimes fail to impart sufficient oil repellency to a substrate. Further, the water-and oil-repellent agent for fiber treatment described in patent document 3 uses an anionic material, and the change in form is small. The production method described in patent document 4 requires a solvent removal step, and cannot be said to be simple.

The present invention addresses the problem of providing a water/oil repellent composition, a fiber treatment agent, a paper treatment agent, a coating agent, and a water/oil repellent treatment method, which have high substrate adsorption properties and can impart high oil repellency and water repellency to a substrate. Further, an object of the present invention is to provide a water-and oil-repellent fiber having high oil repellency and water repellency.

Means for solving the problems

The embodiments of the present invention for achieving the above object are as follows [1] to [15].

1. A water-and oil-repellent agent composition characterized by comprising a copolymer (A), a cationic surfactant (B), an aqueous medium (C) and a polyether-modified polydimethylsiloxane (D),

particles containing the copolymer (A) are dispersed in the aqueous medium (C),

the copolymer (A) contains a structural unit derived from a monomer a1 and a structural unit derived from a monomer a2, the monomer a1 is composed of an alkyl (meth) acrylate in which a portion other than a (meth) acryloyloxy group is a hydrocarbon structure, the monomer a2 is composed of a compound having an ethylenically unsaturated group and an amide group,

the polyether-modified polydimethylsiloxane (D) is a compound in which some or all of the hydrogen atoms of the methyl groups of the polydimethylsiloxane are substituted by polyether chains.

[2] The water-and oil-repellent agent composition according to [1], wherein the content of the cationic surfactant (B) is 0.10 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the copolymer (A),

the content of the polyether-modified polydimethylsiloxane (D) is 0.10 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the copolymer (a).

[3] The water-and oil-repellent agent composition according to [1] or [2], wherein a content of a structural unit derived from the monomer a1 in the copolymer (a) is 80% by mass or more and 99% by mass or less, and a content of a structural unit derived from the monomer a2 in the copolymer (a) is 0.10% by mass or more and 20% by mass or less.

[4] The water-and oil-repellent agent composition according to any one of [1] to [3], wherein the cationic surfactant (B) contains a quaternary ammonium salt.

[5] The water-and oil-repellent agent composition according to any one of [1] to [4], wherein the polyether-modified polydimethylsiloxane (D) has at least one of an alkoxy group and a hydroxyl group at an end of a polyether chain.

[6] The water-and oil-repellent composition according to any one of [1] to [5], wherein the monomer a1 contains an alkyl (meth) acrylate having a hydrocarbon structure in which the moiety other than the (meth) acryloyloxy group has 1 to 8 carbon atoms.

[7] The water-and oil-repellent agent composition according to [6], wherein a content of a structural unit derived from an alkyl (meth) acrylate in which a carbon number of a hydrocarbon structure in a portion other than the (meth) acryloyloxy group is 1 or more and 8 or less in the copolymer (A) is 50% by mass or more and 99% by mass or less.

[8] The water-and oil-repellent composition according to any one of [1] to [7], wherein the monomer a1 contains an alkyl (meth) acrylate having a chain hydrocarbon structure of 9 or more carbon atoms as a hydrocarbon structure other than a (meth) acryloyloxy group.

[9] The water-and oil-repellent agent composition according to any one of [1] to [8], wherein the monomer a2 contains at least one of acrylamide and methacrylamide.

[10] The water-and oil-repellent agent composition according to any one of [1] to [9], wherein the copolymer (A) contains a structural unit derived from a monomer a3 composed of a compound having a structure represented by formula (1),

in the formula (1), R¹Represents a hydrogen atom or a methyl group, R²Represents a C1-6 valent aliphatic group which may contain an ether bond, R³Represents an aliphatic group having 1 to 30 carbon atoms, an aromatic group having 1 to 30 carbon atoms, or a hydroxyl group, h represents any one of 0, 1, and 2, and j represents an integer of 0 to 500.

[11] A fiber treatment agent comprising the water-and oil-repellent composition according to any one of [1] to [10].

[12] A paper treating agent comprising the water-and oil-repellent composition according to any one of [1] to [10].

[13] A coating agent comprising the water-and oil-repellent composition according to any one of [1] to [10].

[14] A water-and oil-repellent treatment method comprising a step of applying the water-and oil-repellent composition described in any one of [1] to [10] to a substrate, and a step of drying the substrate applied with the water-and oil-repellent composition.

[15] A water-and oil-repellent fiber, wherein the copolymer (A), the cationic surfactant (B) and the polyether-modified polydimethylsiloxane (D) contained in the water-and oil-repellent composition according to any one of [1] to [10] are adhered to a fiber as a substrate.

Effects of the invention

The present invention can provide a water/oil repellent composition, a fiber treatment agent, a paper treatment agent, a coating agent, and a water/oil repellent treatment method, which have high substrate adsorbability and can impart high oil repellency and water repellency to a substrate. Further, the present invention can provide a water-and oil-repellent fiber having high oil repellency and water repellency.

Detailed Description

Embodiments of the present invention will be described in detail below. However, the present invention is not limited to the embodiments shown below. The technical features described below can be appropriately modified without departing from the scope of the present invention.

In the following description, the "monomer" refers to a compound having a radical polymerizable ethylenically unsaturated group. "ethylenically unsaturated group" means a double bond between carbon atoms excluding the carbon atoms forming the aromatic ring.

"(meth) acrylic acid" means "acrylic acid" or "methacrylic acid". "(meth) acrylate" means "acrylate", or "methacrylate".

The "nonvolatile component" refers to a component having a boiling point of 130 ℃ or higher at 1 atm (1013hPa) among components contained in the composition and the like.

The "active ingredient" refers to an ingredient in a mixture corresponding to a certain kind of ingredient when the ingredient is used in the form of a mixture such as a solution. For example, the active ingredient of the polyether-modified polydimethylsiloxane in the propylene glycol 1-monomethyl ether solution means all compounds contained in the solution corresponding to the polyether-modified polydimethylsiloxane.

< 1. Water-and oil-repellent agent composition

The water/oil repellent composition of the present embodiment includes a copolymer (a), a cationic surfactant (B), an aqueous medium (C), and a polyether-modified polydimethylsiloxane (D). The water-and oil-repellent composition may contain other components than the above components. In the water/oil repellent composition, a latex (emulsion) in which particles containing the copolymer (a) are dispersed in an aqueous medium (C) is formed. Here, even if the particles containing the copolymer (a) are solid, if the solid is dispersed in the aqueous medium (C), it is considered that a latex is formed. That is, the particles containing the copolymer (a) may be liquid particles or solid particles.

[1-1 ] copolymer (A) ]

The copolymer (A) contains a structural unit derived from a monomer a1 comprising an alkyl (meth) acrylate in which the moiety other than the (meth) acryloyloxy group is a hydrocarbon structure, and a structural unit derived from a monomer a2 comprising a compound having an ethylenically unsaturated group and an amide group. The copolymer (a) may contain either or both of a structural unit produced from a monomer a3 composed of a compound having a structure represented by formula (1) described later and a structural unit produced from another monomer a4, the another monomer a4 being composed of a compound other than any one of the monomers a1 to a 3. The monomers a1 to a4 are described in detail below.

[1-1-1. monomer a1]

By providing the copolymer (a) with a structural unit derived from the monomer a1, a water/oil repellent composition which imparts high oil repellency to a substrate and has good stability can be obtained. The monomer a1 may be composed of 1 type of compound, or may contain 2 or more types of compounds. That is, the constitutional unit derived from the monomer a1 in the copolymer (A) may be composed of 1 species, or may contain 2 or more species.

The kind of the compound contained in the monomer a1 and the content thereof may be appropriately determined in order to adjust, for example, the glass transition temperature Tg of the copolymer (a). When the glass transition temperature of the copolymer (A) is to be lowered, the monomer a1 may contain a large amount of a homopolymer of a compound having a low glass transition temperature. When the glass transition temperature of the copolymer (A) is to be increased, a large amount of a homopolymer of a compound having a high glass transition temperature may be contained as the monomer a 1.

The content of the structural unit derived from the monomer a1 in the copolymer (a) is preferably 80% by mass or more, more preferably 90% by mass or more, and still more preferably 95% by mass or more. This is because a water-and oil-repellent composition having good stability can be obtained.

In view of the content of the structural unit derived from a monomer other than the monomer a1, the content of the structural unit derived from the monomer a1 in the copolymer (a) is preferably 99% by mass or less, more preferably 98% by mass or less.

The hydrocarbon structure containing a portion other than the (meth) acryloyloxy group in the monomer a1 is preferably an alkyl (meth) acrylate having 1 to 8 carbon atoms. This is because the texture of the substrate treated with the water-and oil-repellent composition of the present embodiment can be easily adjusted.

Examples of the alkyl (meth) acrylate having a hydrocarbon structure other than the (meth) acryloyloxy group and having 1 to 8 carbon atoms include methyl (meth) acrylate, ethyl (meth) acrylate, allyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, dimethylhexyl (meth) acrylate, and octyl (meth) acrylate.

In the case of treating paper or fibers with the water-and oil-repellent composition, the compound preferably contains 1 or 2 or more selected from methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate.

The content of the structural unit derived from the alkyl (meth) acrylate in which the number of carbon atoms in the hydrocarbon structure of the portion other than the (meth) acryloyloxy group is 1 to 8 is preferably 50% by mass or more, more preferably 60% by mass or more, and still more preferably 70% by mass or more in the copolymer (a). This is because the texture of the substrate treated with the water-and oil-repellent composition of the present embodiment can be easily adjusted.

In view of the content of other structural units in the copolymer (a), the content of structural units derived from an alkyl (meth) acrylate in which the number of carbon atoms of the hydrocarbon structure in the portion other than the (meth) acryloyloxy group is 1 or more and 8 or less is preferably 99% by mass or less, and more preferably 98% by mass or more.

The monomer a1 may contain an alkyl (meth) acrylate having a "chain hydrocarbon structure having 9 or more carbon atoms" as a hydrocarbon structure other than the "(meth) acryloyloxy group. This is because a water-and oil-repellent composition that can impart better water repellency to a substrate while retaining oil repellency can be obtained.

Examples of the alkyl (meth) acrylate having a chain hydrocarbon structure of 9 or more carbon atoms as a "hydrocarbon structure of a portion other than a (meth) acryloyloxy group" include butyl hexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, and isostearyl (meth) acrylate. Among these compounds, alkyl (meth) acrylates having a hydrocarbon structure in which the main chain having 9 or more carbon atoms is a portion other than the (meth) acryloyloxy group (hereinafter, may be referred to as long-chain alkyl (meth) acrylates) are preferable. Further, the long-chain alkyl (meth) acrylate is preferably one or both of isostearyl (meth) acrylate and lauryl (meth) acrylate. This is because the polymerization stability can be improved.

When the monomer a1 contains a long-chain alkyl (meth) acrylate, the content of the structural unit derived from the long-chain alkyl (meth) acrylate in the copolymer (a) is preferably 0.10% by mass or more, more preferably 1.0% by mass or more, and still more preferably 5.0% by mass or more. This is because a water-and oil-repellent composition which imparts good water repellency to a substrate can be obtained.

The content of the structural unit derived from the long-chain alkyl (meth) acrylate in the copolymer (a) is preferably 20% by mass or less, more preferably 17% by mass or less, and still more preferably 15% by mass or less. This is because the texture of the substrate treated with the water-and oil-repellent composition can be satisfactorily maintained.

[1-1-2. monomer a2]

By providing the copolymer (a) with a structural unit derived from the monomer a2, a water/oil repellent composition which can impart high oil repellency to a substrate can be obtained.

Examples of the monomer a2 include, but are not limited to, acrylamide, methacrylamide, and N-vinylacetamide. The monomer a2 preferably contains at least one of acrylamide and methacrylamide. The monomer a2 may be composed of 1 type of compound, or may contain 2 or more types of compounds. That is, the copolymer (A) may contain only 1 type of structural unit derived from the monomer a2, or may contain 2 or more types of structural units.

The content of the structural unit derived from the monomer a2 in the copolymer (a) is preferably 0.10% by mass or more, more preferably 0.50% by mass or more, and still more preferably 1.0% by mass or more. This is because a water/oil repellent composition which imparts good oil repellency to a substrate can be obtained.

The content of the structural unit derived from the monomer a2 in the copolymer (a) is preferably 20% by mass or less, more preferably 10% by mass or less, still more preferably 5.0% by mass or less, and particularly preferably 3.0% by mass or less. This is because the water-and oil-repellent composition can be obtained at low cost, and the substrate treated with the water-and oil-repellent composition retains good water repellency.

[1-1-3. monomer a3]

The monomer a3 is composed of a compound having a structure represented by the following formula (1).

In the formula (1), R¹Represents a hydrogen atom or a methyl group, R²Represents a C1-6 valent aliphatic group which may contain an ether bond, R³Represents an aliphatic group, an aromatic group or a hydroxyl group having 1 to 30 carbon atoms, and h represents 0, 1 or 2J represents an integer of 0 to 500. R²The number of carbon atoms of (2) is preferably 1 to 4. Preferably R³The number of carbon atoms of (A) is 2 to 18. Further, R is more preferable²And R³Is a hydrocarbon chain. j is preferably an integer of 10 to 300.

The monomer a3 may be composed of 1 type of compound satisfying the conditions of formula (1), or may contain 2 or more types. The number average molecular weight of the monomer a3 is preferably 300 or more, more preferably 1000 or more, and still more preferably 3000 or more. This is because the substrate treated with the water-and oil-repellent composition retains good water repellency. The number average molecular weight of the monomer a3 is preferably 40000 or less, more preferably 20000 or less, and further preferably 15000 or less. This is because the copolymerizability of the monomer a3 can be improved.

The content of the structural unit derived from the monomer a3 in the copolymer (a) is preferably 0.10% by mass or more, more preferably 1.0% by mass or more, and still more preferably 5.0% by mass or more. This is because a water-and oil-repellent composition which imparts good water repellency to a substrate can be obtained.

The content of the structural unit derived from the monomer a3 in the copolymer (a) is preferably 20% by mass or less, more preferably 10% by mass or less, and still more preferably 5.0% by mass or less. This is because the texture of the substrate treated with the water-and oil-repellent composition can be maintained.

[1-1-4. other monomer a4]

The other monomer a4 is a compound having an ethylenically unsaturated group capable of polymerization and is composed of a compound not corresponding to the monomers a1 to a 3. Examples of the other monomer a4 include compounds having an ethylenically unsaturated group and a hydrophilic chain, and compounds having an ethylenically unsaturated group and a functional group other than an ethylenically unsaturated group. The other monomer a4 may be composed of only 1 compound, or may contain 2 or more compounds. That is, the structural unit derived from the other monomer a4 in the copolymer (A) may be composed of 1 type of structural unit, or may contain 2 or more types of structural units.

Examples of the compound having an ethylenically unsaturated group and a hydrophilic chain include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, and polypropylene glycol di (meth) acrylate.

Examples of the compound having an ethylenically unsaturated group and a functional group other than an ethylenically unsaturated group include a compound having an alkoxy group, a compound having an amino group, a compound having a nitrile group, and a salt of a compound having a sulfo group. Examples of the compound having an ethylenically unsaturated group and an alkoxy group include methoxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, and the like. Examples of the compound having an ethylenically unsaturated group and an amino group include dimethylaminoethyl (meth) acrylate and diethylaminoethyl (meth) acrylate. Examples of the compound having an ethylenically unsaturated group and a nitrile group include (meth) acrylonitrile, and examples of the salt of a compound having a sulfo group include sodium p-toluenesulfonate and the like.

The other monomer a4 may contain a hydrocarbon compound having an ethylenically unsaturated group. The hydrocarbon compound having an ethylenically unsaturated group is preferably a compound in which at least one carbon atom constituting the ethylenically unsaturated group is directly bonded to a phenyl group, from the viewpoint of polymerizability. Examples of such compounds include styrene, β -methylstyrene, and divinylbenzene.

Examples of the other monomer a4 include compounds having an ester bond such as vinyl acetate and vinyl propionate.

The other monomer a4 may contain a copolymerizable surfactant. The copolymerizable surfactant is a compound having a polymerizable ethylenically unsaturated group and also having a surfactant function. The copolymerizable surfactant may be any of anionic, cationic, amphoteric and nonionic surfactants. In consideration of the function as the cationic surfactant (B) described later, it is preferable to contain a cationic copolymerizable surfactant as the other monomer a 4.

[ 1-2. cationic surfactant (B) ]

The kind of the cationic surfactant (B) can be appropriately selected depending on the kinds of the copolymer (a) and the aqueous medium (C).

Examples of the cationic surfactant (B) include alkyltrimethylammonium chloride, cetyltrimethylammonium bromide, and laurylpyridinium chloride. The cationic surfactant (B) preferably contains a quaternary ammonium salt, and more preferably contains an alkyl quaternary ammonium salt. More preferred alkyl quaternary ammonium salts are alkyl trimethyl ammonium chlorides.

The content of the cationic surfactant (B) in the water-and oil-repellent composition is preferably 0.10 parts by mass or more, more preferably 0.50 parts by mass or more, and still more preferably 0.80 parts by mass or more, per 100 parts by mass of the copolymer (a). This is because the stability of the latex can be improved.

The content of the cationic surfactant (B) in the water-and oil-repellent composition is preferably 10 parts by mass or less, more preferably 5.0 parts by mass or less, and still more preferably 2.5 parts by mass or less, per 100 parts by mass of the copolymer (a). This is because the water resistance of the substrate treated with the water/oil repellent composition can be kept good.

[ 1-3. aqueous Medium (C) ]

The aqueous medium (C) contains water as an essential component. The aqueous medium (C) may contain a hydrophilic solvent other than water.

Examples of the hydrophilic solvent include alcohols such as methanol, ethanol, 1-monomethyl ether of propylene glycol, N-propanol, isopropanol, t-butanol and benzyl alcohol, and nitrogen-containing organic solvents such as N-methylpyrrolidone. The hydrophilic solvent may contain one kind or two or more kinds.

The content of the hydrophilic solvent in the aqueous medium (C) is preferably 10% by mass or less, and more preferably 5.0% by mass or less. This is because the increase in cost due to the use of a solvent can be suppressed.

The content of the aqueous medium (C) in the water-and oil-repellent composition is preferably determined according to a desired value of the nonvolatile content concentration in the water-and oil-repellent composition. The water-and oil-repellent agent composition has a nonvolatile content concentration of preferably 10% by mass or more, more preferably 20% by mass or more, and still more preferably 30% by mass or more. This is because the water-and oil-repellent agent composition can be used in a small amount to effectively impart a water-and oil-repellent effect to a substrate.

The water-and oil-repellent agent composition preferably has a nonvolatile content concentration of 70% by mass or less, more preferably 60% by mass or less, and even more preferably 50% by mass or less. This is because the storage stability of the water/oil repellent composition can be improved and the water/oil repellent composition can be easily applied to a substrate uniformly.

[ 1-4. polyether-modified polydimethylsiloxane (D) ]

The polyether-modified polydimethylsiloxane (D) is a compound in which some or all of the hydrogen atoms of the methyl groups of the polydimethylsiloxane are substituted by polyether chains. That is, the polyether-modified polydimethylsiloxane is a graft copolymer having a polysiloxane as a main chain and a polyether side chain. The polyether-modified polydimethylsiloxane (D) preferably has at least one of an alkoxy group and a hydroxyl group at the end of the polyether chain, and more preferably has a hydroxyl group. This is because the oil repellency of the water-and oil-repellent composition can be improved.

The number average molecular weight of the polyether-modified polydimethylsiloxane (D) is preferably 1000 to 50000. Commercially available products of polyether-modified polydimethylsiloxane (D) having a hydroxyl group at the end of a polyether chain include BYK silaclean 3720 manufactured by BYK corporation and TEGO (registered trademark) Protect 5100N manufactured by エボニック corporation.

The content of the polyether-modified polydimethylsiloxane (D) is preferably 0.10 parts by mass or more, more preferably 0.50 parts by mass or more, and still more preferably 1.5 parts by mass or more, per 100 parts by mass of the copolymer (a). This is because the water-and oil-repellent composition can impart good oil repellency to a substrate.

The content of the polyether-modified polydimethylsiloxane (D) is preferably 20 parts by mass or less, more preferably 10 parts by mass or less, and still more preferably 5.0 parts by mass or less, per 100 parts by mass of the copolymer (a). This is because the fiber or paper treated with the water-and oil-repellent composition has a good texture.

[ 1-5. other Components ]

Examples of the other components that can be contained in the water/oil repellent composition of the present embodiment include other resins, crosslinking agents, thickeners, pH adjusters, film forming aids, plasticizers, preservatives, defoaming agents, surfactants, and the like. The other components may be contained in 1 type or 2 or more types in the form of the water/oil repellent composition within the range in which the object of the present invention can be achieved.

< 2. Process for producing Water-and oil-repellent agent composition

An example of the method for producing the water/oil repellent composition of the present embodiment includes the steps of: a polymerization step of an aqueous emulsion obtained by emulsion-polymerizing a monomer containing at least the monomer a1 and the monomer a2 in an aqueous medium (C) in the presence of a cationic surfactant (B), and a mixing step of mixing the aqueous emulsion with the polyether-modified polydimethylsiloxane (D). The method for producing the water/oil repellent composition of the present invention is not limited to the method described below. Hereinafter, the monomer which becomes the structural unit of the copolymer (a) is referred to as a monomer a.

[ 2-1. polymerization procedure ]

In the polymerization step, the monomer a, the cationic surfactant (B) and the aqueous medium (C) are mixed and emulsion-polymerized. The monomer a contains a1 monomer and a2 monomer, may also contain a3 monomer, and may also contain a4 monomer.

The content ratio of each monomer in the monomer a is the same as the content ratio (% by mass) of the structural unit derived from the monomer in the produced copolymer (a).

The amount of the cationic surfactant (B) added to 100 parts by mass of the monomer a is the same as the amount of the cationic surfactant (B) contained to 100 parts by mass of the copolymer (a) in the water-and oil-repellent composition. The cationic surfactant (B) may be added all at once in the polymerization step, or may be added in part in the polymerization step and the remainder may be added in a subsequent step.

In the polymerization step, a polymerization initiator is preferably used. As the polymerization initiator, hydrogen peroxide, azo compounds, organic peroxides, and the like can be used. Further, a redox initiator obtained by using these polymerization initiators in combination with a reducing agent can be used.

The amount of the polymerization initiator used is preferably 0.01 to 1.0 part by mass, more preferably 0.05 to 0.80 part by mass, and still more preferably 0.1 to 0.5 part by mass, based on 100 parts by mass of the total amount of the monomers forming the copolymer (A), in order to obtain an appropriate polymerization rate.

In the polymerization step, a chain transfer agent for adjusting the molecular weight of the copolymer (a) may be added. Examples of the chain transfer agent include mercaptans, thioglycolic acid and esters thereof, and β -mercaptopropionic acid and esters thereof.

As the emulsion polymerization method, for example, a method of putting all the above-mentioned components at once to carry out polymerization may be used, or a method of carrying out polymerization while continuously supplying the components may be used. As a method of polymerizing the respective components while continuously supplying them, for example, a method of mixing the monomer a, the aqueous medium (C) and the cationic surfactant (B) in a polymerization initiator solution obtained by mixing a part of the polymerization initiator with the aqueous medium (C) and the cationic surfactant (B) to emulsify them, and continuously supplying the obtained mixed emulsion and the remaining amount of the polymerization initiator while stirring them is included. The temperature for emulsion polymerization may be, for example, 30 to 85 ℃.

[ 2-2. mixing procedure ]

In the mixing step, the aqueous latex obtained in the polymerization step is mixed with the polyether-modified polydimethylsiloxane (D). The mixing method includes, for example, stirring at 500rpm for 5 minutes at 23 ℃ using a homogenizer model 2.5 (manufactured by PRIMIX Co., Ltd.), but is not limited thereto.

< 3. use of Water-and oil-repellent agent composition

The water-and oil-repellent composition of the present embodiment can impart high oil repellency to a substrate and has good adsorption to the substrate. The water/oil repellent composition of the present embodiment can impart high oil repellency and water repellency to a substrate such as fiber, paper, or glass. Therefore, preferable applications of the water/oil repellent composition of the present embodiment include materials for fiber treatment agents, paper treatment agents, and coating agents.

[ 3-1. fiber-treating agent and Water-and oil-repellent fiber ]

The fiber treatment agent of the present embodiment may be composed of the water/oil repellent composition of the present embodiment, or may contain, in addition to the water/oil repellent composition, conventional additives such as a defoaming agent, an antiseptic agent, a pH adjuster, a surfactant, a crosslinking agent, an antistatic agent, a wetting agent, a thickener, and a pigment, as required, in a range not impairing the object of the present invention.

The water-and oil-repellent fiber of the present embodiment has a base material fiber to which the copolymer (a), the cationic surfactant (B), and the polyether-modified polydimethylsiloxane (D) are attached. The total amount of the components (a), (B), and (D) attached is preferably 1.0 part by mass or more, and more preferably 2.0 parts by mass or more, per 100 parts by mass of the fibers as the base material. This is because the water repellency and oil repellency of the fibers are improved. The total amount of the components (a), (B), and (D) attached is preferably 20 parts by mass or less, and more preferably 10 parts by mass or less, per 100 parts by mass of the fibers as the base material. This is because the loss of the texture of the fiber can be suppressed, and the quality of the fiber can be increased.

Examples of the method for impregnating and applying the fiber treatment agent to the base fiber include dipping, spraying, and roll coating. The fibers are impregnated with the fiber treatment agent, and then the amount of the fiber treatment agent attached to the fibers is adjusted. Examples of the method of adjusting the amount of adhesion include a method of squeezing with a roll (MangleRoll) or the like. But is not limited to such. The drying temperature after impregnation of the fiber treatment agent is preferably 80 to 170 ℃, and more preferably 90 to 150 ℃.

The fiber treatment agent of the present embodiment can impart high oil repellency and water repellency to fibers. The form of the fiber treated by the fiber treatment agent may be any form such as short fiber (fiber), cotton linter, roving, sliver, yarn (yarn), woven fabric, knitted fabric, and nonwoven fabric. Examples of the raw material of the fiber to be treated include cellulose fibers such as cotton, flax, jute, hemp, ramie, regenerated cellulose and rayon, and polyvinyl alcohol-based synthetic fibers. The fibers preferably contain 30% or more of the above raw materials.

[ 3-2 ] paper-treating agent and Water-and oil-repellent paper ]

The components, coating method, and amount of adhesion to the substrate of the paper treatment agent of the present embodiment are different from those of the fiber treatment agent only in that the substrate is paper, and the others are as described above. That is, the "fibers" in the positions corresponding to the descriptions of the fiber treatment agent may be read as "paper" instead.

The paper treatment agent of the present embodiment can impart high oil repellency and water repellency to paper. The paper treated with the paper-treating agent is not particularly limited, and examples thereof include general-purpose paper made of pulp cellulose.

[ 3-3. coating agent ]

The coating agent of the present embodiment may be composed of only the water/oil repellent composition of the present embodiment, or may contain, in addition to the water/oil repellent composition, conventional additives such as a defoaming agent, an antiseptic agent, a pH adjuster, a surfactant, a crosslinking agent, an antistatic agent, a wetting agent, a thickener, and a pigment, which are conventionally known, in a range not impairing the object of the present invention.

Examples of the substrate to be coated with the coating agent of the present embodiment include glass, polyolefin resins, polyester resins, polycarbonate resins, acrylonitrile butadiene styrene copolymers (ABS resins), polystyrene resins, and molded articles thereof (films, seats, cups), metals, and the like. However, it is not limited to these.

Examples of the coating method include spraying, brushing, roll coating, troweling, dipping, air knife coating, flow coating, bar coating, roll coating, gravure coating, and a method using an applicator.

The drying temperature at the time of drying the substrate coated with the water-and oil-repellent composition is preferably 80 ℃ or higher, more preferably 100 ℃ or higher. This is because the drying time can be shortened, and high productivity can be obtained. The drying temperature at the time of drying the substrate coated with the water-and oil-repellent composition is preferably 170 ℃ or lower, more preferably 150 ℃ or lower. This can suppress deterioration of the water-and oil-repellent composition due to drying. The drying time is appropriately determined depending on the amount of the water-and oil-repellent composition applied to the substrate, and is not particularly limited.

The coating agent of the present embodiment can impart high water repellency and oil repellency to a substrate.

< 4. Water-and oil-repellent treatment method

The water-and oil-repellent treatment method of the present embodiment includes a step of applying the water-and oil-repellent composition of the present embodiment to a substrate, and a step of drying the substrate applied with the water-and oil-repellent composition.

Examples

The present invention will be described in more detail below with reference to examples and comparative examples. The present invention is not limited to the following embodiments.

< 1. production of composition >

In a five-neck separable flask equipped with a stirrer, a thermometer, a nitrogen inlet, a reflux condenser and a dropping funnel, 120g of ion-exchanged water and 1g of TML (registered trademark) カチオーゲン (B) (alkyl trimethyl ammonium chloride, 30 mass% aqueous solution, manufactured by first Industrial pharmaceutical Co., Ltd.) were charged, and the temperature was raised to 80 ℃. This was used as a first mixed solution (. alpha.).

On the other hand, 420g of ion-exchanged water, 15g of cationic surfactant (B) (カチオーゲン TML), and monomer a were added to a 1-liter beaker, and dispersed with a homomixer to obtain a second mixed solution (β). The mass of each monomer contained in the monomer a in each example and comparative example is shown in tables 1 and 2. In tables 1 and 2, the mass of the cationic surfactant (B) and the ion-exchanged water is the total amount of the mass contained in the first mixed solution (α) and the mass contained in the second mixed solution (β). The aqueous medium (C) may contain a solvent such as a cationic surfactant (B) or polyether-modified polydimethylsiloxane (D) in addition to ion-exchanged water, but the values shown in the columns of ion-exchanged water in tables 1 and 2 are amounts excluding these solvents.

10g of a3 mass% aqueous solution of 2, 2' -azobis (2-methylpropionamidine) dihydrochloride (AAPH) as a polymerization initiator was added to the first mixed solution (. alpha.) kept at 80 ℃ in a five-neck separable flask. Subsequently, the second mixed solution (. beta.) and 44g of a3 mass% aqueous solution of AAPH were stirred from the dropping funnel while dropping them dropwise over 3 hours while keeping the flask at 80 ℃ to carry out emulsion polymerization. After completion of the dropwise addition, the flask was kept at 80 ℃ for 1 hour. Thereafter, the flask was cooled to 30 ℃ to obtain an aqueous emulsion. The values shown in the columns of the polymerization initiators in tables 1 and 2 are the total of the amounts used.

To the obtained aqueous latex, polyether-modified polydimethylsiloxane (D) was added in the amounts and components shown in tables 1 and 2 to obtain the water-and oil-repellent compositions of examples 1 to 12 and the compositions of comparative examples 1 to 5. The nonvolatile matter concentration values shown in tables 1 and 2 are calculated values based on the used amount of the raw materials. That is, the ratio (% by mass) of the amount of the monomer a used, the amount of the cationic surfactant (B) (active ingredient), the amount of the polyether-modified polydimethylsiloxane (D) (active ingredient), and the amount of the polymerization initiator (active ingredient) used to the total amount of the raw materials used is

The content of each structural unit contained in the copolymer (a) is the same as the content of each monomer contained in the monomer a.

(comments in tables 1 and 2)

In addition, the method is as follows: r in the formula (1)¹Is methyl, R²Is a hydrocarbon chain, R³Is a compound having an aliphatic hydrocarbon structure, h ═ 2. The number average molecular weight was 10000.

In addition, 2: manufactured by a first industrial pharmaceutical company. カチオーゲン is a registered trademark. A 30 mass% aqueous solution of alkyltrimethylammonium chloride.

And (2) in color: BYK corporation. A10 mass% propylene glycol 1-monomethyl ether solution of polyether-modified polydimethylsiloxane having a hydroxyl group at the end of the polyether chain. Hydroxyl value in the active ingredient: 29 mgKOH/g.

In addition, 4: manufactured by EVONIK corporation. TEGO is a registered trademark. A dispersion of 10 mass% of a polyether-modified polydimethylsiloxane having a hydroxyl group at the end of a polyether chain. The dispersion medium is water. The hydroxyl value in the active ingredient is 25 mgKOH/g.

In addition, the method is as follows: manufactured by signal シリコーン corporation. A50 mass% propylene glycol 1-monomethyl ether solution of polyether-modified polydimethylsiloxane.

< 2 evaluation of oil repellency >

The following evaluations were carried out using the compositions obtained in examples 1 to 12 and comparative examples 1 to 5. The evaluation results are shown in tables 1 and 2.

[ 2-1. test No. 1]

A200 mm by 200mm cotton cloth (cotton-gold towel No. 3) was dipped in the composition diluted 2 times by mass with ion-exchanged water. This was dried in an oven at 130 ℃ for 5 minutes to obtain a test cloth. In each of examples and comparative examples, the amount of the components (the copolymer (a), the cationic surfactant (B), and the polyether-modified polydimethylsiloxane (D)) adhered to the composition after drying was adjusted to 20 parts by mass based on 100 parts by mass of the cotton cloth.

0.03ml of a test solution (paraffin paste) of grade 1 which is specified in the oil repellency test by AATCC118 method was dropped on one surface of the obtained test cloth, and the state of the test solution after 1 minute was visually observed. The results were evaluated according to the following criteria. Furthermore, the test cloth and the test solution used were those at 23 ℃. In addition, the standing and visual observation of the test solution on the test cloth were carried out in a thermostatic chamber at 23 ℃. The evaluation criteria are as follows.

Very good: the test solution remains as a ball drop.

Well: after the test solution ball drops collapse, the test solution wets and spreads on the test cloth, but does not penetrate into the test cloth.

Slightly better: the test solution is kept stand for 30 seconds and then is infiltrated into the test cloth within 1 minute.

Difference: the test solution penetrated into the test cloth within 30 seconds after the test solution was allowed to stand.

[ 2-2. 2 nd experiment ]

The composition was applied to a glass plate as a substrate with a coater to a coating thickness of 150 μm (in an undried state), and dried at 130 ℃ for 5 minutes in an oven, to obtain a test piece (coating material).

On the surface of the test piece coated with the composition, 2 μ l of a droplet of a test solution (paraffin paste) of oil repellency class 1 specified in the oil repellency test by AATCC118 method was placed, and the contact angle of the test solution after 10 seconds was measured by the θ/2 method using an automatic contact angle meter CA-VP type (manufactured by nippon interface science).

< 3 evaluation of Water repellency

The compositions obtained in examples 1 to 12 and comparative examples 1 to 5 were evaluated based on the water repellency test (spray test) described in JIS L1092 (2009) 7.2. The evaluation criteria are as follows, and the test results are shown in tables 1 and 2.

Level 1: the surface as a whole showed wetting.

And 2, stage: half of the surface showed wetting, showing a state where one small wet spot penetrated the cloth.

And 3, level: the surface shows tiny, one-by-one, drop-like wetting spots.

4, level: the surface was not wet, but small water droplets adhered.

And 5, stage: the surface is not wet and water drops are not attached.

< 4. evaluation of substrate adsorption Property >

The compositions obtained in examples 1 to 12 and comparative examples 1 to 5 were used to evaluate substrate adsorption properties by the following methods. The evaluation results are shown in tables 1 and 2.

A200 mm. times.200 mm cotton cloth (cotton-covered golden cloth No. 3) was impregnated with the composition diluted with ion-exchanged water to a nonvolatile matter concentration of 4% by mass. Thereafter, the cotton cloth was pulled up and dried in an oven at 130 ℃ for 5 minutes to obtain a test cloth. The mass of the test cloth was measured, and the amount of adsorption of the components contained in each composition onto the substrate (substrate adsorption amount) was measured according to the following formula.

The substrate adsorption amount [ parts by mass ] { (mass of test cloth) - (mass of untreated cotton cloth) } × 100/(mass of untreated cotton cloth)

< 5. evaluation result >

[ 5-1. oil repellency ]

As shown in tables 1 and 2, the substrates treated with the water and oil repellent compositions of examples 1 to 12 were less likely to be penetrated by the sample liquid (paraffin paste) (test 1), and had large contact angle values with respect to the droplets of the sample liquid (paraffin paste) (test 2). From this fact, it is understood that the water and oil repellent composition of examples 1 to 12 can impart high oil repellency to the substrate.

On the other hand, the substrates treated with the composition of comparative example 1 containing no polyether-modified polydimethylsiloxane (D) and the compositions of comparative examples 2 to 4 containing no structural unit derived from the monomer a2 in the copolymer (A) were easy to permeate the sample solution and had a small contact angle with respect to the sample solution droplet.

[ 5-2. Water repellency ]

As shown in tables 1 and 2, the substrates treated with the water-and oil-repellent composition of examples 1 to 12 did not show extensive wetting as a result of the water repellency test. From this fact, it is understood that the water and oil repellent compositions of examples 1 to 12 can impart high water repellency to the substrate.

On the other hand, the results of the water repellency test showed that the substrates treated with the composition of comparative example 1 containing no polyether-modified polydimethylsiloxane (D) and the compositions of comparative examples 2 to 4 containing no monomer a2 having an amide group and an ethylenically unsaturated group were wetted in a wide range.

[ 5-3. substrate adsorption ]

As shown in tables 1 and 2, the water-and oil-repellent agent compositions of examples 1 to 12 were evaluated for the amount of adsorption to the substrate, and as a result, the components contained in the water-and oil-repellent agent compositions were sufficiently adsorbed to the substrate. From this fact, it is understood that the water and oil repellent compositions of examples 1 to 12 have high adsorptivity to the substrate.

In the evaluation result of the amount of adsorption to the substrate of the composition of comparative example 5 in which acrylic acid was used instead of the monomer a2 having an amide group and an ethylenically unsaturated group, the amount of adsorption of the components contained in the composition to the substrate was insufficient.

From these results, it is understood that the water and oil repellent composition of the present invention has high substrate adsorptivity and can impart high oil repellency and water repellency to a substrate.