阅读说明：本技术 聚酯系合成纤维结构物的阻燃加工 (Flame-retardant processing of polyester synthetic fiber structure ) 是由 岩城辉文 小山重人 多田祐二 于 2018-06-16 设计创作，主要内容包括：根据本发明提供包含氨基五苯氧基环三磷腈的用于聚酯系合成纤维结构物的阻燃剂、将该阻燃剂在表面活性剂存在下分散于溶剂中而成的用于聚酯系合成纤维结构物的阻燃加工剂。(The present invention provides a flame retardant for polyester synthetic fiber structures, which contains amino pentaphenoxy cyclotriphosphazene, and a flame retardant processing agent for polyester synthetic fiber structures, which is obtained by dispersing the flame retardant in a solvent in the presence of a surfactant.)

1. A flame retardant for a polyester-based synthetic fiber structure, which comprises an amino-pentaphenoxycyclotriphosphazene represented by the following structural formula (1),

[ solution 1]

2. A flame retardant processing agent for a polyester-based synthetic fiber structure, which is obtained by dispersing the flame retardant according to claim 1 in a solvent in the presence of a surfactant.

3. The flame retardant processing agent for a polyester-based synthetic fiber structure according to claim 2, wherein the solvent is water.

4. A flame-retardant processed polyester synthetic fiber structure which is flame-retardant processed by the flame retardant according to claim 1.

5. A method for flame-retardant treatment of a polyester-based synthetic fiber structure, which comprises subjecting a polyester-based synthetic fiber structure to flame-retardant treatment with the flame-retardant treating agent according to claim 2 or 3.

6. A method for flame-retardant treatment of a polyester-based synthetic fiber structure, characterized in that the flame-retardant treating agent according to claim 2 or 3 is attached to a polyester-based synthetic fiber structure, dried, and then heat-treated at a temperature of 80 to 200 ℃.

7. A flame-retardant processed polyester-based synthetic fiber structure which is flame-retardant processed by the flame-retardant processing method according to claim 5 or 6.

Technical Field

The present invention relates to a flame retardant processing for a polyester synthetic fiber structure, and more particularly, to a flame retardant processing for a polyester synthetic fiber structure, which contains amino pentaphenoxy cyclotriphosphazene, imparts flame retardancy to the polyester synthetic fiber structure by post-processing, a polyester synthetic fiber structure flame-retardant processed by such a flame retardant, a flame retardant processing agent containing such a flame retardant, a method for flame retardant processing of a polyester synthetic fiber structure using such a flame retardant processing agent, and a flame retardant processed polyester synthetic fiber structure obtained by such a flame retardant processing method.

Background

Conventionally, various methods for imparting flame retardancy to polyester synthetic fiber structures by post-processing have been known. Typical methods of post-processing include, for example, a bath treatment method and a padding method.

As a method for imparting flame retardancy to a polyester-based synthetic fiber structure by post-processing, a method of imparting a polyester-based synthetic fiber structure by a padding method using a water-soluble salt such as guanidine phosphate or phosphoric acid urethane as a flame retardant processing agent has been the mainstream, but there is a problem that a crystal precipitates on the surface of a fiber structure due to moisture absorption and desorption or ring dyeing called a color pattern occurs when water adheres to the surface of a fiber structure in a flame retardant processed polyester-based synthetic fiber structure processed by such a water-soluble salt (see, for example, patent document 1).

In order to solve the above-mentioned problems, a method of applying a halogen-based compound or a phosphorus-based compound to a polyester-based synthetic fiber structure by a bath treatment method or a padding method by using an emulsion or dispersion has been studied (see, for example, patent documents 2 and 3).

As a representative halogen-based compound, for example, 1,2,5,6,9, 10-Hexabromocyclododecane (HBCD) is known, and in recent years, the use thereof has been limited because the compound is harmful to the environment.

On the other hand, , phosphate esters and phosphoramides are known as the phosphorus-based compounds, and these conventionally known phosphate esters and phosphoramides have insufficient affinity with polyester-based synthetic fibers, and when these phosphate esters and phosphoramides are applied to a polyester-based synthetic fiber structure by padding for flame-retardant treatment, unfixed phosphate esters and phosphoramides remain on the surface of the fiber structure, and therefore, it is necessary to wash the flame-retardant treated polyester-based synthetic fiber structure after the flame-retardant treatment.

further, since the phosphoric acid ester and phosphoramide have a low phosphorus content, they have a problem that they have to be added in a large amount to impart sufficient flame retardancy to a polyester synthetic fiber structure, resulting in a reduced hand feeling.

In addition, since several cyclic phosphazene compounds having an amino group, a phenoxy group, and/or a methoxy group in the molecule have a high phosphorus content, several proposals have been made to use them as a flame retardant for polyester-based synthetic fiber structures (see, for example, patent documents 4 and 5).

However, cyclic phosphazene compounds proposed as flame retardants have various problems such as poor dispersibility in water, poor affinity with polyester synthetic fiber structures, and easy hydrolysis under humid and hot conditions, due to differences in structure and substituent types, and polyester synthetic fiber structures flame-retardant-processed using such cyclic phosphazene compounds as flame retardants have various problems such as chalky marks, colored streaks when water adheres to the surface of the fiber structures, and crystals precipitate on the surface of the fiber structures over time.

Disclosure of Invention

Problems to be solved by the invention

The present inventors have extensively and specifically studied the production of various novel cyclic phosphazene compounds having an amino group and/or a phenoxy group and the flame retardant performance thereof in order to solve the above-mentioned problems of conventional flame retardants for flame-retardant processing of polyester-based synthetic fiber structures, and as a result, have found that amino pentaphenoxy cyclotriphosphazene is difficult to hydrolyze, is stable, and has excellent affinity with polyester-based synthetic fiber structures, and is useful as a flame retardant for polyester-based synthetic fiber structures.

That is, the present inventors have found that when the above-mentioned aminopentaphenoxycyclotriphosphazene is dispersed in a solvent in the presence of a surfactant as a flame retardant processing agent and the flame retardant processing agent is used to flame-retardant a polyester-based synthetic fiber structure, for example, a polyester-based synthetic fiber structure is not subjected to deterioration in physical properties thereof, such as discoloration, chalky marks, reduction in frictional fastness, discoloration with time, and crystallization, without being washed after the flame retardant processing, and satisfactory flame retardancy can be imparted to the polyester-based synthetic fiber structure, thereby completing the present invention.

Means for solving the problems

The present invention provides a flame retardant for polyester synthetic fiber structures, which contains an aminopentaphenoxycyclotriphosphazene represented by the following structural formula (1).

[ solution 1]

Further, the present invention provides a flame retardant processing agent for a polyester synthetic fiber structure, which is obtained by dispersing the above flame retardant in a solvent in the presence of a surfactant.

In particular, a flame retardant processing agent for a polyester synthetic fiber structure, which is obtained by dispersing the above flame retardant in water as a solvent in the presence of a surfactant.

further, the present invention provides a flame-retardant processed polyester synthetic fiber structure which is flame-retardant processed by the flame retardant.

Further, the present invention provides a method for flame-retardant processing of a polyester synthetic fiber structure characterized by flame-retardant processing of a polyester synthetic fiber structure with the flame-retardant processing agent, particularly a method for flame-retardant processing of a polyester synthetic fiber structure comprising attaching the flame-retardant processing agent to a polyester synthetic fiber structure, drying the polyester synthetic fiber structure, and then heat-treating the polyester synthetic fiber structure at a temperature of 80 to 200 ℃, and a method for flame-retardant processing of a polyester synthetic fiber structure comprising treating the polyester synthetic fiber structure at a temperature of 100 to 140 ℃ in a bath with the flame-retardant processing agent.

In addition to the above, the present invention provides a flame-retardant processed polyester-based synthetic fiber structure flame-retardant processed by the above flame-retardant processing method.

Effects of the invention

When a polyester synthetic fiber structure is subjected to flame-retardant processing using a flame-retardant processing agent containing the flame retardant of the present invention, satisfactory flame retardancy can be imparted to the polyester synthetic fiber structure without causing deterioration in physical properties of the polyester synthetic fiber structure such as discoloration, chalky marks, reduction in frictional fastness, discoloration with time, and crystallization. Further, according to the flame-retardant processing of the polyester-based synthetic fiber structure using the flame-retardant processing agent of the present invention, the load of the flame-retardant processing can be greatly reduced because the polyester-based synthetic fiber structure does not need to be washed after the flame-retardant processing.

Detailed Description

In the present invention, the polyester synthetic fiber structure means a fabric comprising at least a fiber of a polyester fiber and a yarn, cotton, woven fabric, nonwoven fabric or the like comprising such a fiber, and preferably means a fabric comprising a polyester fiber, a yarn formed therefrom, cotton, woven fabric, nonwoven fabric or the like, and further , the fabric comprising the woven fabric, nonwoven fabric or the like may be a single layer, or a laminate of 2 or more layers, or may be a composite comprising a yarn, cotton, woven fabric, nonwoven fabric or the like.

In the present invention, the polyester fiber may include, for example, polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polyethylene terephthalate/isophthalate, polyethylene terephthalate/5-sulfoisophthalate, polyethylene terephthalate/polyoxybenzoyl (ポリエチレンテレフタレート/ポリオキシベンゾイル), polybutylene terephthalate/isophthalate, poly (D-lactic acid), poly (L-lactic acid), a copolymer of D-lactic acid and L-lactic acid, a copolymer of D-lactic acid and aliphatic hydroxycarboxylic acid, a copolymer of L-lactic acid and aliphatic hydroxycarboxylic acid, polycaprolactone such as poly-epsilon-caprolactone (PCL), poly (malic acid), polyhydroxybutyric acid, polyhydroxyvaleric acid, β -hydroxybutyric acid (3HB) -3-hydroxyvaleric acid (3HV) random copolymer, poly (ethylene succinate) (PES), polybutylene succinate (PBS), polybutylene adipate, polybutylene succinate-adipate copolymer, and the like, and the functional compound may be used in the functional blending of a diol and an aliphatic dicarboxylic acid, and the like, and when the functional compound is used in the production of the polyester fiber is not limited to polyester, and the functional compound may be used in the production of a flame retardant or the functional compound may be used in the production of the polyester fiber.

The polyester-based synthetic fiber structure subjected to flame retardant processing according to the present invention can be suitably used for, for example, seat cushions, seat covers, curtains, wall papers, ceiling cloths, carpets, curtains, building curing sheets, tents, canvases, and the like.

The flame retardant for a polyester-based synthetic fiber structure of the present invention contains an amino-pentaphenoxy cyclotriphosphazene represented by the following structural formula (1).

[ solution 2]

The aminopentaphenoxycyclotriphosphazene can be obtained, for example, by reacting hexachlorocyclotriphosphazene with sodium phenolate in an appropriate organic solvent to obtain a reaction mixture containing monochloropenphenoxycyclotriphosphazene as a main component, then reacting the compound with ammonia in an appropriate organic solvent under a closed condition in a pressure-resistant container, and removing by-products from the obtained reaction mixture.

Of course, the flame retardant of the present invention may contain other aminophenoxy cyclotriphosphazene and other conventionally known flame retardants within a range not impairing the effects thereof.

According to the present invention, a flame retardant containing the above-mentioned amino pentaphenoxy cyclotriphosphazene can be suitably used as a flame retardant processing agent in which they are dispersed in an appropriate solvent.

That is, the flame retardant processing agent for a polyester-based synthetic fiber structure of the present invention is obtained by dispersing the flame retardant in a solvent in the presence of a surfactant. Here, the preferable solvent, i.e., the dispersion medium, for the flame retardant in the flame retardant processing agent is water.

However, according to the present invention, the dispersion medium may be an organic solvent or a mixture of an organic solvent, particularly a water-soluble organic solvent, and water, as long as the performance as a flame retardant processing agent is not impaired.

Therefore, the flame retardant processing agent of the present invention can be preferably obtained by mixing the above aminopentaphenoxycyclotriphosphazene and the surfactant in water, and pulverizing the mixture by a wet pulverizer.

In the present invention, any kinds of anionic surfactants, nonionic surfactants, and cationic surfactants can be used as the surfactant.

However, according to the present invention, among them, as the surfactant, it is preferable to use at least 1 selected from the following,

(a) polyoxyethylene polyoxypropylene alkyl ether represented by the following general formula (I),

[ solution 3]

(wherein R is a linear or branched alkyl group having 6 to 18 carbon atoms, which may be saturated or unsaturated, m is an average molar number of addition of ethylene oxide and an integer of 1 to 20 on average, and n is an average molar number of addition of propylene oxide and an integer of 1 to 20 on average.)

(b) Sulfuric acid ester salts of arylated phenol ethylene oxide adducts represented by the following general formula (II),

[ solution 4]

(in the formula, R₁M represents a benzyl group, a styryl group or a cumyl group, M is an integer of 1 to 3 on average, n is an integer of 5 to 30 on average, and M1⁺Represents an alkali metal ion or an ammonium ion. )

And

(c) sulfosuccinate salt of styrenated phenol ethylene oxide adduct represented by the following general formula (III)

[ solution 5]

(in the formula, M2⁺Represents an alkali metal ion or an ammonium ion, a and c each independently represent a number of 1 to 3, b and d each independently represent an addition mole number of ethylene oxide, and each independently represent a number of 5 to 30. ).

M1 in the sulfuric acid ester salt of an arylated phenol ethylene oxide adduct represented by the above general formula (II) or the sulfosuccinic acid ester salt of a styrenated phenol ethylene oxide adduct represented by the above general formula (III)⁺Or M2⁺In the case of an alkali metal ion, sodium ion or potassium ion is particularly preferable.

In the present invention, the surfactant is usually used in an amount of 3 to 15 parts by weight based on 100 parts by weight of the aminopentaphenoxycyclotriphosphazene.

When the amount of the surfactant used is more than 15 parts by weight based on 100 parts by weight of the above amino pentaphenoxy cyclotriphosphazene, the resulting flame-retardant processed polyester-based synthetic fiber structure may have low rubbing fastness and may have colored spots. When the amount of the surfactant used is less than 3 parts by weight, the above-mentioned aminopentaphenoxycyclotriphosphazene may not be dispersed in water.

In the present invention, the amount of the flame retardant in the flame retardant processing agent is not particularly limited, and is usually in the range of 20 to 50% by weight.

In the present invention, if necessary, an anionic surfactant or a nonionic surfactant other than the above may be used in combination with the surfactant , and if necessary, a cationic surfactant may be used in place of the above surfactant, insofar as the surfactant does not adversely affect the dispersion of the surfactant in water.

Examples of the anionic surfactant other than the above-mentioned anionic surfactants include higher alcohol sulfate ester salts, higher alkyl ether sulfate ester salts, sulfate ester salts of sulfated fatty acid ester and the like, alkylbenzene sulfonate salts, sulfonate salts of alkylnaphthalene sulfonic acid and the like, higher alcohol phosphate ester salts, phosphate ester salts of alkylene oxide adducts of higher alcohols, alkali metal salts, ammonium salts of hydrolysates of diisobutylene-maleic anhydride copolymers, alkali metal salts, ammonium salts of hydrolysates of styrene-maleic anhydride copolymers, alkali metal salts, ammonium salts of half-esters of diisobutylene-maleic anhydride copolymers, alkali metal salts, ammonium salts of half-esters of styrene-maleic anhydride copolymers, alkali metal salts, ammonium salts, metal salts of styrene- (meth) acrylic acid copolymers, and metal salts of polyacrylic acid.

Examples of the nonionic surfactant other than those mentioned above include polyoxyalkylene type nonionic surfactants such as arylated phenol alkylene oxide adducts, alkylphenol alkylene oxide adducts, higher alcohol alkylene oxide adducts, fatty acid alkylene oxide adducts, polyhydric alcohol aliphatic ester alkylene oxide adducts, higher alkylamine alkylene oxide adducts, fatty acid amide alkylene oxide adducts, and polyhydric alcohol type nonionic surfactants such as alkyl glycosides and sucrose fatty acid esters.

Examples of the cationic surfactant include alkylamine salts, quaternary ammonium salts, polyoxyethylene alkylamines, and polyethylene polyamine derivatives.

In the present invention, when any kinds of the polyoxyethylene polyoxypropylene alkyl ether, the sulfuric acid ester salt of an arylated phenol ethylene oxide adduct, and the sulfosuccinic acid ester salt of a styrenated phenol ethylene oxide adduct are used in combination, the above anionic surfactant, nonionic surfactant, or cationic surfactant may be used alone, or 2 or more kinds thereof may be used in combination as required.

In the present invention, a protective colloid agent such as polyvinyl alcohol, methyl cellulose, carboxymethyl cellulose, guar gum, xanthan gum, starch paste, or the like may be contained as a dispersing aid in order to improve storage stability and disperse the flame retardant in a range not to impair the performance of the flame retardant processing agent, in addition to the surfactant.

In the present invention, examples of the organic solvent that can be used as a dispersion medium for dispersing the flame retardant include alcohols such as methanol and ethanol, aromatic hydrocarbons such as toluene, xylene and alkylnaphthalene, ketones such as acetone and methyl ethyl ketone, ethers such as dioxane and ethyl cellosolve, amides such as dimethylformamide, sulfoxides such as dimethyl sulfoxide, and halogenated hydrocarbons such as dichloromethane and chloroform.

In the present invention, the organic solvent preferably includes water-soluble organic solvents such as alcohols such as methanol, ethers such as acetone and ethyl cellosolve, amides such as dimethylformamide, and sulfoxides such as dimethyl sulfoxide. These organic solvents may be used alone or in combination of 2 or more. In addition, it can be used in admixture with water.

, when a flame retardant is added to a polyester synthetic fiber structure for flame-retarding, the average particle size of the flame retardant has an important influence on the flame-retarding performance imparted to the polyester synthetic fiber structure by the processing, the smaller the average particle size of the flame retardant is, the more high flame-retarding performance can be imparted to the polyester synthetic fiber structure, and therefore, it is preferable, and is not preferable, because the larger the average particle size of the flame retardant is, the lower the storage stability as a flame-retardant processing agent is, and the flame retardant precipitates in the flame-retardant processing agent, and solidifies to form so-called nodules.

Therefore, according to the present invention, when the flame-retardant processing agent is used to perform flame-retardant processing on a polyester-based synthetic fiber structure, it is preferable to use the flame-retardant processing agent in which the aminopentaphenoxycyclotriphosphazene is dispersed in water as fine particles having an average particle size of 3 μm or less, and particularly preferable to disperse the flame retardant in water as fine particles having an average particle size of 0.3 to 1.0 μm so that the flame retardant is sufficiently diffused and attached to the inside of the polyester-based synthetic fiber structure and the flame-retardant performance of the flame retardant is durable.

When the flame retardant processing agent of the present invention is used for flame-retarding a polyester synthetic fiber structure, the flame retardant processing agent is usually diluted in water and used as a processing liquid. Such a working fluid preferably contains the amino pentaphenoxy cyclotriphosphazene of the present invention in an amount of usually 0.5 to 5% by weight.

When a polyester synthetic fiber structure is subjected to flame-retardant processing using the flame-retardant processing agent of the present invention, the amount of the amino pentaphenoxy cyclotriphosphazene, which is a flame retardant, attached to the polyester synthetic fiber structure, is not limited, since it varies depending on the form and type of the polyester synthetic fiber structure to be processed, but is usually in the range of 0.5 to 5% by weight.

When the amount of the adhesion is more than 5% by weight, the polyester-based synthetic fiber structure after flame-retardant processing may have a rough and hard hand.

When flame retardancy is imparted to a polyester-based synthetic fiber structure by using the flame retardant of the present invention, a method of mixing the flame retardant of the present invention at the time of spinning the polyester-based synthetic fiber may be used, but as described above, a method of flame-retarding a polyester-based synthetic fiber structure by using the flame retardant processing agent of the present invention as post-processing is preferable.

The method for imparting flame retardancy to a polyester synthetic fiber structure by post-processing is not particularly limited, and for example, preferred methods include a method in which a flame retardant processing agent is attached to a polyester synthetic fiber structure, dried, and then heat-treated at 80 to 200 ℃ for 1 to 5 minutes to absorb the amino pentaphenoxy cyclotriphosphazene of the present invention into the fiber.

The padding method is a method in which a polyester synthetic fiber structure such as a fabric is impregnated with a flame retardant processing agent or a processing liquid obtained by diluting the flame retardant processing agent, and then the fabric is squeezed with a roll (padding machine) to attach the flame retardant to the fabric. The spraying method is a method of spraying a flame retardant processing agent or a processing liquid obtained by diluting the flame retardant processing agent onto a fabric in a mist form to attach the flame retardant to the fabric. The coating method is a method of thickening the flame retardant processing agent, uniformly coating the agent on the back surface of the fabric, and adhering the flame retardant to the fabric.

According to the present invention, the amino pentaphenoxy cyclotriphosphazene is attached to the polyester synthetic fiber structure, dried, and heat-treated at 80 to 200 ℃ for 1 to 5 minutes as described above to absorb the amino pentaphenoxy cyclotriphosphazene out of the fiber interior, thereby imparting the flame retardant to the polyester synthetic fiber structure and providing excellent flame retardancy.

In addition, as another method for flame-retardant processing of a polyester-based synthetic fiber structure using the flame-retardant processing agent of the present invention, for example, a method using a flow dyeing machine can be mentioned、A package dyeing machine such as a beam dyeing machine or a bobbin dyeing machine, a bath treatment method in which a polyester synthetic fiber structure is immersed in a flame retardant processing agent or a processing liquid obtained by diluting the flame retardant processing agent, and the polyester synthetic fiber structure is treated in a bath at a temperature of 100 to 140 ℃ to suck the flame retardant into the fiber.

According to the present invention, the flame retardant processing agent can be applied to the polyester synthetic fiber structure by such treatment in a bath before, simultaneously with or after dyeing the polyester synthetic fiber structure at any step.

The flame retardant processing agent of the present invention may contain, if necessary, a flame retardant aid for improving the flame retardancy of the flame retardant processing agent, an ultraviolet absorber for improving light fastness, an antioxidant, and the like, in addition to the above-mentioned ones, as long as the performance is not impaired, and may further contain, if necessary, a conventionally known flame retardant.

The flame retardant processing agent of the present invention can be used in combination with other conventionally known fiber processing agents in a range that does not adversely affect the flame retardancy imparted to a polyester-based synthetic fiber structure. Examples of such a fiber processing agent include a softener, an antistatic agent, a water-and oil-repellent agent, a hard processing agent (a gentamizing agent), a texture modifier, and the like.