JP4872069B2 - Flame-retardant finishing agent and flame-retardant processing method for polyester fiber products - Google Patents

Description

  The present invention relates to a flame retardant processing of a polyester fiber product, and more specifically, a flame retardant processing agent capable of imparting a flame retardant having excellent durability without using a halogen flame retardant for a polyester fiber product, and The present invention relates to a flame-retardant processing method using the same and a flame-retardant processed polyester fiber product obtained using the method.

  Conventionally, various methods for imparting flame retardancy to polyester fiber products by post-processing are known. For example, a flame retardant processing agent obtained by dispersing a brominated cycloalkane such as 1,2,5,6,9,10-hexabromocyclododecane as a flame retardant in water using a dispersant is used as a polyester fiber product. A method of attaching is known (see, for example, Patent Document 1).

  However, according to the method for imparting flame retardancy by attaching a halogen-based compound to the polyester fiber product, harmful halogenated gas is generated when such polyester fiber product is burned. There are problems such as this having a harmful effect on the environment. Therefore, in recent years, the use of such a halogen compound as a flame retardant has been regulated.

  Thus, in the past, it has been practiced to impart flame retardancy to a polyester fiber product using a phosphoric acid ester containing no halogen as a flame retardant instead of such a halogen compound. As such phosphoric acid esters, for example, aromatic monophosphates such as tricresyl phosphate and aromatic diphosphates such as resorcinol bis (diphenyl phosphate) are known. However, such an aromatic phosphate ester, which is conventionally known as a flame retardant, can impart flame retardancy excellent in washing resistance to a polyester fiber product, but is not sufficient in dry cleaning resistance. .

  Furthermore, even when such an aromatic phosphate ester is applied to a polyester fiber product and flame-retarded, the aromatic phosphate ester gradually migrates to the surface of the polyester fiber product over time, In addition, disperse dyes used for dyeing polyester fiber products also migrate to the surface together in a state dissolved in this aromatic phosphate, resulting in so-called surface bleed, so that the fastness to dyeing is lowered. There is.

In particular, the aromatic phosphate ester conventionally known as a flame retardant, including those described above, usually has insufficient affinity with the polyester, and even if the polyester is exhausted by treatment in the bath, As mentioned above, bleed occurs, and because of its low affinity, a large amount of use is required. It has many problems such as impairing the wearing ability and contaminating the processing machine.
Japanese Patent Publication No.53-8840

  As a result of diligent research to solve the above-described problems in the flame-retardant processing of conventional polyester fiber products, the present inventors have used a certain aromatic phosphate as a flame retardant, without using a halogen-based flame retardant. It has been found that by using it, it is possible to impart flame retardancy excellent in durability to a polyester fiber product, and the present invention has been achieved. Therefore, the present invention provides a flame retardant processing agent capable of imparting flame resistance with excellent durability to a polyester fiber product, a flame retardant processing method using the same, and a flame retardant obtained using the same. An object is to provide a processed polyester fiber product.

  According to the present invention, at least one aromatic phosphate selected from biphenylyl diphenyl phosphate and naphthyl diphenyl phosphate is emulsified or dispersed in water in the presence of a nonionic surfactant and an anionic surfactant. There is provided a flame retardant processing agent for a polyester fiber product.

  In addition, according to the present invention, there is provided a flame retardant processing method for a polyester fiber product, characterized in that the polyester fiber product is flame retardant processed with the flame retardant processing agent. Hereinafter, this method may be referred to as a first method according to the present invention.

  Furthermore, according to the present invention, there is provided a flame retardant processing method for a polyester fiber product, characterized in that the polyester fiber product is flame retardant processed with the flame retardant processing agent in the presence of a flame retardant exhaust accelerator. The Hereinafter, this method may be referred to as a second method according to the present invention.

  According to the present invention, as the flame retardant exhaust accelerator, at least one selected from alkylnaphthalenes, aromatic imides, glycol ethers and halogenated benzenes is preferably used.

  In addition, according to the present invention, a flame-retardant polyester fiber product obtained by the method as described above is provided.

  The flame retardant processing agent comprising an aromatic phosphate according to the present invention does not contain a halogen atom. Therefore, by using such a flame retardant processing agent, various polyester fiber products can be used without polluting the environment. High performance and durable flame retardancy can be imparted. In particular, according to the present invention, by using a flame retardant comprising the aromatic phosphate ester together with the flame retardant exhaust accelerator, usually a cationic dyeable polyester fiber product that hardly imparts flame retardancy, Also, when dyeing polyester fiber with disperse dyes, especially when dyeing at high concentration and simultaneously flame-retarding, a small amount of flame retardant is used to provide high-performance and durable flame retardancy. be able to.

  In the present invention, the polyester fiber product refers to a fiber containing at least a polyester fiber, a yarn containing such a fiber, cotton, a fabric such as a woven fabric or a non-woven fabric, preferably a polyester fiber, a yarn comprising the same, It refers to fabrics such as cotton, knitted fabric and non-woven fabric.

  Examples of the polyester fiber include polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polyethylene terephthalate / isophthalate, polyethylene terephthalate / 5-sulfoisophthalate, polyethylene terephthalate / polyoxybenzoyl, poly Examples thereof include butylene terephthalate / isophthalate, but are not limited to those exemplified.

  Examples of the polyester-based fiber products flame-retardant processed according to the present invention include seat sheets, seat covers, curtains, wallpaper, ceiling cloths, carpets, notebooks, architectural curing sheets, tents, canvases, blouses, uniforms and other clothes, aprons, etc. Is preferably used.

  The flame retardant for a polyester fiber product according to the present invention comprises at least one aromatic phosphate selected from biphenylyl diphenyl phosphate and naphthyl diphenyl phosphate in the presence of a nonionic surfactant and an anionic surfactant. It is emulsified or dispersed in water.

  In the present invention, the biphenylyl diphenyl phosphate is 2-, 3- or 4-biphenylyl diphenyl phosphate or a mixture of two or more thereof, and naphthyl diphenyl phosphate is 1- or 2-naphthyl diphenyl phosphate or a mixture thereof. It is. These biphenylyl diphenyl phosphates and naphthyl diphenyl phosphates may be used alone or in combination as a mixture.

  According to the present invention, among the above, 2-biphenylyl diphenyl phosphate is preferably used as biphenylyl diphenyl phosphate, and 2-naphthyl diphenyl phosphate is preferably used as naphthyl diphenyl phosphate. These aromatic phosphate esters can be obtained as commercial products.

  A flame retardant for a polyester fiber product according to the present invention is obtained by emulsifying or dispersing the aromatic phosphate ester in water as a flame retardant using a nonionic surfactant and an anionic surfactant. Is.

  In the present invention, when the aromatic phosphate ester to be used is liquid at room temperature, for example, the aromatic phosphate ester is mixed with a surfactant and, if necessary, an organic solvent, heated, and uniform. After making it into a melt, it is allowed to cool to obtain a self-emulsifying flame retardant that is liquid at room temperature. When the polyester fiber product is flame-retardant processed, an emulsion of the flame-retardant processing agent in which the dispersion medium is water can be obtained by adding water to the self-emulsifying flame retardant and stirring.

  On the other hand, in the present invention, when the flame retardant used is solid at room temperature, for example, the aromatic phosphate ester is mixed with a surfactant and, if necessary, an organic solvent, heated, and uniform. If it is made into a melt and is gradually added and emulsified with stirring in warm water and allowed to cool, an emulsion of a flame retardant processing agent in which the dispersion medium is water can be obtained in the same manner as described above.

  In the present invention, when obtaining an emulsion of an aromatic phosphate ester which is a flame retardant, if necessary, the obtained emulsion can be kept uniform or the emulsifiability of the aromatic phosphate ester can be improved. For this purpose, an organic solvent can be used as described above. Examples of the organic solvent include aromatic hydrocarbons such as toluene, xylene and alkylnaphthalene, ketones such as acetone and methyl ethyl ketone, alcohols such as methyl alcohol and ethyl alcohol, glycols such as ethylene glycol and propylene glycol, Ethers such as dioxane, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, alkylene glycol alkyl ethers such as ethylene glycol monoisobutyl ether, amides such as dimethylformamide, sulfoxides such as dimethyl sulfoxide, methylene And halogenated hydrocarbons such as chloride and chloroform. These organic solvents may be used alone or in combination of two or more as required. When such an organic solvent is used, the amount used is usually in the range of 1 to 20% by weight based on the aromatic phosphate.

  When the flame retardant used is a solid at room temperature, for example, the aromatic phosphate ester is mixed with water together with a surfactant, pulverized using a wet pulverizer, and finely divided into fine particles. A dispersion of a flame retardant finish that is water can be obtained.

  In the present invention, as described above, a nonionic surfactant and an anionic surfactant are used in combination when the flame retardant comprising an aromatic phosphate is emulsified or dispersed in water. Here, as the nonionic surfactant, at least one selected from polyoxyalkylene alkyl ether having 5 to 20 oxyalkylene units in the molecule and polyoxyalkylene styrenated phenyl ether is preferably used. Specific examples of such nonionic surfactants include, for example, a 9-mol dodecyl ether ethylene oxide adduct, a 5 mol dodecyl ether ethylene oxide and 9 mol propylene oxide adduct, a 10 mol distyrenated phenol ethylene oxide adduct, and the like. Can be mentioned.

  Examples of the anionic surfactant include alkali metal salts, ammonium salts and bis (polyoxyalkylene styrenated phenyl ethers) of polyoxyalkylene styrenated phenyl ether sulfonates having 5 to 20 oxyalkylene units in the molecule. At least one selected from alkali metal salts and ammonium salts of oxalate ester sulfonates is preferably used. Specific examples of such an anionic surfactant include, for example, ammonium salt, sodium salt and bis (tristyrenated phenyl ether ethylene oxide 10 mol adduct) of tristyrenated phenol ethylene oxide 10 mol adduct. Examples thereof include sodium salts and ammonium salts of acid ester sulfonates.

  Thus, when the flame retardant processing agent according to the present invention is prepared by emulsifying or dispersing in water using the aromatic phosphate ester as a flame retardant, the above-mentioned biphenylyl diphenyl phosphate and In addition to at least one selected from naphthyl diphenyl phosphate, other flame retardants containing a phosphate ester, such as dibiphenylyl phenyl phosphate, as long as they do not adversely affect the flame retardancy imparted to the polyester fiber product Triphenyl phosphate or the like may be used. In such a case, in the present invention, it is usually desirable that the flame retardant used contains at least one selected from the above-mentioned biphenylyl diphenyl phosphate and naphthyl diphenyl phosphate in an amount of 50% by weight or more.

  Next, the flame retardant processing of the polyester fiber product according to the present invention will be described. As described above, the first method according to the present invention comprises at least one aromatic phosphate selected from biphenylyl diphenyl phosphate and naphthyl diphenyl phosphate in the presence of a nonionic surfactant and an anionic surfactant. The polyester fiber product is subjected to flame retardant processing using a flame retardant agent emulsified or dispersed in water.

  Since the flame retardant processing according to the first method according to the present invention is usually performed under high temperature and high pressure, when the flame retardant used has poor emulsification stability with respect to temperature, the flame retardant is used during the flame retardant processing. A certain aromatic phosphate ester causes an emulsification breakage and takes in the polyester oligomer in the polyester fiber, resulting in inconvenience of adhering to the polyester fabric as a soiling substance. Furthermore, there is a disadvantage that the soiled material adhering to the fabric is contaminated in the processing machine.

 Here, when emulsifying or dispersing the aromatic phosphate ester, which is a flame retardant, in water, when using only a nonionic surfactant, the resulting flame retardant processing agent has poor emulsion stability at high temperatures. Inconvenience as described above occurs. Therefore, in accordance with the present invention, by using an anionic surfactant together with a nonionic surfactant, the flame retardant processing agent can have high emulsification stability at high temperatures.

  Thus, in order to obtain a flame retardant having excellent emulsification stability at high temperatures, a nonionic surfactant is used in the range of 5 to 20% by weight with respect to the aromatic phosphate ester which is a flame retardant. In addition, it is preferable to use an anionic surfactant in the range of 5 to 10% by weight.

  When the polyester fiber product is subjected to flame retardant processing using the flame retardant according to the present invention, the amount of aromatic phosphate ester, which is a flame retardant, attached to the polyester fiber product is usually 0.03 to 10% by weight. The range is preferably 0.3 to 5% by weight. When the adhesion amount of the flame retardant to the polyester fiber product is less than 0.03% by weight, sufficient flame retardancy cannot be imparted to the polyester fiber product, and when it exceeds 10% by weight. In addition, problems such as stickiness of the texture of the fiber product after flame retardant processing occur.

  According to the first method of the present invention, a method for imparting a flame retardant to a polyester fiber product and performing flame retardant processing is not particularly limited. For example, one method is flame retardant processing. An example is a method in which a flame retardant phosphate ester is exhausted into the fiber by attaching the agent to a polyester fiber product and heat-treating it at a temperature of 100 to 220 ° C. In this case, the flame retardant can be attached to the polyester fiber product by, for example, a padding method, a spray method, a coating method, or the like. Further, as another method of applying a flame retardant according to the present invention to a polyester fiber product and performing flame retardant processing, the polyester fiber product is immersed in the flame retardant agent and treated in a bath at a temperature of 60 to 140 ° C. And a method of exhausting the flame retardant into the fiber.

  According to the present invention, when the treatment in the bath described above is performed, it can be performed simultaneously with the dyeing. When processing the flame retardant in the bath at the same time as dyeing, in addition to the required dye, if necessary, add a leveling agent, a slow dyeing agent, etc., and use a pH adjuster or pH buffering agent in the bath. It is desirable to adjust the pH to 3-6.

  The flame retardant processing agent according to the present invention may contain a surfactant other than those described above as a dispersant as required, as long as the performance is not hindered. Furthermore, according to the present invention, the flame retardant processing agent is used as a protective colloid agent such as polyvinyl alcohol, methyl cellulose, carboxymethyl cellulose, starch paste, etc. It may contain a flame retardant aid for enhancing flammability, an ultraviolet absorber for enhancing light fastness, an antioxidant, and the like.

  Furthermore, the flame retardant processing agent according to the present invention can be used in combination with other functional processing agents. Examples of such fiber processing agents include softeners, antistatic agents, water and oil repellants, hard finishes, texture modifiers, SR agents, and the like.

  As described above, the second method according to the present invention comprises at least one aromatic phosphate selected from biphenylyl diphenyl phosphate and naphthyl diphenyl phosphate in the presence of a nonionic surfactant and an anionic surfactant. A polyester fiber product is flame-retardant processed by using a flame retardant processing agent emulsified or dispersed in water together with a flame retardant exhaust accelerator.

  According to the present invention, as the flame retardant exhaust accelerator, at least one selected from alkylnaphthalenes, aromatic imides, glycol monoethers and halogenated benzenes is preferably used. Furthermore, according to the present invention, arylalkyl alcohols, di (arylalkyl) ethers, and aryl-substituted phenols are also used as flame retardant exhaust accelerators.

  These flame retardant exhaust accelerators will be described below. The alkylnaphthalenes are preferably represented by the general formula (I)

(In the formula, R ₁ represents an alkyl group having 1 to 4 carbon atoms, and m represents an integer of 1 to 3).
It is represented by In the alkylnaphthalenes represented by the above general formula (I), the alkyl group is a methyl, ethyl, propyl or butyl group, and the alkyl group having 3 or more carbon atoms may be linear or branched. It may be in the shape.

  Therefore, in the present invention, preferable specific examples of the alkylnaphthalenes include, for example, 1-methylnaphthalene, 2-methylnaphthalene, 2,3-dimethylnaphthalene, 1,3-dimethylnaphthalene, 1,4-dimethylnaphthalene, , 5-dimethylnaphthalene and the like.

  The aromatic imides preferably have the general formula (II)

(In the formula, R ₂ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or an aryl group, R ₃ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, or in combination with a benzene ring. (A condensed polycyclic aromatic ring may be formed.)
It is represented by In the aromatic imides represented by the above general formula (II), when R ₂ or R ₃ is an alkyl group, it is a methyl, ethyl, propyl or butyl group, where an alkyl having 3 or more carbon atoms is used. The group may be linear or branched. When R ₂ is an aryl group, it is preferably a phenyl group. When R ₃ forms a condensed polycyclic aromatic ring together with a benzene ring, an example of such a condensed polycyclic aromatic ring is a naphthalene ring.

  Therefore, in the present invention, preferable specific examples of the aromatic imides include, for example, phthalimide, N-methylphthalimide, N-ethylphthalimide, N-propylphthalimide, N-isopropylphthalimide, N-butylphthalimide, N-isobutylphthalimide. N-s-butylphthalimide, Nt-butylphthalimide, N-phenylphthalimide, 1,2-naphthalenedicarboxylic acid imide, and the like.

  The glycol monoethers preferably have the general formula (III)

(In the formula, A represents an ethylene group or a propylene group, R ₄ represents an alkyl group having 1 to 10 carbon atoms, an aryl group, an arylalkyl group or an allyl group, and n represents 0, 1 or 2). It is represented by In the glycol monoethers represented by the general formula (III), the alkyl group is, for example, a methyl, ethyl, propyl, butyl, hexyl, octyl, decyl group, etc., and an alkyl group having 3 or more carbon atoms. The group may be linear or branched. The aryl group is preferably a phenyl group, and the arylalkyl group is preferably a phenylmethyl group (benzyl group) or a phenethyl group (phenylethyl group). In addition, the base glycol is ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol or tripropylene glycol.

  Accordingly, preferred specific examples of the glycol monoethers include, for example, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol mono-n-butyl ether. , Triethylene glycol mono-n-butyl ether, ethylene glycol monoisobutyl ether, diethylene glycol monoisobutyl ether, triethylene glycol monoisobutyl ether, ethylene glycol monohexyl ether, diethylene glycol monohexyl ether, ethylene glycol mono-2-ethylhexyl ether, diethylene glycol mono -2- Tylhexyl ether, ethylene glycol monoallyl ether, diethylene glycol monoallyl ether, ethylene glycol monophenyl ether, diethylene glycol monophenyl ether, ethylene glycol monobenzyl ether, diethylene glycol monobenzyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, tripropylene glycol Examples include monomethyl ether, propylene glycol monopropyl ether, dipropylene glycol monopropyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol mono-n-butyl ether, propylene glycol monophenyl ether, and dipropylene glycol monophenyl ether. Door can be.

  The halogenated benzenes are preferably represented by the general formula (IV)

(In the formula, X represents a halogen atom, R ₅ represents an alkyl group having 1 to 4 carbon atoms, and p represents an integer of 1 to 3).
It is represented by In the halogenated benzenes represented by the above general formula (IV), the halogen atom is preferably chlorine or bromine, and the alkyl group is a methyl, ethyl, propyl or butyl group, wherein the number of carbon atoms is 3 The above alkyl groups may be linear or branched.

  Therefore, in the present invention, preferred specific examples of the halogenated benzenes include monochlorobenzene, methylchlorobenzene, o-dichlorobenzene, 1,3,5-trichlorobenzene and the like.

  The arylalkyl alcohols are preferably represented by the general formula (V)

(In the formula, R ₆ represents a methylene group or an ethylene group, and R ₇ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.)
It is represented by In the arylalkyl alcohols represented by the general formula (V), when R ₇ is an alkyl group, the alkyl group is a methyl, ethyl, propyl, or butyl group, and the alkyl group has 3 or more carbon atoms. The group may be linear or branched. Accordingly, preferred specific examples of the arylalkyl alcohols include benzyl alcohol, methylbenzyl alcohol, phenethyl alcohol and the like.

  The di (arylalkyl) ethers are preferably represented by the general formula (VI)

(In the formula, R ₈ and R ₉ each independently represent a divalent aliphatic hydrocarbon group having 1 to 4 carbon atoms, and R ₁₀ and R ₁₁ each independently represent a hydrogen atom or 1 to 4 carbon atoms. Represents an alkyl group.) In the di (arylalkyl) ethers represented by the general formula (VI), R ₈ and R ₉ are preferably a methylene group or an ethylene group. When R ₁₀ or R ₁₁ is an alkyl group, the alkyl group is a methyl, ethyl, propyl or butyl group, and the alkyl group having 3 or more carbon atoms may be linear or branched. But you can. Accordingly, preferred specific examples of di (arylalkyl) ethers include dibenzyl ether and diphenethyl ether.

  The aryl-substituted phenols are preferably represented by the general formula (VII)

(In the formula, R ₁₂ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.)
It is represented by In the aryl-substituted phenols represented by the above general formula (VII), when R ₁₂ is an alkyl group, the alkyl group is a methyl, ethyl, propyl or butyl group, and the alkyl group has 3 or more carbon atoms. The group may be linear or branched, and the aryl group is preferably a phenyl group. Accordingly, preferred specific examples of aryl-substituted phenols include, for example, o-phenylphenol and p-phenyl. Phenol and the like can be mentioned.

  However, according to the present invention, among the various flame retardant exhaust accelerators described above, alkylnaphthalenes, aromatic imides or glycol ethers are particularly preferably used mainly from the viewpoint of environmental load and flame retardant effect. . In particular, according to the present invention, methylnaphthalenes such as 1-methylnaphthalene and 2-methylnaphthalene, N-alkylphthalimides such as N-methylphthalimide and N-butylphthalimide, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether In addition, ethylene glycol monoethers such as ethylene glycol monophenyl ether are preferably used.

  According to the present invention, in order to emulsify and disperse such a flame retardant exhaust accelerator in a treatment liquid containing a flame retardant, as a surfactant, for example, alkylbenzene sulfonate, sorbitol, sorbitan fatty acid ester, polyoxy Alkylphenyl ether or the like can be appropriately used.

  In the second method according to the present invention, a cationic dyeable polyester mixed woven fabric obtained by mixing a regular polyester fiber yarn and a cationic dyeable polyester fiber yarn is flame-retardant processed by treatment in a bath, or from a regular polyester fiber yarn. When the resulting fabric is dyed with a disperse dye, it is particularly suitable for dyeing at a high concentration by a treatment in a bath and flame-retardant processing.

  As described above, when the flame retardant treatment is performed on the polyester fiber product by the second method according to the present invention, the flame retardant exhaust accelerator is 0 with respect to the treatment liquid for flame retardant processing of the polyester fiber product. 0.01 to 10 g / L, preferably 0.5 to 5 g / L. When the use amount of the exhaust accelerator is less than 0.01 g / L, there is a possibility that a sufficient amount of the flame retardant cannot be exhausted to the polyester fiber product. When the amount used is more than 10 g / L, the flame retardant exhaust accelerator may remain in the flame-treated polyester fiber product, which may impair flame retardancy.

  In the present invention, the cationic dyeable polyester mixed woven fabric is a mixed woven, blended, interwoven, or knitted with other fibers including cationic polyesters and other polyester fibers such as regular polyester fibers. Woven fabrics, knitted fabrics, non-woven fabrics, and the like, and also includes woven fabrics, knitted fabrics, non-woven fabrics and the like made only of cationic dyeable polyester fibers.

  In order to facilitate dyeing with a cationic dye in the polyester molecules forming the polyester fiber, the cationic dyeable polyester mixed woven fabric has a sulfonic acid such as 5-sulfoisophthalate as described above. A dicarboxylic acid monomer component having a group is incorporated into the polyester molecule. The fiber which consists of a polyester molecule which does not contain the monomer component which has such a sulfonic acid group is a regular polyester fiber. Such a cationic dyeable polyester blended fabric is more likely to generate a residue during combustion than a regular polyester fiber product, and the combustion residue generated after combustion functions as a “candle core”. Since it inhibits the drip of regular polyester, it is said that its flame retardancy is difficult. In addition, even when a regular polyester fiber product is dyed with a disperse dye at a high concentration of 3% omf or more, the combustion residue of the disperse dye acts as a “candle core” and inhibits the drip of the regular polyester. It is said that the flame retardancy is difficult.

  For example, conventionally known phosphorus-based flame retardants, such as resorcinol bis (diphenyl phosphate), have low affinity for polyester fibers, and many flame retardants adhere to the fiber surface, so that the texture tends to be sticky. In addition, there is a problem of surface bleeding, and there is a limit to the flame retardant performance that can be imparted. However, the aromatic phosphate ester, which is the flame retardant according to the present invention, has a higher affinity for polyester fibers and better dispersibility than conventional phosphorus flame retardants, so that the flame retardant absorbs well into the fiber. Therefore, a sufficient amount of flame retardant can be applied without causing stickiness in the texture. In the second method, higher flame retardancy can be economically imparted by using a flame retardant exhaust accelerator.

  EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples.

Example 1
(Manufacture of flame retardant finishing agent A)
72.5 parts by weight of an aromatic phosphate ester consisting of 65% by weight of biphenylyl diphenyl phosphate, 20% by weight of dibiphenylyl phenyl phosphate and 15% by weight of triphenyl phosphate, and 5 moles of ethylene oxide and 9 moles of propylene oxide of dodecyl ether 12 parts by weight of product, 6 parts by weight of sodium salt of bis (tristyrenated phenyl ether ethylene oxide adduct) oxalate ester sulfonated product, and 10 parts by weight of isobutyl glycol are mixed and heated to 50 ° C. for uniform melting After being made into a product, it was allowed to cool to obtain a self-emulsifying flame retardant finishing agent A that was liquid at room temperature.

Example 2
(Manufacture of flame retardant finishing agent B)
Addition of 72.5 parts by weight of aromatic phosphate ester consisting of 95% by weight of biphenylyl diphenyl phosphate and 5% by weight of triphenyl phosphate, 12 parts by weight of adduct of 10 moles of distyrenated phenol ethylene oxide, and 10 moles of tristyrenated phenol ethylene oxide 6 parts by weight of ammonium sulfate ester and 10 parts by weight of isobutyl glycol are mixed, heated to 50 ° C. to form a uniform melt, and then allowed to cool to a self-emulsifying flame retardant that is liquid at room temperature. Processing agent B was obtained.

Example 3
(Manufacture of flame retardant finishing agent C)
40 parts by weight of an aromatic phosphate composed of 95% by weight of 2-naphthyl diphenyl phosphate and 5% by weight of triphenyl phosphate, 2 parts by weight of 10-mole adduct of distyrenated phenol ethylene oxide, and 10 mol of adduct of tristyrenated phenol ethylene oxide 1 part by weight of ammonium sulfate ester and 0.1 part by weight of silicone antifoam are mixed with 30 parts by weight of water, and this is charged into a mill filled with glass beads having a diameter of 0.8 mm. The flame retardant processing agent C was obtained by adjusting the non-volatile content concentration to 40% when pulverized until the diameter reached 1.0 μm and drying at a temperature of 105 ° C. for 30 minutes.

Comparative Example 1
(Manufacture of flame retardant finishing agent D)
40 parts by weight of an aromatic phosphate composed of 100% by weight of triphenyl phosphate, 2 parts by weight of an adduct of 10 moles of distyrenated phenol ethylene oxide, 1 part by weight of an ammonium salt of a sulfate ester of 10 moles of adduct of tristyrenated phenol ethylene oxide, 0.1 part by weight of a silicone-based antifoaming agent is mixed with 30 parts by weight of water, and this is charged into a mill filled with glass beads having a diameter of 0.8 mm, and pulverized until the average particle diameter of the flame retardant becomes 1.0 μm. Then, the non-volatile component concentration was adjusted to 40% when dried at a temperature of 105 ° C. for 30 minutes to obtain a flame retardant finishing agent D.

Comparative Example 2
(Manufacture of flame retardant finishing agent E)
72.5 parts by weight of an aromatic phosphate ester consisting of 95% by weight of resorcinol bis (diphenyl phosphate) and 5% by weight of triphenyl phosphate, 12 parts by weight of a 10-mole addition product of distyrenated phenol ethylene oxide, 10 parts of tristyrenated phenol ethylene oxide A mixture of 6 parts by weight of ammonium salt of sulfuric acid ester of a molar adduct and 10 parts by weight of isobutyl glycol, heated to 50 ° C. to obtain a uniform melt, allowed to cool, and then self-emulsified at room temperature. Flame retardant finishing agent E was obtained.

Comparative Example 3
(Manufacture of flame retardant finishing agent F)
1,2,5,6,9,10-hexabromocyclododecane 40 parts by weight, dioctyl sodium sulfosuccinate 3.5 parts by weight and silicone-based antifoaming agent 0.1 part by weight are mixed with 25 parts by weight of water, This was charged in a mill filled with glass beads having a diameter of 0.8 mm, pulverized until the average particle diameter of the flame retardant became 1.0 μm, and the non-volatile content concentration was 40 minutes when dried at a temperature of 105 ° C. for 30 minutes. % To obtain a flame retardant finishing agent F.

  Examples of flame retardant processing of polyester fiber fabrics according to the first method of the present invention will be given below.

Example 4
A regular polyester fiber of 84 dtex 36 filaments made of full-dal polyester fiber (containing 3.5% by weight of titanium oxide) is used as the warp, and a polyester fiber of 167 dtex 48 filaments made of black original polyester fiber is used as the weft. Sewed and pre-set by a conventional method on a woven / 2.54 cm × 100 horizontal / 2.54 cm double-sided satin weave to give a polyester fiber fabric to be treated.

  The above-mentioned fabric to be treated was flame-retardant processed using the flame retardant processing agent A according to the present invention as described below to obtain a flame-retardant processed polyester fiber product according to the present invention.

(Flame retardant processing method)
The dyeing bath is composed of a disperse dye (Sumicaron Blue E-RPD) 0.2% omf, a dye dispersant 1.0 g / L, a flame retardant according to the present invention or a flame retardant as a comparative example, and 8.0% omf. The pH was adjusted to 3.5 to 5.0 with glacial acetic acid (80%) to a bath ratio of 1:15.

  The polyester fiber fabric to be treated is put into a dye bath, heated from 40 ° C. to 130 ° C. at a rate of 2 ° C./minute, held at that temperature for 45 minutes, and then lowered to 60 ° C. at a rate of 3 ° C./minute. Then, the mixture was soaped at 80 ° C. for 15 minutes using warm water in which 2 g / L of anhydrous sodium carbonate and 2 g / L of nonionic scouring agent were dissolved. Subsequently, it was washed with hot water at 60 ° C. for 10 minutes, washed with water for 5 minutes, dried, and then heat treated at 170 ° C. for 1 minute, and flame-retardant processed simultaneously with dyeing. Thus, about the polyester fiber fabric which carried out the flame retardant process, the adhesion amount of the flame retardant, the initial flame retardant performance, the flame retardant performance after water washing and dry cleaning were measured. The results are shown in Table 1.

Example 5
In Example 4, the flame-retardant processed polyester fiber fabric according to the present invention was obtained in the same manner except that the flame-retardant processing agent B according to the present invention was used. About this flame-retardant-processed polyester fiber fabric, the adhesion amount of the flame retardant, the initial flame-retardant performance, the flame-retardant performance after water washing and dry cleaning were measured. The results are shown in Table 1.

Example 6
In Example 4, the flame-retardant processed polyester fiber fabric according to the present invention was obtained in the same manner except that the flame-retardant processing agent C according to the present invention was used. About this flame-retardant-processed polyester fiber fabric, the adhesion amount of the flame retardant, the initial flame-retardant performance, the flame-retardant performance after water washing and dry cleaning were measured. The results are shown in Table 1.

Example 7
After scouring and presetting the same double-sided satin weave as used in Example 4 by a conventional method, it is dyed with a disperse dye (Sumicaron Blue E-RPD, 0.2% omf) and treated. A polyester fiber fabric was obtained.

  A flame retardant treatment liquid consisting of 10% by weight of flame retardant B and 90% by weight of water was attached to the treated fabric by a padding method with a pickup of 90%. Subsequently, after drying at 120 ° C. for 2 minutes, heat treatment was performed at 180 ° C. for 1 minute. Next, soaping was performed at 80 ° C. for 15 minutes using hot water in which 2 g / L of anhydrous sodium carbonate and 2 g / L of a nonionic scouring agent were dissolved. Next, after water washing at 60 ° C. for 10 minutes, water washing for 5 minutes, drying, and heat treatment at 170 ° C. for 1 minute to obtain a flame-retardant processed polyester fiber fabric. About this flame-retardant-processed polyester fiber fabric, the adhesion amount of the flame retardant, the initial flame-retardant performance, the flame-retardant performance after water washing and dry cleaning were measured. The results are shown in Table 1.

Comparative Example 4
In Example 4, the flame-retardant processed polyester fiber fabric by the comparative example was obtained similarly except having used the flame-retardant processing agent D as a comparative example. About this flame-retardant-processed polyester fiber fabric, the adhesion amount of the flame retardant, the initial flame-retardant performance, the flame-retardant performance after water washing and dry cleaning were measured. The results are shown in Table 1.

(Amount of flame retardant attached)
In the flame retardant processing, when dyeing is not performed at the same time, if the weight of the fabric to be treated before the flame retardant processing is W ₀ and the weight of the treated fabric subjected to the flame retardant processing is W, the weight change rate of the fabric before and after the flame retardant processing ΔW is the adhesion amount R of the flame retardant. Therefore, the adhesion amount R of the flame retardant is given by the formula
R = ΔW = ((W−W _{0 /} W ₀ )) × 100 (%)
It is requested from.

In flame retardant processing, when dyeing is performed at the same time, if the weight change rate due only to the dyeing process is w (%), the adhesion amount R of the flame retardant is given by the formula
R = ΔW−w (%)
It is requested from.

  In Example 7, the weight change rate w before and after dyeing of the polyester fiber fabric to be treated was 0%. Moreover, in Example 7, since only the flame retardant processing was performed by the padding method after the dyeing process, the weight change rate of the fabric before and after the flame retardant processing was defined as the amount of the flame retardant attached.

(Flame retardant performance test)
Flame retardancy was evaluated by JIS L 1091 method A-1 (microburner method) and JIS L 1091 method D (coil method). In the micro-burner method, if the afterflame is within 3 seconds, the residual dust is within 5 seconds, and the carbonized area is within 30 cm ^{2 for} both heating for 1 minute and heating for 3 seconds after flameing, the conditions are not satisfied. Was marked with x. In the coil method, if the number of times of flame contact is 3 or more, it can be said that the flame retardancy is excellent.

(Water washing)
According to JIS K 3371, a weak alkaline first-class detergent was used at a rate of 1 g / L, and a bath ratio of 1:40 was washed with water at 60 ± 2 ° C. for 15 minutes, and then rinsed at 40 ± 2 ° C. for 5 minutes. This was repeated for 5 minutes, followed by centrifugal dehydration for 2 minutes, followed by hot air drying at 60 ± 5 ° C. for 1 cycle.

(Dry cleaning (DC))
1 g of sample, 12.6 mL of tetrachloroethylene, 0.265 g of charge soap (weight composition of charge soap is nonionic surfactant (nonylphenol ether ethylene oxide 10 mol adduct) / anionic surfactant (dioctyl succinate sodium salt) The process of cleaning for 15 minutes at 30 ± 2 ° C. using / water = 10/10/1 was defined as 1 cycle, and this was performed for 5 cycles.

  As shown in Examples 4 to 7, the flame retardancy of the polyester fiber fabric using the flame retardant processing agent according to the present invention can be imparted with higher flame resistance that is superior in durability.

  Next, examples of flame retardant processing of polyester fiber fabrics according to the second method of the present invention will be given.

Example 8
A regular polyester fiber of 84 dtex 36 filaments made of full-dal polyester fiber (containing 3.5% by weight of titanium oxide) is used as the warp, and a polyester fiber of 167 dtex 48 filaments made of black original polyester fiber is used as the weft. Sewed and pre-set by a conventional method on a woven / 2.54 cm × 100 horizontal / 2.54 cm double-sided satin weave to give a polyester fiber fabric to be treated.

  The treatment bath for the flame retardant processing is 1.0% omf (0.7% omf as the flame retardant) of the flame retardant A according to the present invention, and 1.6 g / N-butylphthalimide as the flame retardant exhaust accelerator. L was blended and adjusted to pH 3.5-5.0 with glacial acetic acid (80%) to a bath ratio of 1:15.

  The polyester fiber fabric to be treated is put into a treatment bath, heated from 40 ° C. to 130 ° C. at a heating rate of 2 ° C. per minute, held at that temperature for 45 minutes, and then cooled to 3 ° C. per minute to 60 ° C. Then, the mixture was soaped at 80 ° C. for 15 minutes using warm water in which 2 g / L of anhydrous sodium carbonate and 2 g / L of nonionic scouring agent were dissolved. Subsequently, it was washed with hot water at 60 ° C. for 10 minutes, washed with water for 5 minutes, dried, heat-treated at 170 ° C. for 1 minute, and flame-retarded to obtain a flame-retardant-treated polyester fiber fabric according to the present invention. The results of the flame retardant performance test are shown in Table 2.

Example 9
Dye bath is 4% omf of disperse dye (Kayalon polyester black ECX300), 0.5 g / L of dye dispersant, 1.5% omf (1.0% omf as a flame retardant) of flame retardant processing agent B according to the present invention, 1.6 g / L of N-butylphthalimide was blended as a flame retardant exhaust accelerator, adjusted to pH 3.5 to 5.0 with glacial acetic acid (80%), and the bath ratio was 1:15.

  The same polyester fiber fabric to be treated as used in Example 8 was put into a dye bath, heated from 40 ° C. to 130 ° C. at a rate of 2 ° C. per minute, held at that temperature for 45 minutes, and then to 60 ° C. The mixture was cooled at a rate of temperature decrease of 3 ° C. per minute, and then soaped at 80 ° C. for 15 minutes using hot water in which 2 g / L of anhydrous sodium carbonate and 2 g / L of nonionic scouring agent were dissolved. Subsequently, it was washed with hot water at 60 ° C. for 10 minutes, washed with water for 5 minutes, dried, heat treated at 170 ° C. for 1 minute, and flame-retarded simultaneously with dyeing to obtain a flame-retardant-treated polyester fiber fabric according to the present invention. The results of the flame retardant performance test are shown in Table 2.

Example 10
The dyeing bath is a disperse dye (Kayalon polyester black ECX300) 4% omf, a dye dispersant 0.5 g / L, a flame retardant processing agent B according to the present invention 1.0% omf (0.7% omf as a flame retardant), As a flame retardant exhaust accelerator, 2.8 g / L of ethylene glycol monophenyl ether was blended, adjusted to pH 3.5 to 5.0 with glacial acetic acid (80%), and the bath ratio was 1:15.

  The same polyester fiber fabric to be treated as used in Example 8 was put into a dye bath, heated from 40 ° C. to 130 ° C. at a rate of 2 ° C. per minute, held at that temperature for 45 minutes, and then to 60 ° C. The mixture was cooled at a rate of temperature decrease of 3 ° C. per minute, and then soaped at 80 ° C. for 15 minutes using hot water in which 2 g / L of anhydrous sodium carbonate and 2 g / L of nonionic scouring agent were dissolved. Subsequently, it was washed with hot water at 60 ° C. for 10 minutes, washed with water for 5 minutes, dried, heat treated at 170 ° C. for 1 minute, and flame-retarded simultaneously with dyeing to obtain a flame-retardant-treated polyester fiber fabric according to the present invention. The results of the flame retardant performance test are shown in Table 2.

Example 11
The dyeing bath is a disperse dye (Kayalon polyester black ECX300) 4% omf, a dye dispersant 0.5 g / L, a flame retardant processing agent C according to the present invention 3.6% omf (1.4% omf as a flame retardant), Monochlorobenzene 1.0 g / L was blended as a flame retardant exhaust accelerator and adjusted to pH 3.5 to 5.0 with glacial acetic acid (80%) to a bath ratio of 1:15.

  The same polyester fiber fabric to be treated as used in Example 8 was put into a dye bath, heated from 40 ° C. to 130 ° C. at a rate of 2 ° C. per minute, held at that temperature for 45 minutes, and then to 60 ° C. The mixture was cooled at a rate of temperature decrease of 3 ° C. per minute, and then soaped at 80 ° C. for 15 minutes using hot water in which 2 g / L of anhydrous sodium carbonate and 2 g / L of nonionic scouring agent were dissolved. Subsequently, it was washed with hot water at 60 ° C. for 10 minutes, washed with water for 5 minutes, dried, heat treated at 170 ° C. for 1 minute, and flame-retarded simultaneously with dyeing to obtain a flame-retardant-treated polyester fiber fabric according to the present invention. The results of the flame retardant performance test are shown in Table 2.

Example 12
The dyeing bath is a disperse dye (Kayalon polyester black ECX300) 4% omf, a dye dispersant 0.5 g / L, a flame retardant processing agent C according to the present invention 3.6% omf (1.4% omf as a flame retardant), As a flame retardant exhaust accelerator, 1-methylnaphthalene (2.0 g / L) was blended, adjusted to pH 3.5 to 5.0 with glacial acetic acid (80%), and a bath ratio of 1:15 was obtained.

  The same polyester fiber fabric to be treated as used in Example 8 was put into a dye bath, heated from 40 ° C. to 130 ° C. at a rate of 2 ° C. per minute, held at that temperature for 45 minutes, and then to 60 ° C. The mixture was cooled at a rate of temperature decrease of 3 ° C. per minute, and then soaped at 80 ° C. for 15 minutes using hot water in which 2 g / L of anhydrous sodium carbonate and 2 g / L of nonionic scouring agent were dissolved. Subsequently, it was washed with hot water at 60 ° C. for 10 minutes, washed with water for 5 minutes, dried, heat treated at 170 ° C. for 1 minute, and flame-retarded simultaneously with dyeing to obtain a flame-retardant-treated polyester fiber fabric according to the present invention. The results of the flame retardant performance test are shown in Table 2.

Example 13
Using 84 dtex 36-filament cationic dyeable polyester fiber as the warp and 167 dtex 48 filament black original regular polyester fiber as the weft, density length 360 / 2.54 cm x width 100 / 2.54 cm, double-faced satin The woven fabric was scoured and pre-set by a conventional method to obtain a polyester fiber fabric to be treated. Using this treated polyester fiber fabric, replacing the disperse dye (Kayalon Polyester Black ECX300) 4% omf with a cationic dye (Kayakrill Yellow 3RL-ED) 0.5% omf, and A flame retardant polyester fiber fabric was obtained in the same manner as in Example 9 except that the pH was adjusted to 3 to 4 using a malic acid / sodium phosphate buffer instead of glacial acetic acid. The results of the flame retardant performance test are shown in Table 2.

Example 14
Using 84 dtex 36-filament cationic dyeable polyester fiber as the warp and 167 dtex 48 filament black original regular polyester fiber as the weft, density length 360 / 2.54 cm x width 100 / 2.54 cm, double-faced satin The woven fabric was scoured and pre-set by a conventional method, and then dyed by a conventional method with a cationic dye kayakryl yellow 3RL-ED) 0.5% omf to obtain a treated polyester fiber fabric. .

  By adding ethylene glycol monophenyl ether as a flame retardant exhaustion accelerator at a rate of 0.1 g / L to a treatment liquid composed of 5% by weight of flame retardant B and 95% by weight of water, a flame retardant treatment liquid is obtained. A flame retardant processed polyester fiber fabric was obtained in the same manner as in Example 7, except that was attached to the treated polyester fiber fabric with a pickup of 90%. The results of the flame retardant performance test are shown in Table 2.

Comparative Example 5
The dyeing bath is 4% omf of disperse dye (Kayalon Polyester Black ECX300), 0.5 g / L of dye dispersant, 2.0% omf as a comparative example (1.4% omf as a flame retardant) Blended and adjusted to pH 3.5-5.0 with glacial acetic acid (80%) to a bath ratio of 1:15.

  The same polyester fiber fabric to be treated as used in Example 8 was put into a dye bath, heated from 40 ° C. to 130 ° C. at a rate of 2 ° C. per minute, held at that temperature for 45 minutes, and then to 60 ° C. The mixture was cooled at a rate of temperature decrease of 3 ° C. per minute, and then soaped at 80 ° C. for 15 minutes using hot water in which 2 g / L of anhydrous sodium carbonate and 2 g / L of nonionic scouring agent were dissolved. Subsequently, it was washed with hot water at 60 ° C. for 10 minutes, washed with water for 5 minutes, dried, heat treated at 170 ° C. for 1 minute, and flame-retarded simultaneously with dyeing to obtain a flame-retardant-treated polyester fiber fabric according to the present invention. The results of the flame retardant performance test are shown in Table 2.

Comparative Example 6
The dyeing bath is 4% omf of disperse dye (Kayalon polyester black ECX300), 0.5 g / L of dye dispersant, 6.0% omf as a comparative example (4.3% omf as a flame retardant) Blended and adjusted to pH 3.5-5.0 with glacial acetic acid (80%) to a bath ratio of 1:15.

  The same polyester fiber fabric to be treated as used in Example 8 was put into a dye bath, heated from 40 ° C. to 130 ° C. at a rate of 2 ° C. per minute, held at that temperature for 45 minutes, and then to 60 ° C. The mixture was cooled at a rate of temperature decrease of 3 ° C. per minute, and then soaped at 80 ° C. for 15 minutes using hot water in which 2 g / L of anhydrous sodium carbonate and 2 g / L of nonionic scouring agent were dissolved. Subsequently, it was washed with hot water at 60 ° C. for 10 minutes, washed with water for 5 minutes, dried, heat treated at 170 ° C. for 1 minute, and flame-retarded simultaneously with dyeing to obtain a flame-retardant polyester fiber fabric. The results of the flame retardant performance test are shown in Table 2.

Comparative Example 7
The dyeing bath is 4% omf of disperse dye (Kayalon polyester black ECX300), 0.5 g / L of dye dispersant, 3.6% omf of flame retardant processing agent F as a comparative example (1.4% omf as flame retardant) Blended and adjusted to pH 3.5-5.0 with glacial acetic acid (80%) to a bath ratio of 1:15.

  The same polyester fiber fabric to be treated as used in Example 8 was put into a dye bath, heated from 40 ° C. to 130 ° C. at a rate of 2 ° C. per minute, held at that temperature for 45 minutes, and then to 60 ° C. The mixture was cooled at a rate of temperature decrease of 3 ° C. per minute, and then soaped at 80 ° C. for 15 minutes using hot water in which 2 g / L of anhydrous sodium carbonate and 2 g / L of nonionic scouring agent were dissolved. Subsequently, it was washed with hot water at 60 ° C. for 10 minutes, washed with water for 5 minutes, dried, heat treated at 170 ° C. for 1 minute, and flame-retarded simultaneously with dyeing to obtain a flame-retardant polyester fiber fabric. The results of the flame retardant performance test are shown in Table 2.

Comparative Example 8
The dyeing bath is 4% omf of disperse dye (Kayalon Polyester Black ECX300), 0.5 g / L of dye dispersant, 3.6% omf as a comparative example (1.4% omf as a flame retardant) As a flame retardant exhaust accelerator, 2.0 g / L of 1-methylnaphthalene was blended, adjusted to pH 3.5 to 5.0 with glacial acetic acid (80%), and the bath ratio was 1:15.

  The same polyester fiber fabric to be treated as used in Example 8 was put into a dye bath, heated from 40 ° C. to 130 ° C. at a rate of 2 ° C. per minute, held at that temperature for 45 minutes, and then to 60 ° C. The mixture was cooled at a rate of temperature decrease of 3 ° C. per minute, and then soaped at 80 ° C. for 15 minutes using hot water in which 2 g / L of anhydrous sodium carbonate and 2 g / L of nonionic scouring agent were dissolved. Subsequently, it was washed with hot water at 60 ° C. for 10 minutes, washed with water for 5 minutes, dried, heat treated at 170 ° C. for 1 minute, and flame-retarded simultaneously with dyeing to obtain a flame-retardant polyester fiber fabric. The results of the flame retardant performance test are shown in Table 2.

Comparative Example 9
The dyeing bath was formulated with 4% omf of disperse dye (Kayalon Polyester Black ECX300) and 0.5 g / L of a dye dispersant, adjusted to pH 3.5 to 5.0 with glacial acetic acid (80%), and a bath ratio of 1: It was set to 15.

  The same polyester fiber fabric to be treated as used in Example 8 was put into a dye bath, heated from 40 ° C. to 130 ° C. at a rate of 2 ° C. per minute, held at that temperature for 45 minutes, and then to 60 ° C. The mixture was cooled at a rate of temperature decrease of 3 ° C. per minute, and then soaped at 80 ° C. for 15 minutes using hot water in which 2 g / L of anhydrous sodium carbonate and 2 g / L of nonionic scouring agent were dissolved. Subsequently, it was washed with hot water at 60 ° C. for 10 minutes, washed with water for 5 minutes, dried, heat-treated at 170 ° C. for 1 minute, and dyed to obtain a flame-retardant processed polyester fiber fabric. The results of the flame retardant performance test are shown in Table 2.

(Amount of flame retardant attached)
It was determined by the same method as described above. In Example 8, since only the flame retardant processing was performed on the polyester fiber fabric to be treated in the bath, the weight change rate before and after the flame retardant processing of the fabric was defined as the flame retardant adhesion amount. In Examples 9 to 13, since the polyester fiber fabrics to be treated were subjected to flame retardant treatment simultaneously with the dyeing treatment, it was difficult to reduce the weight change rate of the fabric before and after the flame retardant treatment from the weight change rate only by the dyeing treatment. It was set as the adhesion amount of the flame retardant. In Example 13, the weight change rate when only the dyeing treatment was performed on the polyester fiber fabric to be treated was -0.1%. In Example 14, since the polyester fiber fabric to be treated was dyed, and then subjected to flame retardant processing by the padding method, the weight change rate of the fabric before and after flame retardant processing was defined as the amount of flame retardant attached.

(Flame retardant performance test 1)
As the flame retardancy performance test 1, it was evaluated by the A-1 method (micro burner method) of JIS L 1091. In the micro burner method, when heating is performed for 1 minute and heating for 3 seconds after flaming, the residual flame is within 3 seconds, the residual dust is within 5 seconds, and the carbonized area is within 30c. X.

(Water washing)
According to JIS K 3371, a weak alkaline first-class detergent was used at a rate of 1 g / L, and a bath ratio of 1:40 was washed with water at 60 ± 2 ° C. for 15 minutes, and then rinsed at 40 ± 2 ° C. for 5 minutes. This was repeated for 5 minutes, followed by centrifugal dehydration for 2 minutes, followed by hot air drying at 60 ± 5 ° C. for 1 cycle.

(Dry cleaning (DC))
1 g of sample, 12.6 mL of tetrachloroethylene, 0.265 g of charge soap (weight composition of charge soap is nonionic surfactant (nonylphenol ether ethylene oxide 10 mol adduct) / anionic surfactant (dioctyl succinate sodium salt) The process of cleaning for 15 minutes at 30 ± 2 ° C. using / water = 10/10/1 was defined as 1 cycle, and this was performed for 5 cycles.

(Flame retardant performance test 2)
As flame retardant performance test 2, FMVSS No. A combustion test was conducted in accordance with 302 (Automobile interior material combustion test standard). The case where the fire was extinguished at a combustion distance of 38 mm or less, or the case where the fire was extinguished at a combustion distance of 50 mm or less and the combustion time was 60 seconds or less was rated as ◯, and the case where these conditions were not satisfied was rated as x.

(Evaluation of fastness to friction)
A friction test in a dry state was conducted by a dyeing fastness test method for friction of JIS L 0849, and a determination was made on a gray scale for contamination.

  As is apparent from the results shown in Table 2, according to the present invention, in the presence of a flame retardant exhaust accelerator, at least one selected from biphenylyl diphenyl phosphate and 2-naphthyl diphenyl phosphate is used as a flame retardant. When a polyester fiber fabric is flame-retarded, excellent flame retardancy can be imparted by using a small amount of flame retardant, and excellent friction fastness can be imparted (Examples 8 to 14). ).

  In contrast, when resorcinol bis (diphenyl phosphate) as a comparative example is used as a flame retardant, it is not acceptable for flame retardant performance test 2 even if it is used at the same concentration as diphenylyl diphenyl phosphate or 2-naphthyl diphenyl phosphate. It was a pass. If resorcinol bis (diphenyl phosphate) is used at a high concentration, the flame retardancy test 2 is passed, but the fastness is markedly reduced (Comparative Examples 5 and 6).

When TPP (triphenyl phosphate) is used as the flame retardant, even if 1-methylnaphthalene is used as the flame retardant exhaustion accelerator, the flame retardant performance test 1 fails in terms of flame retardant after washing. (Comparative Example 8). When the polyester fiber fabric was only dyed without using any flame retardant or flame retardant exhaust accelerator, the fastness to friction was good, but of course the flame retardancy was not acceptable (Comparative Example). 9).

Claims (13)

Emulsified in water at least one aromatic phosphoric acid ester in the presence of a nonionic surfactant and an anionic surfactant selected from the biphenylyl diphenyl phosphate and naphthyl diphenyl phosphate, or dispersed allowed by such Lupo Riesuteru The anionic surfactant is at least one selected from alkali metal salts of bis (polyoxyalkylene styrenated phenyl ether) oxalate sulfonates and ammonium salts thereof. A flame retardant processing agent for a polyester fiber product , wherein the nonionic surfactant is a polyoxyalkylene alkyl ether having 5 to 20 oxyalkylene units in the molecule . A flame retardant processing method for a polyester fiber product, wherein the polyester fiber product is flame retardant processed with the flame retardant processing agent according to claim 1 . A flame retardant processing method for a polyester fiber product, comprising attaching the flame retardant processing agent according to claim 1 to a polyester fiber product and performing a heat treatment at a temperature of 100 to 220 ° C. A flame retardant processing method for a polyester fiber product, which comprises treating the polyester fiber product with a flame retardant processing agent according to claim 1 in a bath at a temperature of 60 to 140 ° C. Flame retarding polyester fiber product obtained by the method according to any of claims 2 4. A flame-retardant processed polyester fiber product, which is flame-retardant processed with the flame-retardant processing agent according to claim 1 . A method for flame-retardant processing of a polyester-based fiber product, characterized in that a polyester-based fiber product is flame-retardant processed with the flame-retardant processing agent according to claim 1 in the presence of a flame retardant exhaust accelerator. The method for flame retardant processing of a polyester fiber product according to claim 7 , wherein the flame retardant exhaust accelerator is at least one selected from alkylnaphthalenes, aromatic imides, glycol ethers and halogenated benzenes. The method according to claim 7 or 8 , wherein a flame retardant finish is attached to a polyester fiber product in the presence of a flame retardant exhaust accelerator and heat treated at a temperature of 100 to 220 ° C. Flame-retardant processing method for textiles. The method according to claim 7 or 8 , wherein the polyester fiber is treated with a flame retardant processing agent in a bath at a temperature of 60 to 140 ° C in the presence of a flame retardant exhaust accelerator. Product flame retardant processing method. The method according to claim 9 or 10 , wherein the polyester fiber product is a cationic dyeable polyester mixed woven fabric. The method according to claim 10 , wherein a fabric made of regular polyester fiber yarn is dyed with a disperse dye having a concentration of 3% omf or more and simultaneously flame-retardant processed. Flame retarding polyester fiber product obtained by the method according to any one of claims 7 12.