JP2017115291A - Flame retardant process of polyester synthetic fiber structure and manufacturing flame retardant composition therefor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a flame retardant composition and a flame retardant processing agent having no needs for washing a polyester synthetic fiber structure after flame retardant processing, no generation of water mark and chalk mark and no reduction of rubbing fastness and capable of providing satisfactory flame retardancy to the polyester synthetic fiber structure, a flame retardant process method of the polyester synthetic fiber structure using the flame retardant processing agent and further a manufacturing method of the flame retardant composition.SOLUTION: There is provided a flame retardant composition for a polyester synthetic fiber structure containing aminophenoxy cyclotriphosphazene of 2,4,6-triamino-2,4,6-triphenoxy cyclotriphosphazene (1) and 2,4-diamino-2,4,6,6-tetraphenoxy cyclotriphosphazene (2) of total 95 wt.% or more and aminophenoxy cyclotriphosphazene other than the above described (1) and (2) of 5 wt.% or less, wherein the (1) is 10 to 80 wt.% and the (2) is 90 to 20 wt.% of total amount 100 wt.% of the (1) and (2). There is provided a flame retardant processing agent for the polyester synthetic fiber structure by dispersing the flame retardant composition in a solvent in presence of a surfactant.SELECTED DRAWING: None

Description

  TECHNICAL FIELD The present invention relates to flame retardant processing of a polyester-based synthetic fiber structure and production of a flame retardant composition therefor, and more specifically, a polyester-based synthetic fiber structure comprising a mixture of a predetermined aminophenoxycyclotriphosphazene in a predetermined ratio. A flame retardant composition for imparting flame retardancy by post-processing, a flame retardant processed polyester-based synthetic fiber structure flame retardant processed with such a flame retardant composition, and a flame retardant comprising such a flame retardant composition Flame retardant, flame retardant processing method of polyester synthetic fiber structure using such flame retardant, flame retardant polyester synthetic fiber structure obtained by such flame retardant, and the above-mentioned difficulty The present invention relates to a method for producing a fuel composition.

  Conventionally, various methods for imparting flame retardancy to polyester-based synthetic fiber structures by post-processing are known. As typical post-processing methods, for example, an in-bath treatment method and a padding method can be given.

  As a method for imparting flame retardancy to polyester-based synthetic fiber structures by post-processing, in the past, polyester-based synthetic fibers by padding method using water-soluble salts such as guanidine phosphate and carbamate phosphate as flame retardant processing agents. Although the method of imparting to the structure has been the mainstream, the flame-retardant processed polyester-based synthetic fiber structure processed with the above water-soluble salts has crystals deposited on the surface of the fiber structure when moisture is absorbed and released. In addition, there has been a problem that a ring stain, also referred to as “sticking”, occurs when water adheres to the surface of the fiber structure (see, for example, Patent Document 1).

  So far, in order to cope with the above-mentioned problems, a halogen-based compound or a phosphorus-based compound is used as an emulsion or a dispersion, which is applied to a polyester-based synthetic fiber structure by a bath treatment method or a padding method. Methods have been studied (see, for example, Patent Documents 2 and 3).

  For example, 1,2,5,6,9,10-hexabromocyclododecane (HBCD) is known as a representative example of the halogen compound, but in recent years, this compound is harmful to the environment. Therefore, its use has been regulated.

  On the other hand, phosphoric acid esters and phosphoric acid amides are known as the phosphorus compounds. Since these phosphate esters and phosphate amides are highly hydrophobic, they are used by emulsifying and dispersing in water. At that time, a relatively large amount of a surfactant is required, and therefore these phosphate esters and phosphates are used. When acid amide is applied to a polyester-based synthetic fiber structure and flame-retarded, a large amount of surfactant remains on the surface of the fiber structure. It was essential to wash later. And when the washing | cleaning after the said flame-retardant process is not performed, there existed a problem that the polyester-type synthetic fiber structure obtained falls remarkably in friction fastness.

  Furthermore, since the phosphoric acid ester and the phosphoric acid amide have a low phosphorus content, a large amount of the flame retardant is imparted in order to achieve sufficient flame retardancy by imparting them to the polyester-based synthetic fiber structure. There is also a problem that the texture is lowered and chalk marks are generated.

  On the other hand, some cyclic phosphazene compounds having an amino group and / or phenoxy group in the molecule have a high phosphorus content, so that some of them have already been proposed for use as flame retardants for polyester-based synthetic fiber structures. (For example, see Patent Document 4).

  However, conventionally, cyclic (amino) phenoxyphosphazenes having many phenoxy groups (with amino groups), such as hexaphenoxycyclophosphazenes and pentaphenoxycyclophosphazenes, have high hydrophobicity. In order to achieve this, a large amount of surfactant was required.

  Therefore, since such a flame retardant processing agent contains a large amount of surfactant, the above-mentioned phosphoric acid ester and phosphoric acid amide are used for the polyester-based synthetic fiber structure subjected to the flame retardant processing using these flame retardant processing agents. As with the flame retardant processing, cleaning after the flame retardant processing is essential, and if this is not done, the resulting flame retardant polyester synthetic fiber structure has a problem that the friction fastness is significantly reduced. . In addition, the above-described polyester-based synthetic fiber structure in which flame-retardant processing is performed using such cyclic (amino) phenoxyphosphazene as a flame retardant has a problem that the above-described sticking easily occurs.

  On the other hand, cyclic phosphazenes having many amino groups (together with phenoxy groups), typically, for example, hexaaminocyclophosphazene, phenoxypentaaminocyclophosphazene, diphenoxytetraaminocyclophosphazene are bound to one phosphorus atom in the molecule. Since it has two bonded amino groups, that is, geminal (hereinafter referred to as gem) -diamino group, it is easily hydrolyzed under wet heat. Conventionally, cyclic phosphazenes having many amino groups (together with phenoxy groups) It is used as a flame retardant as a mixture containing various isomers having different amino and phenoxy group bonding positions to the phosphazene skeleton, and thus often contains an aminophenoxycyclophosphazene having a gem-diamino group. Use such cyclic phosphazenes Polyester-based synthetic fiber structure when flame retarding are, there is a problem to produce colored polyester synthetic fiber structure Te.

  About 2,2-diamino-4,4,6,6-tetraphenoxycyclotriphosphazene, 2,2,4-triamino-4,6,6-triphenoxycyclotriphosphazene, etc. having a gem-diamino group in the molecule Of course, there was a similar problem because it was also easily hydrolyzed under wet heat.

  In addition, when a polyester-based synthetic fiber structure is flame-retardant processed with a flame retardant processing agent containing aminophenoxycyclophosphazene as a flame retardant, the dye is used 3 to 5% owf, and when dyed darkly, The resulting polyester-based synthetic fiber structure has a significant decrease in friction fastness, and therefore, after using a phosphoric ester or phosphoric acid amide as a flame retardant, cleaning after flame retardant processing was essential (for example, And Patent Documents 5 and 6).

JP 2002-38374 A Japanese Patent Publication No.53-8840 JP 2003-193368 A JP-A-8-291467 JP 2002-105881 A Japanese Patent Laid-Open No. 10-298188

  In order to solve the above-described problems in flame retardants for flame retardant processing of conventional polyester-based synthetic fiber structures, the present inventors have produced various cyclic phosphazene compounds having amino groups and / or phenoxy groups. Their flame retardancy was studied extensively and in detail.

  As a result, the present inventors have in particular 2,4,6-triamino-2,4,6-triphenoxycyclotriphosphazene and 2,4-diamino-2,4,6,6-tetraphenoxycyclotriphosphazene. Independently or in combination, both are difficult to hydrolyze, are stable, have excellent dispersibility in solvents in the presence of surfactants, and are easily formulated into flame retardant processing agents. The obtained flame retardant can impart high flame retardancy to a polyester synthetic fiber structure with a small amount of adhesion. Particularly, for example, it can be applied to a polyester synthetic fiber structure by a padding method. To give satisfactory flame retardancy without deteriorating physical properties of the polyester fiber structure such as stickiness, generation of chalk marks, and decrease in fastness to friction, without cleaning after flame retardant processing. It was found that it is possible to impart the polyester-based synthetic fiber structure.

  Therefore, the present inventors have described the industry of 2,4,6-triamino-2,4,6-triphenoxycyclotriphosphazene and 2,4-diamino-2,4,6,6-tetraphenoxycyclotriphosphazene. In order to develop a particularly advantageous production method, as a result of further research, the above 2,4,6-triamino-2,4,6-triphenoxycyclotriphosphazene and 2,4-diamino were obtained under certain reaction conditions. A combination of a predetermined range of ratios of -2,4,6,6-tetraphenoxycyclotriphosphazene can be obtained relatively easily with the by-products of other aminophenoxycyclotriphosphazenes within a certain limit. And 2,4,6-triamino-2,4,6-triphenoxycyclotriphosphazene and 2,4-diamino-2,4,6,6 The combination of a rate of a predetermined range of tetraphenoxysilane Cyclotriphosphazene has been found to be effective as a flame retardant composition for polyester synthetic fiber structure as described above.

  Therefore, the present invention provides the above-mentioned 2,4,6-triamino-2,4,6-triphenoxycyclotriphosphazene and 2,4-diamino-2,4,6,6-tetraphenoxycyclotriphosphazene in a predetermined ratio. In addition, the above-mentioned 2,4,6-triamino-2,4,6-triphenoxycyclotriphosphazene and 2,4-diamino-2,4,6,6 are provided. An object of the present invention is to provide a production method capable of industrially advantageously producing a flame retardant composition containing tetraphenoxycyclotriphosphazene in a predetermined ratio.

According to the present invention,
(A) Structural formula (1)

2,4,6-triamino-2,4,6-triphenoxycyclotriphosphazene represented by the following structural formula (2)

A total of 95% by weight or more of 2,4-diamino-2,4,6,6-tetraphenoxycyclotriphosphazene represented by:
(B) A flame retardant composition for a polyester-based synthetic fiber structure containing 5% by weight or less of aminophenoxycyclotriphosphazene other than (1) and (2) above, wherein (1) and (2) A flame retardant composition for a polyester-based synthetic fiber structure in which (1) is 10 to 80% by weight and (2) is 90 to 20% by weight of the total amount of 100% by weight is provided. The

Moreover, according to this invention, the flame retardant processing agent for the polyester-type synthetic fiber structure formed by disperse | distributing the said flame retardant composition to a solvent in the presence of surfactant, Preferably, water is provided.
Furthermore, according to this invention, the polyester-type synthetic fiber structure flame-retardant-processed with the said flame retardant is provided.

  In addition, according to the present invention, a flame retardant processing method for a polyester synthetic fiber structure, in which a polyester synthetic fiber structure is flame retardant processed with the flame retardant processing agent, in particular, the flame retardant processing agent is converted into a polyester synthetic fiber structure. The polyester-based synthetic fiber structure is subjected to heat treatment at a temperature of 100 to 220 ° C. after being attached to an object and dried, and the flame-retardant processing agent is added to the polyester-based synthetic fiber structure at a temperature of 100 to 140 ° C. Provided is a flame retardant processing method for a polyester-based synthetic fiber structure which is exhausted in a bath at a temperature.

  Also provided is a flame retardant polyester-based synthetic fiber structure that is flame retardant processed by the flame retardant processing method.

Furthermore, in addition to the above, according to the present invention, 1.00 mol part of hexachlorocyclotriphosphazene is reacted with 3.50 to 4.10 mol part of alkali metal phenoxide to obtain 2,4,6-trichloro-2,4. , 6-triphenoxycyclotriphosphazene and 2,4-dichloro-2,4,6,6-tetraphenoxycyclotriphosphazene are synthesized, and then the chlorophenoxycyclotriphosphazene mixture is synthesized. A method for producing a flame retardant composition for a polyester-based synthetic fiber structure according to claim 1, wherein ammonia is reacted with the phosphazene mixture.

  According to the present invention, preferably, in the above production method, hexachlorocyclotriphosphazene and alkali metal phenoxide are reacted in a first organic solvent to produce 2,4,6-trichloro-2,4,6-trimethyl. A chlorophenoxycyclotriphosphazene mixture based on phenoxycyclotriphosphazene and 2,4-dichloro-2,4,6,6-tetraphenoxycyclotriphosphazene is synthesized and then in the presence of a second organic solvent. Ammonia is reacted with the chlorophenoxycyclotriphosphazene mixture.

  In particular, according to the present invention, preferably, in the production method, in the first organic solvent, the alkali metal phenoxide is added to hexachlorocyclotriphosphazene at a temperature ranging from −50 ° C. to the boiling point of the first organic solvent. It is preferable to react ammonia with the obtained chlorophenoxycyclotriphosphazene mixture at a temperature in the range of -20 to 100 ° C.

  The flame retardant composition according to the present invention is not easily hydrolyzed even under wet heat conditions, and is excellent in dispersibility in a solvent and exhaustibility in a polyester-based synthetic fiber structure. Therefore, by using a flame retardant processing agent containing such a flame retardant composition, by applying flame retardant processing to the polyester-based synthetic fiber structure, without the occurrence of sticking and chalk marks and a decrease in friction fastness, Satisfactory flame retardancy can be imparted to the polyester-based synthetic fiber structure.

  Moreover, according to the flame-retardant processing of the polyester-based synthetic fiber structure using the flame-retardant processing agent according to the present invention, it is not necessary to wash the polyester-based synthetic fiber structure after the flame-retardant processing. It can be greatly reduced.

  Furthermore, according to the present invention, it is possible to efficiently produce a flame retardant composition containing two kinds of aminophenoxycyclotriphosphazenes at a predetermined ratio described above.

  In the present invention, the polyester-based synthetic fiber structure refers to a fiber including at least a polyester fiber and a fabric including such a fiber, such as yarn, cotton, a woven fabric, and a non-woven fabric, and preferably includes a polyester fiber. It refers to fabrics such as yarn, cotton, knitted fabric and non-woven fabric. Furthermore, the fabric such as a woven fabric or a non-woven fabric may be a single layer or a laminate of two or more layers, or a composite made of yarn, cotton, a woven fabric or a non-woven fabric.

  In the present invention, the polyester fiber is, for example, polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polyethylene terephthalate / isophthalate, polyethylene terephthalate / 5-sulfoisophthalate, polyethylene terephthalate / polyoxy. Benzoyl, polybutylene terephthalate / isophthalate, poly (D-lactic acid), poly (L-lactic acid), copolymer of D-lactic acid and L-lactic acid, copolymer of D-lactic acid and aliphatic hydroxycarboxylic acid, Copolymer of L-lactic acid and aliphatic hydroxycarboxylic acid, polycaprolactone such as poly-ε-caprolactone (PCL), polymalic acid, polyhydroxycarboxylic butyric acid, polyhydroxyvaleric acid, β -Polyaliphatic hydroxycarboxylic acid such as hydroxybutyric acid (3HB) -3-hydroxyvaleric acid (3HV) random copolymer, polyethylene succinate (PES), polybutylene succinate (PBS), polybutylene adipate, polybutylene succin Examples thereof include polyesters of glycols such as nate-adipate copolymers and aliphatic dicarboxylic acids, but are not limited to those exemplified, and further. A product obtained by copolymerizing a functional compound such as a flame retardant with a polyester during production of the polyester or a blend of a functional compound such as an antibacterial agent during polymerization or yarn production may be used.

  The flame retardant polyester-based synthetic fiber structure subjected to flame retardant processing according to the present invention is suitably used for, for example, a seat sheet, a seat cover, a curtain, a wallpaper, a ceiling cloth, a carpet, a notebook, an architectural curing sheet, a tent, a canvas, and the like. It is done.

The flame retardant composition for the polyester-based synthetic fiber structure according to the present invention is:
(A) Structural formula (1)

2,4,6-triamino-2,4,6-triphenoxycyclotriphosphazene represented by the following structural formula (2)

A total of 95% by weight or more of 2,4-diamino-2,4,6,6-tetraphenoxycyclotriphosphazene represented by:
(B) A flame retardant composition for a polyester-based synthetic fiber structure containing 5% by weight or less of aminophenoxycyclotriphosphazene other than (1) and (2) above, wherein (1) and (2) (1) is 10 to 80% by weight, and (2) is 90 to 20% by weight.

  That is, according to a preferred embodiment, the flame retardant composition according to the present invention comprises 2,4,6-triamino-2,4,6-triphenoxycyclotriphosphazene (1) and 2,4-diamino-2,4, A total of 95% by weight or more of 6,6-tetraphenoxycyclotriphosphazene (2) and 5% by weight or less of aminophenoxycyclotriphosphazene other than the above (1) and (2), 100% by weight of the flame retardant composition Configure.

  When the aminophenoxycyclotriphosphazene other than the above (1) and (2) in the flame retardant composition exceeds 5% by weight, the composition aggregates in the solvent and is difficult to disperse to obtain a flame retardant processing agent. I can't.

  Of the total amount of (1) and (2) above, if an attempt is made to obtain a flame retardant composition in which (1) is less than 10% by weight and (2) is more than 90% by weight, The amount of aminophenoxycyclotriphosphazene other than the above (1) and (2) produced exceeds 5% by weight.

  On the other hand, when (1) is more than 80% by weight and (2) is less than 20% by weight of the total amount of (1) and (2) above, the polyester system of the flame retardant composition Since the adhesion rate to the synthetic fiber structure is low, sufficient flame retardancy cannot be imparted to the polyester-based synthetic fiber structure. In particular, in the treatment in the bath, since the amount of the flame retardant composition attached to the polyester synthetic fiber structure is not sufficient, the obtained polyester synthetic fiber structure does not have sufficient flame retardancy. Moreover, if it is going to obtain such a flame retardant composition, the production | generation of the undesirable by-product which has gem-diamino group will increase, and the yield of the target flame retardant composition will be low.

  According to the present invention, the flame retardant composition containing the aminophenoxycyclotriphosphazene (1) and (2) in a predetermined ratio is suitably used as a flame retardant processing agent dispersed in an appropriate solvent.

  The flame retardant processing agent for a polyester-based synthetic fiber structure according to the present invention is obtained by dispersing the above-mentioned flame retardant composition in a solvent in the presence of a surfactant. Here, a preferred dispersion medium for the flame retardant composition 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 and water as long as the performance as a flame retardant finish is not impaired.

Therefore, the flame retardant processing agent according to the present invention is preferably prepared by mixing a flame retardant composition containing the aminophenoxycyclotriphosphazene of the above-mentioned predetermined ratios (1) and (2) with water and a wet pulverizer. Can be obtained by pulverizing and making fine particles.
In the present invention, as the surfactant, any of an anionic surfactant, a nonionic surfactant and a cationic surfactant can be used.

However, according to the present invention, among the surfactants,
(A) The following general formula (I)

(Wherein R ¹ represents a benzyl group, a styryl group or a cumyl group, m is an integer of 1 to 3 on average, and n is an integer of 5 to 50 on average)
An arylated phenol ethylene oxide adduct represented by:
(B) The following general formula (II)

Wherein R ¹ 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 M is an alkali metal ion or ammonium ion Is shown.)
A sulfate ester salt of an arylated phenol ethylene oxide adduct represented by formula (III):

(In the formula, M ′ represents an alkali metal ion or an ammonium ion, a and c are each independently an average of 1 to 3, and b and d are each independently an average of 5 to 30. )
Preferably, at least one selected from sulfosuccinic acid ester salts of styrenated phenol ethylene oxide adducts represented by the formula:

In the sulfate ester salt of an arylated phenol ethylene oxide adduct represented by the general formula (II) or the sulfosuccinate ester salt of a styrenated phenol ethylene oxide adduct represented by the general formula (III), M or M When 'is an alkali metal ion, specifically, it is preferably a sodium ion or a potassium ion.

  In the present invention, when the amount of the surfactant used is more than 5.0 parts by weight with respect to 100 parts by weight of the flame retardant composition, the friction fastness of the obtained flame-retardant processed polyester synthetic fiber structure is high. There is a risk that it will be lowered and sticking out. On the other hand, when the amount of the surfactant used is less than 0.9 parts by weight, the flame retardant composition may not be dispersed in water.

  In the present invention, an anionic surfactant other than the above and a nonionic surfactant are added together with the surfactant as necessary, as long as the surfactant is not adversely affected when dispersed in water. You may use together. Moreover, you may use a cationic surfactant instead of the said surfactant as needed.

  Examples of other anionic surfactants other than those described above include sulfate esters such as higher alcohol sulfates, higher alkyl ether sulfates, sulfated fatty acid ester salts, alkylbenzene sulfonates, and alkylnaphthalene sulfonates. Examples thereof include sulfonates, higher alcohol phosphates, and alkylene oxide adduct phosphates of higher alcohols.

  Nonionic surfactants other than the above include, for example, higher alcohol alkylene oxide adducts, alkylphenol alkylene oxide adducts, fatty acid alkylene oxide adducts, polyhydric alcohol aliphatic ester alkylene oxide adducts, higher alkylamine alkylene oxide adducts, Examples include polyoxyalkylene type nonionic surfactants such as fatty acid amide alkylene oxide adducts, and polyhydric alcohol type nonionic surfactants such as alkylglycoxides and sucrose fatty acid esters.

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

  In the present invention, when used in combination with the arylated phenol ethylene oxide, sulfate ester salt of arylated phenol ethylene oxide adduct or sulfosuccinate ester salt of styrenated phenol ethylene oxide adduct, the other anionic surfactants and nonions Surfactants and cationic surfactants may be used singly or in combination of two or more as required.

  In the present invention, examples of the organic solvent that can be used as a dispersion medium for dispersing the flame retardant composition include alcohols such as methanol and ethanol, aromatic hydrocarbons such as toluene, xylene, and alkylnaphthalene, Examples thereof include 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 methylene chloride and chloroform.

  In particular, in the present invention, the organic solvent is preferably a water-soluble organic solvent such as alcohols such as methanol, ethers such as acetone and ethyl cellosolve, amides such as dimethylformamide, and sulfoxides such as dimethyl sulfoxide. Can be mentioned. These organic solvents can be used alone or in combination of two or more. It is also used by mixing with water.

  In general, when a flame retardant composition is applied to a polyester-based synthetic fiber structure and flame-retarded, the average particle size of the flame retardant composition is the flame-retardant performance imparted to the polyester-based synthetic fiber structure by the processing. Has an important impact on The flame retardant composition is more preferable as its average particle size is smaller because it can give high flame retardancy to the polyester-based synthetic fiber structure. On the contrary, the flame retardant composition has a poorer storage stability as the flame retardant when the average particle size is larger, and the flame retardant composition precipitates in the flame retardant and becomes a solid, so-called hard Since a cake is formed, it is not preferable.

  Therefore, according to the present invention, the flame retardant composition is sufficiently diffused inside the polyester synthetic fiber structure when the flame retardant processing agent is used to perform the flame retardant processing on the polyester synthetic fiber structure. The flame retardant composition may be used as a flame retardant processing agent that is dispersed in water as fine particles having an average particle size of 2 μm or less so that the flame retardant performance by the flame retardant composition is durable. In particular, it is particularly preferable that fine particles having an average particle diameter in the range of 0.3 to 1 μm are dispersed in water.

  When flame-retarding a polyester synthetic fiber structure using the flame-retardant processing agent according to the present invention, the flame-retardant processing agent is usually diluted with water and used as a processing liquid. Such a working fluid preferably contains the flame retardant composition according to the present invention in a range of usually 0.5 to 5% by weight.

  In addition, when the polyester-based synthetic fiber structure is flame-retardant processed using the flame-retardant processing agent according to the present invention, the adhesion amount of the flame-retardant composition to the polyester-based synthetic fiber structure varies depending on the form and type, Usually, the amount of the flame retardant composition is in the range of 0.1 to 5% by weight, preferably 1 to 5% by weight.

  However, the adhesion amount of the flame retardant composition to the polyester-based synthetic fiber structure does not limit the adhesion amount of the flame retardant composition according to the present invention. This is because, depending on the polyester-based synthetic fiber structure, even if the amount of the flame retardant composition according to the present invention is about 0.5% by weight, the polyester-based synthetic fiber structure may be provided with sufficient flame retardancy. it can. On the other hand, depending on the polyester-based synthetic fiber structure, when the amount of the flame retardant composition according to the present invention is less than 1% by weight, sufficient flame retardancy may not be imparted to the polyester-based synthetic fiber structure. is there.

  On the other hand, when it exceeds 5% by weight, problems such as roughening of the texture of the polyester-based synthetic fiber structure after the flame-retardant processing occur.

  In order to impart flame retardancy to the polyester-based synthetic fiber structure using the flame-retardant composition according to the present invention, it is possible to use a method of kneading the flame-retardant composition according to the present invention during spinning of the polyester-based synthetic fiber. As described above, it is preferable to use a flame retardant processing agent according to the present invention and a method of performing a flame retardant processing as a post-processing on a polyester synthetic fiber structure.

  The method of imparting flame retardancy to the polyester-based synthetic fiber structure by post-processing is not particularly limited. For example, as one preferable method, a flame-retardant processing agent is attached to the polyester-based synthetic fiber structure. And a method of exhausting the flame retardant composition according to the present invention into the fiber after heat treatment at a temperature of 100 to 220 ° C. for 1 to 5 minutes. In this method, the flame retardant finish can be attached to the polyester synthetic fiber structure by, for example, a padding method, a spray method, a coating method, or the like.

  In the padding method, a flame retardant composition is prepared by immersing a polyester-based synthetic fiber structure such as a fabric in a flame retardant processing agent or a processing liquid diluted with the same, and then squeezing the fabric with a roller (mangle). Is attached to the fabric. The spray method is a method in which a flame retardant processing agent or a processing liquid diluted with the flame retardant is sprayed on a fabric in a mist state to attach the flame retardant to the fabric. The coating method is a method in which the flame retardant is thickened and uniformly applied to the back surface of the fabric so that the flame retardant adheres to the fabric.

  According to the present invention, after the flame retardant composition is attached to the polyester-based synthetic fiber structure in this way, it is dried and heat-treated at a temperature of 100 to 220 ° C. for 1 to 5 minutes as described above. The flame retardant composition can be exhausted to the inside of the fiber, and thus a flame retardant can be imparted to the polyester-based synthetic fiber structure to give excellent flame retardancy.

  In addition, as another method for flame retardant processing of a polyester synthetic fiber structure using the flame retardant processing agent according to the present invention, for example, a package dyeing machine such as a liquid dyeing machine, a beam dyeing machine, a cheese dyeing machine or the like is used. In the bath, the polyester-based synthetic fiber structure is immersed in a flame retardant processing agent or a processing solution diluted with the flame retardant, and is treated in a bath at a temperature of 100 to 140 ° C. to exhaust the flame retardant composition into the fiber. The law can be mentioned.

  According to the present invention, the application of the flame retardant processing agent to the polyester-based synthetic fiber structure by the treatment in the bath is performed before dyeing the polyester-based synthetic fiber structure, at the same time as or after dyeing. You may go on time.

  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. In addition, according to the present invention, the flame retardant processing agent can be used as a protective colloid agent such as polyvinyl alcohol, methyl cellulose, carboxymethyl cellulose, starch paste, or the like, in order to increase the storage stability as necessary. It may contain a flame retardant aid for enhancing flammability, an ultraviolet absorber for enhancing light fastness, an antioxidant, and the like. If necessary, a conventionally known flame retardant may be included.

  Furthermore, the flame retardant processing agent according to the present invention may contain a polyester resin emulsion or a urethane resin emulsion, if necessary, in order to improve the friction fastness of the polyester-based synthetic fiber structure subjected to the flame retardant processing. Good. The urethane resin emulsion may be any of polyether, polyester, and polycarbonate. From the viewpoint of light fastness and heat resistance of the resulting polyester synthetic fiber structure, polyester or polycarbonate may be used. preferable.

  In addition, a smoothing agent obtained by emulsifying paraffin wax, polyethylene wax, polypropylene wax, oxide wax, carnauba wax, montan wax, etc. in water to improve the sewing properties of the flame-retardant polyester synthetic fiber structure. May be included.

  The flame retardant processing agent according to the present invention can be used in combination with other conventionally known fiber processing agents within a range that does not adversely affect the flame retardant performance given to the polyester synthetic fiber structure. Examples of such fiber finishing agents include softeners, antistatic agents, water and oil repellents, hard finishes, and texture modifiers.

The production of the flame retardant composition according to the present invention will be described below. A flame retardant composition for a polyester-based synthetic fiber structure according to the present invention is hexachlorocyclotriphosphazene 1.0.
Alkaline metal phenoxide (3.50 to 4.10 mole part) is reacted with 0 mole part to obtain 2,4,6-trichloro-2,4,6-triphenoxycyclotriphosphazene and 2,4-dichloro-2,4. , 6,6-Tetraphenoxycyclotriphosphazene can be obtained as a solid by synthesizing a chlorophenoxycyclotriphosphazene mixture mainly composed of 1,6,6-tetraphenoxycyclotriphosphazene and then reacting the chlorophenoxycyclotriphosphazene mixture with ammonia.

  First, according to the method of the present invention, preferably, 2,4,6-trichloro-2,4,6-triphenoxy is obtained by reacting hexachlorocyclotriphosphazene with an alkali metal phenoxide in a first organic solvent. A chlorophenoxycyclotriphosphazene mixture in which cyclotriphosphazene and 2,4-dichloro-2,4,6,6-tetraphenoxycyclotriphosphazene are the main components is obtained.

  The first organic solvent is not particularly limited as long as it does not adversely influence the reaction. Usually, ether systems such as diethyl ether, tetrahydrofuran (THF), 1,4-dioxane, 1,2-dimethoxyethane, butyl methyl ether, diisopropyl ether, 1,2-diethoxyethane, diphenyl ether, benzene, toluene, chlorobenzene, Aromatic hydrocarbons such as nitrobenzene, xylene, ethylbenzene, isopropylbenzene, halogenated hydrocarbons such as chloroform and methylene chloride, and aliphatic hydrocarbons such as pentane, hexane, cyclohexane, heptane, octane, nonane, undecane, and dodecane In addition, an organic solvent such as cyanide and acetone is used. Of these, toluene, THF or 1,4-dioxane is particularly preferably used.

  Moreover, as an alkali metal in an alkali metal phenoxide, lithium, sodium, potassium salt or cesium is usually preferable, and sodium or potassium is particularly preferable. Alkali metal phenoxide is obtained from a dehydrogenation reaction between phenol and metal lithium, metal sodium, or metal potassium, or from a mixture of phenol and an alkali metal hydroxide such as lithium hydroxide, sodium hydroxide, or potassium hydroxide. It can be prepared by a dehydration reaction.

  The organic solvent for the alkali metal phenoxide is not particularly limited as long as it does not adversely influence the reaction. Usually, ether system such as diethyl ether, THF, 1,4-dioxane, 1,2-dimethoxyethane, butyl methyl ether, diisopropyl ether, 1,2-diethoxyethane, diphenyl ether, benzene, toluene, chlorobenzene, nitrobenzene, xylene , Aromatic hydrocarbons such as ethylbenzene and isopropylbenzene, halogenated hydrocarbons such as chloroform and methylene chloride, aliphatic hydrocarbons such as pentane, hexane, cyclohexane, heptane, octane, nonane, undecane and dodecane, pyridine, etc. These heterocyclic aromatic hydrocarbons, tertiary amines, cyanide compounds, acetone and the like are used. Among these, THF or 1,4-dioxane is particularly preferably used.

  According to the present invention, the amount of alkali metal phenoxide with respect to hexachlorocyclotriphosphazene is in the range of 3.50 to 4.10 mol parts with respect to 1.00 mol parts of hexachlorocyclotriphosphazene.

  More specifically, according to the present invention, when 3.50 mole part of alkali metal phenoxide is used with respect to 1.00 mole part of hexachlorocyclotriphosphazene, 2,4,6-triamino-2,4,6- When the total amount of triphenoxycyclotriphosphazene (1) and 2,4-diamino-2,4,6,6-tetraphenoxycyclotriphosphazene (2) is 100% by weight, aminophenoxycyclotriphosphazenes other than the above In general, the former (1) can be obtained at a ratio of 70% by weight or more while keeping the amount below 5% by weight.

  On the other hand, when 4.10 mol parts of alkali metal phenoxide is used with respect to 1.00 mol parts of hexachlorocyclotriphosphazene, the latter (usually, the aminophenoxycyclotriphosphazene other than the above is suppressed to less than 5% by weight. 2) can be obtained in a proportion of 80% by weight or more.

  According to the present invention, an aminophenoxy other than the above (1) and (2) is used by using the amount of the alkali metal phenoxide in the range of 3.50 to 4.10 mol parts with respect to 1.00 mol parts of hexachlorocyclotriphosphazene. While suppressing cyclotriphosphazene to 5% by weight or less, out of the total amount of 100% by weight of the above (1) and (2), (1) is 10 to 80% by weight, and (2) is 90 to 20%. It is possible to obtain a flame retardant composition for the mixture which is% by weight, ie for the polyester-based synthetic fiber structure according to the invention.

  Further, according to the present invention, by increasing the amount of alkali metal phenoxide with respect to 1.00 mol part of hexachlorocyclotriphosphazene in the range from 3.50 mol part to 4.10 mol part, (2) to (1) A mixture of the above (1) and (2) with an increased ratio can be obtained.

  When the amount of the alkali metal phenoxide is less than 3.50 mole part relative to 1.00 mole part of hexachlorocyclotriphosphazene, 2,2,4,6-tetrachloro-4,6-diphenoxycyclotriphosphazene or 2, An intermediate having two chloro groups at one phosphorus atom in the cyclotriphosphazene molecule is formed, such as 2,4-trichloro-4,6,6-triphenoxycyclotriphosphazene. When these intermediates are aminated, 2,2,4,6-tetraamino-4,6-diphenoxycyclotriphosphazene, 2,2,4-triamino-4,6,6-triphenoxycyclotriphosphazene, etc. Thus, a compound in which two amino groups are bonded to one phosphorus atom in the cyclotriphosphazene molecule, that is, a compound having a geminal-diamino group is formed. However, such a compound having a geminal-diamino group is not suitable for use as a flame retardant because it easily hydrolyzes under high temperature and high humidity.

  On the other hand, when the amount of the alkali metal phenoxide is more than 4.10 mol parts with respect to 1.00 mol parts of hexachlorocyclotriphosphazene, aminopentaphenoxycyclotriphosphazene having a melting point of 76 ° C. is obtained by amination of the obtained intermediate. A product containing a large amount of aminophenoxycyclotriphosphazene having a relatively low melting point, such as a step of solidifying and removing such an undesirable reaction product. Since the mixture of said (1) and (2) cannot be obtained with a high yield, it is industrially disadvantageous.

  The reaction temperature when the alkali metal phenoxide is reacted with hexachlorocyclotriphosphazene is appropriately determined in consideration of the thermal stability of the reaction product, the boiling point or melting point of the organic solvent used, and the like. For example, when performing the said reaction using an organic solvent, it is the temperature range from -50 degreeC to the boiling point of a solvent normally, Preferably, it is the range of -20-150 degreeC, More preferably, it is 0-120. It is in the range of ° C. On the other hand, when performing the said reaction without a solvent, reaction temperature is the range of 0-200 degreeC normally, Preferably, it is the range of 10-150 degreeC.

  In this way, preferably after obtaining a chlorophenoxycyclotriphosphazene mixture in a first organic solvent, the resulting reaction mixture is initially dissolved in aqueous sodium hydroxide to remove unreacted phenol. And an alkaline aqueous solution such as an aqueous potassium hydroxide solution, and then washed with demineralized water an appropriate number of times. Thereafter, the first organic solvent is removed from the reaction mixture to obtain the chlorophenoxycyclotriphosphazene mixture.

  According to the method of the present invention, the chlorophenoxycyclotriphosphazene mixture thus obtained is preferably charged into a pressure vessel together with a second organic solvent, then ammonia is added to the pressure vessel and the chlorophenoxy React with the cyclotriphosphazene mixture.

  Here, the second organic solvent is not particularly limited as long as it does not adversely affect the reaction, but usually diethyl ether, THF, 1,4-dioxane, 1,2-dimethoxy. Ethers such as ethane, butyl methyl ether, diisopropyl ether, 1,2-diethoxyethane, diphenyl ether, aromatic hydrocarbons such as benzene, toluene, chlorobenzene, nitrobenzene, xylene, ethylbenzene, isopropylbenzene, chloroform, methylene chloride, etc. Halogenated hydrocarbons such as pentane, hexane, cyclohexane, heptane, octane, nonane, undecane, dodecane, etc., heterocyclic aromatic hydrocarbons such as pyridine, tertiary amines, cyanide compounds List organic solvents such as acetone Can. Of these, THF, 1,4-dioxane or toluene is particularly preferably used.

  The amount of ammonia used in the above reaction can be determined from the amount of amino group substituting the chlorine atom of the chlorophenoxycyclotriphosphazene mixture, which is a reactant, with an amino group. Here, since ammonia is used as a substituting agent and a deoxidizing agent, 2 equivalents of ammonia are required for 1 equivalent of chlorine. For example, to introduce one amino group into (trichloro) (triphenoxy) cyclotriphosphazene to obtain amino (dichloro) (triphenoxy) cyclotriphosphazene, ammonia is equivalent to 2 equivalents per 1 equivalent of chlorine. Of ammonia is used.

  Accordingly, in the present invention, although not limited, ammonia is usually 3.80 depending on the intended aminophenoxycyclotriphosphazene, based on 1.00 mol part of hexachlorocyclotriphosphazene used. It is used in the range of ˜100 mol parts.

  The reaction temperature when the chlorophenoxycyclotriphosphazene mixture is reacted with ammonia can be appropriately set in consideration of the thermal stability of the reaction product or the vapor pressure of ammonia. Usually, it is the temperature of -20 degreeC to 100 degreeC, Preferably it is the range of 0-80 degreeC, More preferably, it is the range of 10-60 degreeC.

  After reacting the chlorophenoxycyclotriphosphazene mixture with ammonia in this way, the resulting reaction mixture was diluted with an appropriate organic solvent, for example, the second organic solvent, and a by-product salt such as ammonium chloride was formed. Is removed by washing with water and the like, and the resulting reaction product is purified, and then the organic solvent is concentrated to obtain the target product as a solid.

  Hereinafter, the present invention will be described in detail with reference to examples showing synthesis examples of the flame retardant composition according to the present invention, production examples of the flame retardant processing agent according to the present invention, and examples illustrating the flame retardant processing according to the present invention together with comparative examples. However, the present invention is not limited to these examples.

  In the following, the non-volatile content in the flame retardant processing agent means the ratio of the flame retardant composition in the flame retardant processing agent, and the flame retardant processing agent together with the flame retardant composition, surfactant, antifoaming agent and other When the auxiliary agent is included, it means the ratio of the total amount of nonvolatile components in the flame retardant composition, the surfactant, the antifoaming agent and the other auxiliary agent.

  The average particle diameter of the flame retardant composition is a volume-based median obtained by measuring the particle size distribution of the flame retardant composition in the flame retardant processing agent with a laser diffraction particle size distribution analyzer SALD-2000J manufactured by Shimadzu Corporation. The diameter.

  In the following, unless otherwise specified, “%” and “parts” mean “% by weight” and “parts by weight”, respectively.

  2,4,6-triamino-2,4,6-triphenoxycyclotriphosphazene and 2,4-diamino-2,4,6,6 in the flame retardant compositions obtained in the following examples and comparative examples -Tetraphenoxycyclotriphosphazene and other aminophenoxycyclotriphosphazenes are identified based on the results of HPLC analysis, LC / MS analysis and analysis of elemental chlorine (residual chlorine) by potentiometric titration using silver nitrate, The contents of 4,6-triamino-2,4,6-triphenoxycyclotriphosphazene and 2,4-diamino-2,4,6,6-tetraphenoxycyclotriphosphazene were determined by HPLC analysis, and Were measured for melting temperature and 5% weight loss temperature by TG / DTA analysis.

A. Production Example 1 of Flame Retardant Composition
(Synthesis of flame retardant composition A containing 2,4,6-triamino-2,4,6-triphenoxycyclotriphosphazene and 2,4-diamino-2,4,6,6-tetraphenoxycyclotriphosphazene)
Into a 10 L flask equipped with a stirrer, a thermometer and a reflux condenser, 521 g (1.50 mol) of hexachlorocyclotriphosphazene was charged, and 2000 mL of toluene was added and dissolved to obtain a hexachlorocyclotriphosphazene solution.

  A solution obtained by adding 2400 mL of THF to 610 g (5.25 mol) of sodium phenoxide was added dropwise to the hexachlorocyclotriphosphazene solution at an internal temperature of 20 ° C. to 35 ° C., and the temperature was raised and refluxed for 1 hour. Next, THF was distilled off from the reaction solution, followed by stirring at 110 ° C. for 8 hours.

  The reaction mixture thus obtained was washed with 2000 mL of 2% aqueous sodium hydroxide solution and then twice with 1000 mL of demineralized water. Toluene and a small amount of water were distilled off from the obtained toluene layer to obtain 816 g of a chlorophenoxycyclotriphosphazene mixture.

  As a result of analyzing this mixture by HPLC using a sample prepared in advance, 2,4,6-trichloro-2,4,6-triphenoxycyclotriphosphazene and 2,4-dichloro-2,4,6,6 were obtained. -It was confirmed that tetraphenoxycyclotriphosphazene was the main component.

  815 g of the above chlorophenoxycyclotriphosphazene mixture and 320 mL of toluene are placed in a 2 L stainless steel pressure vessel, then the pressure inside the pressure vessel is reduced to 400 hPa, 221 g (13.0 mol) of ammonia is added, and sealed at 50 ° C. Stir for 15 hours. Thereafter, the pressure vessel was opened, the reaction product was diluted with 3500 mL of toluene, washed with demineralized water, and the solvent was distilled off to obtain 462 g of a white solid.

  The result of analyzing this white solid is shown below.

HPLC:
(Analysis condition 1)
Analytical compound: 2,4,6-triamino-2,4,6-triphenoxycyclotriphosphazene,
Equipment: Agilent Technologies 1260 Infinity,
Column: Inertsil HILIC, 3 μm, 4.6 mm D. 250mm
L (manufactured by GL Sciences),
Column temperature: 40 ° C
Mobile phase: 0.1% aqueous formic acid / acetonitrile = 10/90,
Flow rate: 1.0 mL / min,
Detector: UV 254 nm,
Sample concentration: 5 mg / mL (solvent acetonitrile),
Injection volume: 1 μL.

(Analysis condition 2)
Analytical compound: 2,4-diamino-2,4,6,6-tetraphenoxycyclotriphosphazene,
Equipment: Agilent Technologies 1260 Infinity,
Column: Inertsil ODS-2, 5 μm, 4.6 mm D. , 250 mm L (manufactured by GL Sciences)
Column temperature: 40 ° C
Mobile phase A: 0.1% phosphoric acid aqueous solution,
B: acetonitrile,
Gradient: 0-12 min: B = 60%, 12-15 min: B = 100%
15-25 min: B = 100%
Detector: UV 254 nm,
Flow rate: 1.0 mL / min,
Sample concentration: 5 mg / mL (solvent acetonitrile),
Injection volume: 1 μL,
LC / MS (positive-ESI):
2,4,6-triamino-2,4,6-triphenoxycyclotriphosphazene: m / z: 463 (M + H ⁺ ),
2,4-diamino-2,4,6,6-tetraphenoxycyclotriphosphazene: m / z: 540 (M + H ⁺ ).

Under HPLC analysis condition 1, a peak having a retention time consistent with a 2,4,6-triamino-2,4,6-triphenoxycyclotriphosphazene standard product was confirmed, and the peak was determined by LC / MS analysis. It was confirmed that z: 463 (M + H ⁺ ).

In addition, in the analysis condition 2, it was confirmed that the retention time coincided with the 2,4-diamino-2,4,6,6-tetraphenoxycyclotriphosphazene standard product, and the peak was analyzed by LC / MS analysis. M / z: 540 (M + H ⁺ ).

  Further, the contents of these two components are quantified, and the rest are mixed with other aminophenoxycyclotriphosphazene components (2,2,4,6-tetraamino-4,6-diphenoxycyclotriphosphazene, 2,2,4-triamino). -4,6,6-triphenoxycyclotriphosphazene, 2,2-diamino-4,4,6,6-tetraphenoxycyclotriphosphazene and monoaminopentaphenoxycyclotriphosphazene).

Hydrolyzed chlorine: 0.01% or less,
TG / DTA analysis:
Melting temperature: 100 ° C. or higher,
5% weight loss temperature: 274 ° C.

  From the above analysis results, the white solids are 2,4,6-triamino-2,4,6-triphenoxycyclotriphosphazene and 2,4-diamino-2,4,6,6-tetraphenoxycyclotriphosphazene. The composition was 76% and 20%, respectively, and the other aminophenoxycyclotriphosphazene components were 4%. Yield 61.5%.

Example 2
(Synthesis of flame retardant composition B containing 2,4,6-triamino-2,4,6-triphenoxycyclotriphosphazene and 2,4-diamino-2,4,6,6-tetraphenoxycyclotriphosphazene)
Into a 10 L flask equipped with a stirrer, a thermometer and a reflux condenser, 521 g (1.50 mol) of hexachlorocyclotriphosphazene was charged, and 2000 mL of toluene was added and dissolved to obtain a hexachlorocyclotriphosphazene solution.

  A solution obtained by adding 2700 mL of THF to 688 g (5.93 mol) of sodium phenoxide was added dropwise to the above hexachlorocyclotriphosphazene solution at an internal temperature of 20 ° C. to 35 ° C., and the temperature was raised and refluxed for 1 hour. Next, THF was distilled off from the reaction solution, followed by stirring at 110 ° C. for 8 hours.

  The reaction mixture thus obtained was washed with 2000 mL of 2% aqueous sodium hydroxide solution and then twice with 1000 mL of demineralized water. Toluene and a small amount of water were distilled off from the obtained toluene layer to obtain 854 g of a chlorophenoxycyclotriphosphazene mixture.

  As a result of analyzing this mixture by HPLC using a sample prepared in advance, 2,4,6-trichloro-2,4,6-triphenoxycyclotriphosphazene and 2,4-dichloro-2,4,6,6 were obtained. -It was confirmed that tetraphenoxycyclotriphosphazene was the main component.

  Put 853 g of the above chlorophenoxycyclotriphosphazene mixture and 330 mL of toluene in a 2 L stainless steel pressure vessel, then reduce the pressure vessel to 400 hPa, add 182 g (10.7 mol) of ammonia, and seal at 50 ° C. Stir for 15 hours. Thereafter, the pressure vessel was opened, the reaction product was diluted with 3500 mL of toluene, washed with demineralized water, and then the solvent was distilled off to obtain 661 g of a white solid.

  The result of analyzing this white solid is shown below.

HPLC and LC / MS (positive-ESI):
The measurement was performed under the same conditions and method as in Example 1. As a result, under HPLC analysis conditions 1 and 2, 2,4,6-triamino-2,4,6-triphenoxycyclotriphosphazene standard product or 2,4-diamino-2,4,6,6-tetraphenoxycyclo Peaks having the same retention times as those of the triphosphazene standard were confirmed, and these peaks were confirmed by LC / MS analysis to be m / z: 463 (M + H ⁺ ) or 540 (M + H ⁺ ), respectively. .

Hydrolyzed chlorine: 0.01% or less,
TG / DTA analysis:
Melting temperature: 80 ° C or higher,
5% weight loss temperature: 289 ° C.

  From the above analysis results, the white solids are 2,4,6-triamino-2,4,6-triphenoxycyclotriphosphazene and 2,4-diamino-2,4,6,6-tetraphenoxycyclotriphosphazene. The composition was 15% and 83%, respectively, and the other aminophenoxycyclotriphosphazene components were 2%. Yield 82.3%.

Example 3
(Synthesis of flame retardant composition C containing 2,4,6-triamino-2,4,6-triphenoxycyclotriphosphazene and 2,4-diamino-2,4,6,6-tetraphenoxycyclotriphosphazene)
To a 10 L flask equipped with a stirrer, a thermometer and a reflux condenser, 521 g (1.50 mol) of hexachlorocyclotriphosphazene was charged, and 2000 mL of toluene was added and dissolved to obtain a hexachlorocyclotriphosphazene solution.

  A solution obtained by adding 2600 mL of THF to 662 g (5.70 mol) of sodium phenoxide was added dropwise to the above hexachlorocyclotriphosphazene solution at an internal temperature of 20 ° C. to 35 ° C., and the temperature was raised and refluxed for 1 hour. Next, THF was distilled off from the reaction solution, followed by stirring at 110 ° C. for 8 hours.

  The reaction mixture thus obtained was washed with 2000 mL of 2% aqueous sodium hydroxide solution and then twice with 1000 mL of demineralized water. Toluene and a small amount of water were distilled off from the obtained toluene layer to obtain 842 g of a chlorophenoxycyclotriphosphazene mixture.

  As a result of analyzing this mixture by HPLC using a sample prepared in advance, 2,4,6-trichloro-2,4,6-triphenoxycyclotriphosphazene and 2,4-dichloro-2,4,6, It was confirmed that 6-tetraphenoxycyclotriphosphazene was the main component.

  Place 841 g of the above chlorophenoxycyclotriphosphazene mixture and 330 mL of toluene in a 2 L stainless steel pressure vessel, then depressurize the pressure vessel to 400 hPa, add 195 g (11.4 mol) of ammonia, and seal at 50 ° C. Stir for 15 hours. Thereafter, the pressure vessel was opened, and 3500 mL of toluene was added to the reaction for dilution. After washing with demineralized water, the solvent was distilled off to obtain 707 g of a white solid.

  The result of analyzing this white solid is shown below.

HPLC and LC / MS (positive-ESI):
The measurement was performed under the same conditions and method as in Example 1. As a result, under HPLC analysis conditions 1 and 2, 2,4,6-triamino-2,4,6-triphenoxycyclotriphosphazene standard product or 2,4-diamino-2,4,6,6-tetraphenoxycyclo Peaks having the same retention times as those of the triphosphazene standard were confirmed, and these peaks were confirmed by LC / MS analysis to be m / z: 463 (M + H ⁺ ) or 540 (M + H ⁺ ), respectively. .

Hydrolyzed chlorine: 0.01% or less TG / DTA analysis:
Melting temperature: 80 ° C or higher 5% weight loss temperature: 277 ° C

  From the above analysis results, the white solid was found to be 2,4,6-triamino-2,4,6-triphenoxycyclotriphosphazene and 2,4-diamino-2,4,6,6-tetraphenoxycyclotriphosphazene. The compositions were 32% and 64%, respectively, and the other aminophenoxycyclotriphosphazene components were 4%. Yield 90.0%.

Example 4
(Synthesis of flame retardant composition D containing 2,4,6-triamino-2,4,6-triphenoxycyclotriphosphazene and 2,4-diamino-2,4,6,6-tetraphenoxycyclotriphosphazene)
Into a 10 L flask equipped with a stirrer, a thermometer and a reflux condenser, 521 g (1.50 mol) of hexachlorocyclotriphosphazene was charged, and 2000 mL of toluene was added and dissolved to obtain a hexachlorocyclotriphosphazene solution.

  A solution obtained by adding 2800 mL of THF to 705 g (6.08 mol) of sodium phenoxide was added dropwise to the above hexachlorocyclotriphosphazene solution at an internal temperature of 20 ° C. to 35 ° C., then the temperature was raised and refluxed for 1 hour. Next, THF was distilled off from the reaction solution, followed by stirring at 110 ° C. for 8 hours.

  The reaction mixture thus obtained was washed with 2000 mL of 2% aqueous sodium hydroxide solution and then twice with 1000 mL of demineralized water. Toluene and a small amount of water were distilled off from the obtained toluene layer to obtain 863 g of a chlorophenoxycyclotriphosphazene mixture.

  As a result of analyzing this mixture by HPLC using a sample prepared in advance, 2,4,6-trichloro-2,4,6-triphenoxycyclotriphosphazene and 2,4-dichloro-2,4,6,6 were obtained. -It was confirmed that tetraphenoxycyclotriphosphazene was the main component.

  862 g of the above chlorophenoxycyclotriphosphazene mixture and 340 mL of toluene are placed in a 2 L stainless steel pressure vessel, then the pressure inside the pressure vessel is reduced to 400 hPa, 173 g (10.1 mol) of ammonia is added, and the mixture is sealed at 50 ° C. Stir for 15 hours. Thereafter, the pressure vessel was opened, and 3500 mL of toluene was added to the reaction for dilution. After washing with demineralized water, the solvent was distilled off to obtain 694 g of a white solid.

  The result of analyzing this white solid is shown below.

HPLC and LC / MS (positive-ESI):
The measurement was performed under the same conditions and method as in Example 1. As a result, under HPLC analysis conditions 1 and 2, 2,4,6-triamino-2,4,6-triphenoxycyclotriphosphazene standard product or 2,4-diamino-2,4,6,6-tetraphenoxycyclo Peaks having the same retention times as those of the triphosphazene standard were confirmed, and these peaks were confirmed by LC / MS analysis to be m / z: 463 (M + H ⁺ ) or 540 (M + H ⁺ ), respectively. .

Hydrolyzed chlorine: 0.01% or less,
TG / DTA analysis:
Melting temperature: 80 ° C or higher,
5% weight loss temperature: 290 ° C.

  From the above analysis results, the white solids are 2,4,6-triamino-2,4,6-triphenoxycyclotriphosphazene and 2,4-diamino-2,4,6,6-tetraphenoxycyclotriphosphazene. The composition was 10% and 88%, respectively, and the other aminophenoxycyclotriphosphazene components were 2%. Yield 85.1%.

Example 5
(Synthesis of flame retardant composition E containing 2,4,6-triamino-2,4,6-triphenoxycyclotriphosphazene and 2,4-diamino-2,4,6,6-tetraphenoxycyclotriphosphazene)
Into a 10 L flask equipped with a stirrer, a thermometer and a reflux condenser, 521 g (1.50 mol) of hexachlorocyclotriphosphazene was charged, and 2000 mL of toluene was added and dissolved to obtain a hexachlorocyclotriphosphazene solution.

  A solution obtained by adding 2500 mL of THF to 627 g (5.40 mol) of sodium phenoxide was added dropwise to the hexachlorocyclotriphosphazene solution at an internal temperature of 20 ° C. to 35 ° C. Then, the temperature was raised and refluxed for 1 hour. Next, THF was distilled off from the reaction solution, followed by stirring at 110 ° C. for 8 hours.

  The reaction mixture thus obtained was washed with 2000 mL of 2% aqueous sodium hydroxide solution and then twice with 1000 mL of demineralized water. Toluene and a small amount of water were distilled off from the obtained toluene layer to obtain 824 g of a chlorophenoxycyclotriphosphazene mixture.

  As a result of analyzing this mixture by HPLC using a sample prepared in advance, 2,4,6-trichloro-2,4,6-triphenoxycyclotriphosphazene and 2,4-dichloro-2,4,6,6 were obtained. -It was confirmed that tetraphenoxycyclotriphosphazene was the main component.

  Put 823 g of the above chlorophenoxycyclotriphosphazene mixture and 320 mL of toluene in a 2 L stainless steel pressure vessel, then depressurize the pressure vessel to 400 hPa, add 212 g (12.5 mol) of ammonia, and seal at 50 ° C. Stir for 15 hours. Thereafter, the pressure vessel was opened, the reaction product was diluted with 3500 mL of toluene, washed with demineralized water, and then the solvent was distilled off to obtain 597 g of a white solid.

  The result of analyzing this white solid is shown below.

HPLC and LC / MS (positive-ESI):
The measurement was performed under the same conditions and method as in Example 1. As a result, under HPLC analysis conditions 1 and 2, 2,4,6-triamino-2,4,6-triphenoxycyclotriphosphazene standard product or 2,4-diamino-2,4,6,6-tetraphenoxycyclo Peaks having the same retention times as those of the triphosphazene standard were confirmed, and these peaks were confirmed by LC / MS analysis to be m / z: 463 (M + H ⁺ ) or 540 (M + H ⁺ ), respectively. .

Hydrolyzed chlorine: 0.01% or less,
TG / DTA analysis:
Melting temperature: 80 ° C or higher,
5% weight loss temperature: 276 ° C.

  From the above analysis results, the white solids are 2,4,6-triamino-2,4,6-triphenoxycyclotriphosphazene and 2,4-diamino-2,4,6,6-tetraphenoxycyclotriphosphazene. The composition was 62% and 36%, respectively, and the other aminophenoxycyclotriphosphazene components were 2%. Yield 78.2%.

Example 6
(Synthesis of flame retardant composition F containing 2,4,6-triamino-2,4,6-triphenoxycyclotriphosphazene and 2,4-diamino-2,4,6,6-tetraphenoxycyclotriphosphazene)
Into a 10 L flask equipped with a stirrer, a thermometer and a reflux condenser, 521 g (1.50 mol) of hexachlorocyclotriphosphazene was charged, and 2000 mL of toluene was added and dissolved to obtain a hexachlorocyclotriphosphazene solution.

  A solution obtained by adding 2550 mL of THF to 644 g (5.55 mol) of sodium phenoxide was added dropwise to the above hexachlorocyclotriphosphazene solution at an internal temperature of 20 ° C. to 35 ° C., and the mixture was heated up and refluxed for 1 hour. Next, THF was distilled off from the reaction solution, followed by stirring at 110 ° C. for 8 hours.

  The reaction mixture thus obtained was washed with 2000 mL of 2% aqueous sodium hydroxide solution and then twice with 1000 mL of demineralized water. Toluene and a small amount of water were distilled off from the obtained toluene layer to obtain 833 g of a chlorophenoxycyclotriphosphazene mixture.

  As a result of analyzing this mixture by HPLC using a sample prepared in advance, 2,4,6-trichloro-2,4,6-triphenoxycyclotriphosphazene and 2,4-dichloro-2,4,6,6 were obtained. -It was confirmed that tetraphenoxycyclotriphosphazene was the main component.

  Put 832 g of the above chlorophenoxycyclotriphosphazene mixture and 320 mL of toluene in a 2 L stainless steel pressure vessel, then depressurize the pressure vessel to 400 hPa, add 204 g (12.0 mol) of ammonia, and seal at 50 ° C. Stir for 15 hours. Thereafter, the pressure vessel was opened, the reaction product was diluted with 3500 mL of toluene, washed with demineralized water, and then the solvent was distilled off to obtain 629 g of a white solid.

  The result of analyzing this white solid is shown below.

HPLC and LC / MS (positive-ESI):
The measurement was performed under the same conditions and method as in Example 1. As a result, under HPLC analysis conditions 1 and 2, 2,4,6-triamino-2,4,6-triphenoxycyclotriphosphazene standard product or 2,4-diamino-2,4,6,6-tetraphenoxycyclo Peaks having the same retention times as those of the triphosphazene standard were confirmed, and these peaks were confirmed by LC / MS analysis to be m / z: 463 (M + H ⁺ ) or 540 (M + H ⁺ ), respectively. .

Hydrolyzed chlorine: 0.01% or less,
TG / DTA analysis:
Melting temperature: 80 ° C or higher,
5% weight loss temperature: 278 ° C.

  From the above analysis results, the white solids are 2,4,6-triamino-2,4,6-triphenoxycyclotriphosphazene and 2,4-diamino-2,4,6,6-tetraphenoxycyclotriphosphazene. The composition was 45% and 52%, respectively, and the other aminophenoxycyclotriphosphazene components were 3%. Yield 81.2%.

Comparative Example 1
(Synthesis of flame retardant composition G containing 2,4,6-triamino-2,4,6-triphenoxycyclotriphosphazene and 2,4-diamino-2,4,6,6-tetraphenoxycyclotriphosphazene)
Into a 10 L flask equipped with a stirrer, a thermometer and a reflux condenser, 521 g (1.50 mol) of hexachlorocyclotriphosphazene was charged, and 2000 mL of toluene was added and dissolved to obtain a hexachlorocyclotriphosphazene solution.

  A solution obtained by adding 2050 mL of THF to 522 g (4.50 mol) of sodium phenoxide was added dropwise to the above hexachlorocyclotriphosphazene solution at an internal temperature of 20 ° C. to 35 ° C., and the temperature was raised and refluxed for 1 hour. Next, THF was distilled off from the reaction solution, followed by stirring at 110 ° C. for 8 hours.

  The reaction mixture thus obtained was washed with 2000 mL of 2% aqueous sodium hydroxide solution and then twice with 1000 mL of demineralized water. Toluene and a small amount of water were distilled off from the obtained toluene layer to obtain 773 g of a chlorophenoxycyclotriphosphazene mixture.

  As a result of analyzing this mixture by HPLC using a sample prepared in advance, 2,4,6-trichloro-2,4,6-triphenoxycyclotriphosphazene and 2,4-dichloro-2,4,6,6 were obtained. -It was confirmed that tetraphenoxycyclotriphosphazene was the main component.

  772 g of the above chlorophenoxycyclotriphosphazene mixture and 446 mL of toluene are placed in a 2 L stainless steel pressure vessel, then the pressure inside the pressure vessel is reduced to 400 hPa, 266 g (15.6 mol) of ammonia is added, and sealed at 50 ° C. Stir for 15 hours. Thereafter, the pressure vessel was opened, the reaction product was diluted with 3500 mL of toluene, washed with demineralized water, and then the solvent was distilled off to obtain 324 g of a white solid.

  The results of analyzing the white solid are as follows.

HPLC and LC / MS (positive-ESI):
The measurement was performed under the same conditions and method as in Example 1. As a result, under HPLC analysis conditions 1 and 2, 2,4,6-triamino-2,4,6-triphenoxycyclotriphosphazene standard product or 2,4-diamino-2,4,6,6-tetraphenoxycyclo Peaks having the same retention times as those of the triphosphazene standard were confirmed, and these peaks were confirmed by LC / MS analysis to be m / z: 463 (M + H ⁺ ) or 540 (M + H ⁺ ), respectively. .

Hydrolyzed chlorine: 0.01% or less TG / DTA analysis:
Melting temperature: 70 ° C or higher
5% weight loss temperature: 278 ° C

  From the above analysis results, the white solid was found to be 2,4,6-triamino-2,4,6-triphenoxycyclotriphosphazene and 2,4-diamino-2,4,6,6-tetraphenoxycyclotriphosphazene. The compositions were 90% and 9%, respectively, and the other aminophenoxycyclotriphosphazene components were 1%. Yield 46.7%.

Comparative Example 2
(Synthesis of flame retardant composition H containing 2,4,6-triamino-2,4,6-triphenoxycyclotriphosphazene and 2,4-diamino-2,4,6,6-tetraphenoxycyclotriphosphazene)
Into a 10 L flask equipped with a stirrer, a thermometer and a reflux condenser, 521 g (1.50 mol) of hexachlorocyclotriphosphazene was charged, and 2000 mL of toluene was added and dissolved to obtain a hexachlorocyclotriphosphazene solution.

  A solution obtained by adding 2900 mL of THF to 731 g (6.30 mol) of sodium phenoxide was added dropwise to the above hexachlorocyclotriphosphazene solution at an internal temperature of 20 ° C. to 35 ° C., and the temperature was raised and refluxed for 1 hour. Next, THF was distilled off from the reaction solution, followed by stirring at 110 ° C. for 8 hours.

  The reaction mixture thus obtained was washed with 2000 mL of 2% aqueous sodium hydroxide solution and then twice with 1000 mL of demineralized water. Toluene and a small amount of water were distilled off from the obtained toluene layer to obtain 876 g of a chlorophenoxycyclotriphosphazene mixture.

  As a result of analyzing this mixture by HPLC using a sample prepared in advance, 2,4,6-trichloro-2,4,6-triphenoxycyclotriphosphazene and 2,4-dichloro-2,4,6,6 were obtained. -It was confirmed that tetraphenoxycyclotriphosphazene was the main component.

  875 g of the above chlorophenoxycyclotriphosphazene mixture and 340 mL of toluene are put into a 2 L stainless steel pressure vessel, and after reducing the pressure inside the pressure vessel to 400 hPa, 159 g (9.40 mol) of ammonia is added and sealed at 50 ° C. Stir for 15 hours. Thereafter, the pressure vessel was opened, the reaction product was diluted with 3500 mL of toluene, washed with demineralized water, and then the solvent was distilled off to obtain 347 g of a white solid.

  The results of analyzing the white solid are as follows.

HPLC and LC / MS (positive-ESI):
The measurement was performed under the same conditions and method as in Example 1. As a result, under HPLC analysis conditions 1 and 2, 2,4,6-triamino-2,4,6-triphenoxycyclotriphosphazene standard product or 2,4-diamino-2,4,6,6-tetraphenoxycyclo Peaks having the same retention times as those of the triphosphazene standard were confirmed, and these peaks were confirmed by LC / MS analysis to be m / z: 463 (M + H ⁺ ) or 540 (M + H ⁺ ), respectively. .

Hydrolyzed chlorine: 0.01% or less TG / DTA analysis:
Melting temperature: 70 ° C or higher 5% weight loss temperature: 290 ° C

From the above analysis results, the white solids are 2,4,6-triamino-2,4,6-triphenoxycyclotriphosphazene and 2,4-diamino-2,4,6,6-tetraphenoxycyclotriphosphazene. The composition was 3% and 90%, respectively, and the other aminophenoxycyclotriphosphazene components were 7%. Yield 41.7%.
B. Manufacture of flame retardants

Example 7
(Production of flame retardant finishing agent A1)
100 parts by weight of flame retardant composition A, 5.0 parts by weight of ammonium salt of sulfuric ester of tristyrenated phenol ethylene oxide 10 mol adduct and 0.1 parts by weight of silicone antifoaming agent were mixed in 130 parts by weight of water. . This mixture was charged in a mill filled with glass beads having a diameter of 0.8 mm, and pulverized for 4 hours, whereby the aminophenoxycyclotriphosphazene contained in the flame retardant composition A was converted into fine particles having an average particle diameter of 0.491 μm. Dispersed. When the obtained dispersion was dried at a temperature of 105 ° C. for 40 minutes, the amount of water was adjusted so that the concentration of the nonvolatile content was 30% by weight to obtain a flame retardant processing agent A1 according to the present invention.

Example 8
(Manufacture of flame retardant finishing agent B1)
100 parts by weight of the flame retardant composition B, 5.0 parts by weight of an ammonium salt of a sulfate ester of tristyrenated phenol ethylene oxide 10 mol adduct and 0.1 parts by weight of a silicone-based antifoaming agent were mixed in 130 parts by weight of water. . This mixture was charged into a mill filled with glass beads having a diameter of 0.8 mm, and pulverized for 4 hours, whereby the aminophenoxycyclotriphosphazene contained in the flame retardant composition B was converted into fine particles having an average particle diameter of 0.541 μm. Dispersed. When the obtained dispersion was dried at a temperature of 105 ° C. for 40 minutes, the amount of water was adjusted so that the concentration of the nonvolatile content was 30% by weight to obtain a flame retardant processing agent B1 according to the present invention.

Example 9
(Production of flame retardant finishing agent B2)
100 parts by weight of flame retardant composition B, 5.0 parts by weight of sodium salt of sulfate ester of tristyrenated phenol ethylene oxide 10 mol adduct and 0.1 parts by weight of silicone antifoaming agent were mixed with 130 parts by weight of water. . This mixture was charged into a mill filled with glass beads having a diameter of 0.8 mm, and pulverized for 4 hours, whereby the aminophenoxycyclotriphosphazene contained in the flame retardant composition B was converted into fine particles having an average particle diameter of 0.500 μm. Dispersed. When the obtained dispersion was dried at a temperature of 105 ° C. for 40 minutes, the amount of water was adjusted so that the concentration of the nonvolatile content was 30% by weight to obtain a flame retardant processing agent B2 according to the present invention.

Example 10
(Production of flame retardant finishing agent B3)
100 parts by weight of flame retardant composition B, 5.0 parts by weight of sodium salt of sulfosuccinate ester of adduct of 15 moles of tristyrenated phenol ethylene oxide and 0.1 parts by weight of silicone antifoaming agent in 130 parts by weight of water Mixed. This mixture was charged into a mill filled with glass beads having a diameter of 0.8 mm, and pulverized for 4 hours, whereby the aminophenoxycyclotriphosphazene contained in the flame retardant composition B was converted into fine particles having an average particle diameter of 0.562 μm. Dispersed. When the obtained dispersion was dried at a temperature of 105 ° C. for 40 minutes, the amount of water was adjusted so that the concentration of the nonvolatile content was 30% by weight to obtain a flame retardant processing agent B3 according to the present invention.

Example 11
(Production of flame retardant finishing agent B4-1)
100 parts by weight of flame retardant composition B, 5.0 parts by weight of an adduct of 16 moles of tristyrenated phenol ethylene oxide and 0.1 parts by weight of a silicone-based antifoaming agent were mixed in 130 parts by weight of water. This mixture was charged in a mill filled with glass beads having a diameter of 0.8 mm, and pulverized for 4 hours, whereby the aminophenoxycyclotriphosphazene contained in the flame retardant composition B was converted into fine particles having an average particle diameter of 0.831 μm. Dispersed. When the obtained dispersion was dried at a temperature of 105 ° C. for 40 minutes, the amount of water was adjusted so that the concentration of the nonvolatile content was 30% by weight to obtain the flame retardant processing agent B4-1 according to the present invention. It was.

Example 12
(Production of flame retardant finishing agent B4-2)
100 parts by weight of the flame retardant composition B, 5.0 parts by weight of a 25 mol adduct of tristyrenated phenol ethylene oxide and 0.1 parts by weight of a silicone-based antifoaming agent were mixed in 130 parts by weight of water. This mixture was charged in a mill filled with glass beads having a diameter of 0.8 mm, and pulverized for 4 hours, whereby the aminophenoxycyclotriphosphazene contained in the flame retardant composition B was converted into fine particles having an average particle diameter of 1.081 μm. Dispersed. When the obtained dispersion was dried at a temperature of 105 ° C. for 40 minutes, the amount of water was adjusted so that the concentration of the nonvolatile content was 30% by weight to obtain the flame retardant processing agent B4-2 according to the present invention. It was.

Example 13
(Production of flame retardant finishing agent B5-1)
100 parts by weight of flame retardant composition B, 5.0 parts by weight of adduct of 13 moles of distyrenated phenol ethylene oxide and 0.1 parts by weight of silicone antifoaming agent were mixed in 130 parts by weight of water. This mixture was charged into a mill filled with glass beads having a diameter of 0.8 mm, and pulverized for 4 hours, whereby the aminophenoxycyclotriphosphazene contained in the flame retardant composition B was converted into fine particles having an average particle diameter of 0.822 μm. Dispersed. When the obtained dispersion was dried at a temperature of 105 ° C. for 40 minutes, the amount of water was adjusted so that the concentration of the nonvolatile content was 30% by weight to obtain the flame retardant processing agent B5-1 according to the present invention. It was.

Example 14
(Production of flame retardant finishing agent B5-2)
100 parts by weight of the flame retardant composition B, 5.0 parts by weight of a 20 mol adduct of distyrenated phenol ethylene oxide and 0.1 parts by weight of a silicone-based antifoaming agent were mixed in 130 parts by weight of water. This mixture was charged into a mill filled with glass beads having a diameter of 0.8 mm, and pulverized for 4 hours, whereby the aminophenoxycyclotriphosphazene contained in the flame retardant composition B was converted into fine particles having an average particle diameter of 0.771 μm. Dispersed. When the obtained dispersion was dried at a temperature of 105 ° C. for 40 minutes, the amount of water was adjusted so that the concentration of the nonvolatile content was 30% by weight to obtain the flame retardant processing agent B5-2 according to the present invention. It was.

Example 15
(Production of flame retardant finishing agent B5-3)
100 parts by weight of flame retardant composition B, 5.0 parts by weight of adduct of 50 moles of distyrenated phenol ethylene oxide and 0.1 parts by weight of silicone antifoam were mixed in 130 parts by weight of water. This mixture was charged into a mill filled with glass beads having a diameter of 0.8 mm, and pulverized for 4 hours, whereby the aminophenoxycyclotriphosphazene contained in the flame retardant composition B was converted into fine particles having an average particle diameter of 1.162 μm. Dispersed. When the obtained dispersion was dried at a temperature of 105 ° C. for 40 minutes, the amount of water was adjusted so that the concentration of the nonvolatile content was 30% by weight to obtain the flame retardant processing agent B5-3 according to the present invention. It was.

Example 16
(Manufacture of flame retardant finishing agent B6)
100 parts by weight of flame retardant composition B, 5.0 parts by weight of adduct of 7 mol of distyrenated methylphenol ethylene oxide and 0.1 parts by weight of silicone antifoam were mixed in 130 parts by weight of water. This mixture was charged into a mill filled with glass beads having a diameter of 0.8 mm, and pulverized for 4 hours, whereby the aminophenoxycyclotriphosphazene contained in the flame retardant composition B was converted into fine particles having an average particle diameter of 1.430 μm. Dispersed. When the obtained dispersion was dried at a temperature of 105 ° C. for 40 minutes, the amount of water was adjusted so that the concentration of the nonvolatile content was 30% by weight to obtain a flame retardant processing agent B6 according to the present invention.

Example 17
(Manufacture of flame retardant finishing agent B7)
100 parts by weight of flame retardant composition B, 5.0 parts by weight of an adduct of 14 mol of tribenzylated phenol ethylene oxide and 0.1 parts by weight of a silicone-based antifoaming agent were mixed in 130 parts by weight of water. This mixture was charged into a mill filled with glass beads having a diameter of 0.8 mm, and pulverized for 4 hours, whereby the aminophenoxycyclotriphosphazene contained in the flame retardant composition B was converted into fine particles having an average particle diameter of 0.911 μm. Dispersed. When the obtained dispersion was dried at a temperature of 105 ° C. for 40 minutes, the amount of water was adjusted so that the nonvolatile content concentration was 30% by weight to obtain a flame retardant processing agent B7 according to the present invention.

Example 18
(Manufacture of flame retardant finishing agent B8)
100 parts by weight of the flame retardant composition B, 5.0 parts by weight of an adduct of 11 moles of cumylated phenol ethylene oxide and 0.1 parts by weight of a silicone-based antifoaming agent were mixed in 130 parts by weight of water. This mixture was charged into a mill filled with glass beads having a diameter of 0.8 mm, and pulverized for 4 hours, whereby the aminophenoxycyclotriphosphazene contained in the flame retardant composition B was converted into fine particles having an average particle diameter of 0.500 μm. Dispersed. When the obtained dispersion was dried at a temperature of 105 ° C. for 40 minutes, the amount of water was adjusted so that the nonvolatile content concentration was 30% by weight to obtain a flame retardant processing agent B8 according to the present invention.

Example 19
(Production of flame retardant finishing agent B9)
100 parts by weight of flame retardant composition B, 5.0 parts by weight of stearyltrimethylammonium chloride and 0.1 parts by weight of a silicone-based antifoaming agent were mixed in 130 parts by weight of water. This mixture was charged into a mill filled with glass beads having a diameter of 0.8 mm, and pulverized for 4 hours, whereby the aminophenoxycyclotriphosphazene contained in the flame retardant composition B was converted into fine particles having an average particle diameter of 1.572 μm. Dispersed. When the obtained dispersion was dried at a temperature of 105 ° C. for 40 minutes, the amount of water was adjusted so that the concentration of the nonvolatile content was 30% by weight to obtain a flame retardant processing agent B9 according to the present invention.

Example 20
(Manufacture of flame retardant finishing agent B10)
100 parts by weight of flame retardant composition B, 5.0 parts by weight of sodium dioctyl sulfosuccinate and 0.1 parts by weight of a silicone-based antifoaming agent were mixed in 130 parts by weight of water. This mixture was charged into a mill filled with glass beads having a diameter of 0.8 mm, and pulverized for 4 hours, whereby the aminophenoxycyclotriphosphazene contained in the flame retardant composition B was converted into fine particles having an average particle size of 1.560 μm. Dispersed. When the obtained dispersion was dried at a temperature of 105 ° C. for 40 minutes, the amount of water was adjusted so that the concentration of the nonvolatile content was 30% by weight to obtain a flame retardant processing agent B10 according to the present invention.

Example 21
(Production of flame retardant finishing agent B11)
100 parts by weight of flame retardant composition B, 5.0 parts by weight of polyoxyethylene (20) sorbitan monostearate and 0.1 parts by weight of a silicone-based antifoaming agent were mixed in 130 parts by weight of water. This mixture was charged into a mill filled with glass beads having a diameter of 0.8 mm, and pulverized for 4 hours, whereby the aminophenoxycyclotriphosphazene contained in the flame retardant composition B was converted into fine particles having an average particle diameter of 1.611 μm. Dispersed. When the obtained dispersion was dried at a temperature of 105 ° C. for 40 minutes, the amount of water was adjusted so that the concentration of the nonvolatile content was 30% by weight to obtain a flame retardant processing agent B11 according to the present invention.

Example 22
(Production of flame retardant finishing agent B12)
100 parts by weight of flame retardant composition B, 5.0 parts by weight of polyoxyethylene (15) tridesilyl ether phosphate and 0.1 parts by weight of a silicone-based antifoaming agent were mixed in 130 parts by weight of water. This mixture was charged into a mill filled with glass beads having a diameter of 0.8 mm, and pulverized for 4 hours, whereby the aminophenoxycyclotriphosphazene contained in the flame retardant composition B was converted into fine particles having an average particle diameter of 1.350 μm. Dispersed. When the obtained dispersion was dried at a temperature of 105 ° C. for 40 minutes, the amount of water was adjusted so that the nonvolatile content concentration was 30% by weight to obtain a flame retardant processing agent B12 according to the present invention.

Example 23
(Production of flame retardant finishing agent B13)
100 parts by weight of flame retardant composition B, 5.0 parts by weight of polyoxyethylene (40) hydrogenated castor oil and 0.1 parts by weight of a silicone-based antifoaming agent were mixed in 130 parts by weight of water. This mixture was charged into a mill filled with glass beads having a diameter of 0.8 mm, and pulverized for 4 hours, whereby the aminophenoxycyclotriphosphazene contained in the flame retardant composition B was converted into fine particles having an average particle diameter of 1.491 μm. Dispersed. When the obtained dispersion was dried at a temperature of 105 ° C. for 40 minutes, the amount of water was adjusted so that the concentration of the nonvolatile content was 30% by weight to obtain a flame retardant processing agent B13 according to the present invention.

Example 24
(Manufacture of flame retardant finishing agent B14)
100 parts by weight of flame retardant composition B, 5.0 parts by weight of polyoxyethylene (8) stearylamine and 0.1 parts by weight of a silicone-based antifoaming agent were mixed in 130 parts by weight of water. This mixture was charged into a mill filled with glass beads having a diameter of 0.8 mm, and pulverized for 4 hours, whereby the aminophenoxycyclotriphosphazene contained in the flame retardant composition B was converted into fine particles having an average particle diameter of 1.790 μm. Dispersed. When the obtained dispersion was dried at a temperature of 105 ° C. for 40 minutes, the amount of water was adjusted so that the nonvolatile content concentration was 30% by weight to obtain a flame retardant processing agent B14 according to the present invention.

Example 25
(Production of flame retardant finish B1B5-2)
100 parts by weight of flame retardant composition B, 2.5 parts by weight of ammonium salt of sulfuric ester of tristyrenated phenol ethylene oxide 10 mol adduct, 2.5 parts by weight of distyrenated phenol ethylene oxide 20 mol adduct and silicone 0.1 part by weight of foaming agent was mixed with 130 parts by weight of water. This mixture was charged in a mill filled with glass beads having a diameter of 0.8 mm, and pulverized for 4 hours, whereby the aminophenoxycyclotriphosphazene contained in the flame retardant composition B was converted into fine particles having an average particle diameter of 0.710 μm. Dispersed. When the obtained dispersion was dried at a temperature of 105 ° C. for 40 minutes, the amount of water was adjusted so that the concentration of the nonvolatile content was 30% by weight to obtain the flame retardant processing agent B1B5-2 according to the present invention. It was.

Example 26
(Production of flame retardant finishing agent B5-1A)
100 parts by weight of flame retardant composition B and 5.0 parts by weight of an adduct of 13 moles of distyrenated phenol ethylene oxide were mixed with 130 parts by weight of isopropyl alcohol. This mixture was charged into a mill filled with glass beads having a diameter of 0.8 mm, and pulverized for 4 hours, whereby the aminophenoxycyclotriphosphazene contained in the flame retardant composition B was converted into fine particles having an average particle diameter of 1.850 μm. Dispersed. When the obtained dispersion was dried at a temperature of 105 ° C. for 40 minutes, the amount of isopropyl alcohol was adjusted so that the nonvolatile content concentration was 30% by weight, and the flame retardant processing agent B5-1A according to the present invention was added. Obtained.

Example 27
(Manufacture of flame retardant finishing agent C1)
100 parts by weight of flame retardant composition C, 5.0 parts by weight of ammonium salt of sulfuric ester of tristyrenated phenol ethylene oxide 10 mol adduct and 0.1 parts by weight of silicone antifoaming agent were mixed in 130 parts by weight of water. . This mixture was charged into a mill filled with glass beads having a diameter of 0.8 mm, and pulverized for 4 hours, whereby the aminophenoxycyclotriphosphazene contained in the flame retardant composition C was converted into fine particles having an average particle diameter of 0.520 μm. Dispersed. When the obtained dispersion was dried at a temperature of 105 ° C. for 40 minutes, the amount of water was adjusted so that the concentration of the nonvolatile content was 30% by weight to obtain a flame retardant processing agent C1 according to the present invention.

Example 28
(Production of flame retardant finishing agent D1)
100 parts by weight of flame retardant composition D, 5.0 parts by weight of ammonium salt of sulfuric ester of tristyrenated phenol ethylene oxide 10 mol adduct and 0.1 parts by weight of silicone antifoaming agent were mixed in 130 parts by weight of water. . This mixture was charged in a mill filled with glass beads having a diameter of 0.8 mm, and pulverized for 4 hours, whereby the aminophenoxycyclotriphosphazene contained in the flame retardant composition D was converted into fine particles having an average particle diameter of 0.550 μm. Dispersed. When the obtained dispersion was dried at a temperature of 105 ° C. for 40 minutes, the amount of water was adjusted so that the concentration of the nonvolatile content was 30% by weight to obtain a flame retardant processing agent D1 according to the present invention.

Example 29
(Production of flame retardant E1)
100 parts by weight of flame retardant composition E, 5.0 parts by weight of ammonium salt of sulfuric ester of tristyrenated phenol ethylene oxide 10 mol adduct and 0.1 parts by weight of silicone antifoam were mixed with 130 parts by weight of water. . This mixture was charged into a mill filled with glass beads having a diameter of 0.8 mm, and pulverized for 4 hours, so that the aminophenoxycyclotriphosphazene contained in the flame retardant composition E was converted into fine particles having an average particle diameter of 0.501 μm. Dispersed. When the obtained dispersion was dried at a temperature of 105 ° C. for 40 minutes, the amount of water was adjusted so that the concentration of the nonvolatile content was 30% by weight to obtain a flame retardant processing agent E1 according to the present invention.

Example 30
(Manufacture of flame retardant finish F1)
100 parts by weight of flame retardant composition F, 5.0 parts by weight of ammonium salt of sulfuric ester of tristyrenated phenol ethylene oxide 10-mole adduct and 0.1 parts by weight of silicone antifoam were mixed with 130 parts by weight of water. . This mixture was charged in a mill filled with glass beads having a diameter of 0.8 mm, and pulverized for 4 hours, so that the aminophenoxycyclotriphosphazene contained in the flame retardant composition F was converted into fine particles having an average particle diameter of 0.510 μm. Dispersed. When the obtained dispersion was dried at a temperature of 105 ° C. for 40 minutes, the amount of water was adjusted so that the concentration of the nonvolatile content was 30% by weight to obtain a flame retardant processing agent F1 according to the present invention.

Comparative Example 3
(Manufacture of flame retardant finishing agent G1)
100 parts by weight of flame retardant composition G, 5.0 parts by weight of ammonium sulfate ester of tristyrenated phenol ethylene oxide 10-mol adduct and 0.1 parts by weight of silicone antifoam were mixed with 130 parts by weight of water. . This mixture was charged into a mill filled with glass beads having a diameter of 0.8 mm, and pulverized for 4 hours, whereby the aminophenoxycyclotriphosphazene contained in the flame retardant composition G was converted into fine particles having an average particle diameter of 0.541 μm. Dispersed. When the obtained dispersion was dried at a temperature of 105 ° C. for 40 minutes, the amount of water was adjusted so that the concentration of the nonvolatile content was 30% by weight to obtain a flame retardant processing agent G1 according to the present invention.

Comparative Example 4
(Manufacture of flame retardant H1)
100 parts by weight of the flame retardant composition H, 5.0 parts by weight of an ammonium salt of a sulfate ester of tristyrenated phenol ethylene oxide 10 mol adduct and 0.1 parts by weight of a silicone-based antifoaming agent were mixed with 130 parts by weight of water. . This mixture was charged in a mill filled with glass beads having a diameter of 0.8 mm and pulverized for 4 hours. The aminophenoxycyclotriphosphazene contained in the flame retardant composition H could be aggregated and dispersed. There wasn't.

Comparative Example 5
(Production of flame retardant finishing agent I)
47 parts by weight of guanidine phosphate was dissolved in 53 parts by weight of water to obtain a flame retardant finishing agent I according to a comparative example.

Comparative Example 6
(Manufacture of flame retardant finishing agent J)
100 parts by weight of anilinodiphenyl phosphate, 6.1 parts by weight of sodium dioctyl sulfosuccinate and 0.1 parts by weight of a silicone-based antifoaming agent were mixed with 130 parts by weight of water. This mixture was charged in a mill filled with glass beads having a diameter of 0.8 mm and pulverized for 4 hours to disperse the phosphoric acid amide as fine particles having an average particle diameter of 0.526 μm. When the obtained dispersion was dried at a temperature of 105 ° C. for 40 minutes, the amount of water was adjusted so that the concentration of the nonvolatile content was 40% by weight to obtain a flame retardant processing agent J according to a comparative example.

Comparative Example 7
(Manufacture of flame retardant finishing agent K)
100 parts by weight of crystalline powder of tetra (2,6-dimethylphenyl) -m-phenylene phosphate, 8.8 parts by weight of 10 moles of ethylene oxide adduct of octylphenol and 0.1 parts by weight of silicone antifoaming agent are added to 130 parts by weight of water. The mixture was pulverized at 6000 rpm for 3 hours or more using a homomixer to obtain a treatment liquid having an average particle size of 50 μm or less.

  Next, this processing solution is charged into a mill filled with glass beads having the same volume of 0.8 mm in diameter, and the phosphate is pulverized to an average particle size of 0.996 μm, and then at a temperature of 105 ° C. for 40 minutes. The amount of water was adjusted so that the non-volatile content concentration when dried was 40% by weight to obtain a flame retardant finishing agent K according to a comparative example.

C. Flame Retardant Processing of Polyester Synthetic Fiber Structure (1) Preparation of Treated Fabric Polyester knit (weight per unit weight: 200 g / m ² ) is dispersed at 130 ° C. with disperse dye Dianix Black AM-SLR (manufactured by DyStar) 4% owf After dyeing in the bath for a minute, the polyester knit dyed black was obtained by reducing and washing in a conventional manner and drying.

In the following examples and comparative examples including Example 35, the polyester knit dyed in black was flame-retardant processed as a fabric to be treated.
(2) Simultaneous flame retardant treatment in bath

Example 31
In the dyeing process of the polyester knit, the flame retardant processing agent A1 according to the present invention is 25.0% owf and disperse dye Dianix Black AM-SLR (manufactured by DyStar) at 130 ° C. at 4% owf. After flame retardant treatment for 30 minutes, it was subjected to reduction cleaning by a conventional method and dried to obtain a flame retardant polyester fabric dyed black.

  The flame retardant utilization rate was 25.4%. Here, the flame retardant utilization rate indicates the ratio of the flame retardant contained in the flame retardant processing agent attached to the polyester fabric.

Example 32
Except that the flame retardant processing agent was used at 12.0% owf in place of B1, a flame retardant polyester fabric dyed black was obtained by carrying out a simultaneous flame retardant treatment in the same manner as in Example 31. Flame retardant utilization rate is 57.9%.

Example 33
In Example 32, except that the temperature of the dyeing process was set to 140 ° C., a flame retardant polyester fabric dyed black was obtained in the same manner as in the dyeing simultaneous flame retardant treatment. Flame retardant utilization rate 58.1%.

Example 34
Except that the flame retardant processing agent was used at 14.5% owf instead of C1, it was subjected to simultaneous flame retardant treatment in the same manner as in Example 31 to obtain a flame retardant polyester fabric dyed black. The flame retardant utilization rate is 48.0%.

Comparative Example 8
In the same manner as in Example 31, a flame retardant polyester fabric dyed black was obtained by using the flame retardant agent G1 at 25.0% owf and performing flame retardant treatment simultaneously with dyeing. Flame retardant utilization rate 15.1%.

  Table 1 shows the results of performance tests on the flame retardant polyester fabrics described in Examples 31 to 34 and Comparative Example 8.

  The amount of flame retardant attached in the above-mentioned simultaneous dyeing flame retardant treatment in the bath is calculated from the sum of the reduced weight before and after the processing of the polyester fabric dyed without adding the flame retardant processing agent to the increased weight of the polyester fabric before and after the flame retardant processing. And asked.

  For flame retardant performance, 1.0% by weight of silicone resin is attached to the flame retardant polyester fabric by padding method, dried at 130 ° C for 5 minutes, and heat treated at 150 ° C for 1 minute for flame retardant evaluation. A fabric was obtained and subjected to a combustion test. The silicone resin was added as a substance that inhibits flame retardancy.

(3) Padding Method Example 35 and Comparative Example 9
Flame Retardant A1, B1, B2, B3, B4-1, B4-2, B5-1, B5-2, B5-3, B6, B7, B8, B9, B10, B11, B12, B13 , B14, B1B5-2, B5-1A, C1, D1, E1 and F1 and the flame retardant processing agents I, J and K according to comparative examples, or the processing fluid diluted with water, respectively, to the black described above. The dyed polyester knit was flame-retardant processed as a treated fabric to obtain a flame-retardant polyester fabric according to the present invention and a polyester fabric as Comparative Example 9. Tables 2 to 4 show the results of performance tests of these flame-retardant polyester fabrics and the blank as Comparative Example 9.

Example 36
100 parts by weight of flame retardant composition B, 5.0 parts by weight of ammonium salt of sulfate ester of adduct of 10 moles of tristyrenated phenol ethylene oxide, 0.1 part by weight of silicone-based antifoaming agent and 25 parts by weight of polyester-based urethane resin emulsion Parts (non-volatile content 50%, glass transition temperature (Tg) -42 ° C.) were mixed with 105 parts by weight of water.

  The obtained mixture was charged in a mill filled with glass beads having a diameter of 0.8 mm, and pulverized for 4 hours, so that the aminophenoxycyclotriphosphazene contained in the flame retardant composition B had an average particle size of 0.509 μm. Dispersed as fine particles. When the obtained dispersion was dried at a temperature of 105 ° C. for 40 minutes, 92 parts by weight of the flame retardant processing agent obtained by adjusting the amount of water so that the non-volatile content concentration was 36.5% by weight was obtained. 8 parts by weight of a wax emulsion composed of paraffin wax and oxidized paraffin (non-volatile content: 26%, content of paraffin wax and oxidized paraffin: 21%) was mixed to obtain a flame retardant processing agent L according to the present invention. The non-volatile content of the flame retardant finishing agent L was 35.7% by weight.

Example 37
Using the flame retardant processing agent L obtained in Example 36, the treated fabric was flame retardant processed in the same manner as in Example 35 to obtain a flame retardant polyester fabric according to the present invention. Table 4 shows the results of performance tests on the flame-retardant polyester fabric.

  In the flame retardant processing by the padding method using the above flame retardant processing agent, the flame retardant adhesion amount is the difference in weight of the polyester fabric before and after the flame retardant processing, the concentration of the flame retardant processing agent diluted with the solvent and the difficulty in the flame retardant processing agent. It calculated | required by calculation based on flame-retardant content.

D. Performance test The performance test of the flame retardant polyester fabric was performed as follows. That is, using the flame retardant processing agent according to the present invention, the polyester knit dyed in black as described above is treated as a fabric to be flame retardant by the padding method, dried at 100 ° C. for 5 minutes, and 1 ° C. at 130 ° C. Heat treated for minutes. Moreover, only the flame-retardant processed polyester fabric by the flame-retardant processing agent A1 was heat-treated at 210 ° C. for 1 minute. The flame-retardant polyester fabric thus obtained was evaluated as it was without washing, as it was, as it was, with respect to friction fastness, stickiness, chalk mark, bleed-out, light fastness and wet heat test.

  In addition, regarding flame retardancy, using a single bath containing 1.0% by weight of a silicone resin and a flame retardant, the polyester knit dyed in black as described above is used as a fabric to be treated by padding. After adhering the flame retardant, it was dried at 130 ° C. for 5 minutes and heat treated at 150 ° C. for 1 minute to obtain a flame-treated fabric, which was subjected to a combustion test. Moreover, only the flame-retardant processed polyester fabric by the flame-retardant processing agent A1 was heat-treated at 210 ° C. for 1 minute. The silicone resin was added as a substance that inhibits flame retardancy.

(Friction fastness)
The fire-treated processed fabric was tested by the dyeing fastness test method for friction of JIS L 0849, and the friction tester type II (Gakuken type) described in 8.1.2 of JIS L 0849 was used. The series was determined by a gray scale for contamination (JIS L 0805). Grade 5 had the highest friction fastness, and grade 3 and above were good.

(Breakness)
Place the fabric to be fire-treated on urethane foam, drop 5mL of pure water, boiling water, and 3% aqueous solution of calcium chloride on the surface, and observe the surface of the sample 24 hours later. Those in which no etc. were observed were considered good.
Evaluation criteria ○: No ring stain or sticking is observed.
X: A ring stain and a sticking are seen.

(Chalk mark)
The surface of the flame-treated fabric was lightly rubbed with nails, and the degree of whitening due to scratches was confirmed.
Evaluation criteria ○: No whitening or powder fall off.
X: Whitening and powder fall are observed.

(Bleed out)
Polyester taffeta, filter paper and 800 g of weight are placed in this order on the surface of the flame-treated fabric and treated in a load of 800 g / 15.9 cm 2 at 100 ° C. for 2 hours to transfer the polyester taffeta to the contamination gray. Evaluation was made with a scale (JIS L 0805). Grade 5 had the least contamination, and Grade 3 and above were considered good.

(Light fastness)
The test was conducted by the dyeing fastness test method for ultraviolet carbon arc lamp light of JIS L 0842. Using a fade meter (manufactured by Suga Test Instruments Co., Ltd.), a carbon arc lamp was irradiated at 83 ° C. for 144 hours on the flame-treated fabric. Subsequently, the series was determined by a gray scale for color fading (JIS L 0804). Grade 5 was the fastest and grade 3 or higher was considered good.

(Moist heat test)
After the flame-treated fabric to be treated was left in an atmosphere of 70 ° C. and 95% RH for 1 month, the presence or absence of discoloration was confirmed.
Evaluation criteria ○: No discoloration.
X: Discoloration is observed.

(Flame retardant performance test)
FMVSS (Federal Automobile Safety Standards) No. The horizontal burning rate was measured based on the automotive interior material burning test standard of 302, and the burning rate of less than 101 mm / min was considered good.
Evaluation criteria ◎: Flame retardancy, self-extinguishing ○: Less than 1 to 61 mm / min. Δ: Less than 61 to 101 mm / min. X: More than 101 mm / min.

  As shown in Tables 1 to 4, the polyester fabric flame-treated with the flame retardant processing agent according to the present invention has good flame retardancy, fastness to friction and fastness to light. Without cleaning, no sticking or chalk marks occur, and bleed-out is also suppressed.

  Table 4 shows the test results of the treated fabric itself before the flame-retardant processing as a blank. Even in comparison with this blank, in particular, the flame retardant finishes A1, B1, C1, D1, E1 and F1 in Tables 1 to 4 can be used in a small amount of flame retardant, in terms of stickiness and friction fastness. There is no dark blue. Although the flame retardant processing agent G1 of Comparative Example 3 containing the flame retardant composition G was used for the treatment in the bath in Comparative Example 8, the utilization rate of the flame retardant composition is low, and it is difficult enough for the polyester-based synthetic fiber structure. Could not give flammability.

  Although production of a flame retardant processing agent was attempted using the flame retardant composition H, the flame retardant composition was agglomerated and the flame retardant composition could not be dispersed.

  Comparative Examples 5 to 7 were prepared by using crystalline powders of guanidine phosphate, anilinodiphenyl phosphate and tetra (2,6-dimethylphenyl) -m-phenylene phosphate as flame retardants, respectively. As shown in Comparative Example 9 in Table 4, when any flame retardant processing agent was used, the polyester fabric subjected to the flame retardant processing was noticeable. Further, as shown in Comparative Example 9 in Table 4, the flame retardant finishing agents J and K were inferior in both the fastness to friction and the fastness to light, and the bleed-out was also remarkable.

  In Example 37, in order to improve the friction fastness of the polyester fabric, in addition to the flame retardant composition B, a polyester-based urethane emulsion is included. Further, in order to improve the sewability, it is difficult to include the wax emulsion. Using the flame retardant, the fabric to be treated was subjected to flame retardant processing, and the obtained flame retardant polyester fabric was evaluated for performance.

As a result, the obtained flame-retardant processed polyester fabric was excellent in flame retardancy, friction fastness and light fastness as in Example 35, and it was noticeable without washing the flame-retardant processed textile. No choke marks and bleed-out.

Claims (11)

(A) Structural formula (1)

2,4,6-triamino-2,4,6-triphenoxycyclotriphosphazene represented by the following structural formula (2)

A total of 95% by weight or more of 2,4-diamino-2,4,6,6-tetraphenoxycyclotriphosphazene represented by:
(B) A flame retardant composition for a polyester-based synthetic fiber structure containing 5% by weight or less of aminophenoxycyclotriphosphazene other than (1) and (2) above, wherein (1) and (2) The flame retardant composition for a polyester-based synthetic fiber structure in which (1) is 10 to 80% by weight and (2) is 90 to 20% by weight in a total amount of 100% by weight.   A flame retardant processing agent for a polyester-based synthetic fiber structure, wherein the flame retardant composition according to claim 1 is dispersed in a solvent in the presence of a surfactant.   The flame retardant processing agent for a polyester-based synthetic fiber structure according to claim 2, wherein the solvent is water.   A polyester-based synthetic fiber structure that is flame-retardant processed with the flame retardant according to claim 1.   A method for flame-retarding a polyester-based synthetic fiber structure, comprising: flame-retarding a polyester-based synthetic fiber structure with the flame-retardant processing agent according to claim 2.   A polyester-based synthetic fiber structure, wherein the flame-retardant processing 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 100 to 220 ° C. Flame retardant processing method.   A method for flame-retardant processing of a polyester-based synthetic fiber structure, wherein the flame-retardant processing agent according to claim 2 or 3 is exhausted in a bath at a temperature of 100 to 140 ° C on a polyester-based synthetic fiber structure. .   A flame-retardant polyester-based synthetic fiber structure that has been flame-retardant processed by the flame-retardant processing method according to claim 5. 2. Alkali metal phenoxide in 1.00 mol part of hexachlorocyclotriphosphazene
50 to 4.10 mole parts are reacted to produce 2,4,6-trichloro-2,4,6-triphenoxycyclotriphosphazene and 2,4-dichloro-2,4,6,6-tetraphenoxycyclotri The polyester-based synthetic fiber structure according to claim 1, wherein a chlorophenoxycyclotriphosphazene mixture containing phosphazene as a main component is synthesized, and then ammonia is reacted with the chlorophenoxycyclotriphosphazene mixture. A method for producing a flame retardant composition.   In a first organic solvent, hexachlorocyclotriphosphazene and alkali metal phenoxide are reacted to produce 2,4,6-trichloro-2,4,6-triphenoxycyclotriphosphazene and 2,4-dichloro-2,4. Synthesizing a chlorophenoxycyclotriphosphazene mixture based on 1,6,6-tetraphenoxycyclotriphosphazene and then reacting the chlorophenoxycyclotriphosphazene mixture with ammonia in the presence of a second organic solvent. The manufacturing method of the flame retardant composition for the polyester-type synthetic fiber structure of Claim 9 characterized by the above-mentioned.   In a first organic solvent, hexachlorocyclotriphosphazene is reacted with alkali metal phenoxide at a temperature ranging from −50 ° C. to the boiling point of the first organic solvent, and ammonia is added to the resulting chlorophenoxycyclotriphosphazene mixture. The method for producing a flame retardant composition for a polyester-based synthetic fiber structure according to claim 10, wherein the reaction is performed at a temperature in the range of -20 to 100 ° C.