JPWO2017110785A1 - Flame retardant processing of polyester synthetic fiber structures - Google Patents

Abstract

According to the invention, at least one selected from 2,4,6-triamino-2,4,6-triphenoxycyclotriphosphazene and 2,4-diamino-2,4,6,6-tetraphenoxycyclotriphosphazene. Flame Retardant for Polyester Synthetic Fiber Structures Composed of Various Aminophenoxycyclotriphosphazenes and Flame Retardant for Polyester Synthetic Fiber Structures Dispersed in Solvents in the Presence of Surfactants A processing agent is provided. Furthermore, the flame-retardant processing method of the polyester type synthetic fiber structure which flame-retardant-processes a polyester type synthetic fiber structure using the said flame-retardant processing agent is provided.

Description

  TECHNICAL FIELD The present invention relates to flame retardant processing for polyester-based synthetic fiber structures, and more specifically, a polyester system comprising a certain kind of aminophenoxycyclotriphosphazene and imparting flame retardancy to polyester-based synthetic fiber structures by post-processing. Flame Retardant for Synthetic Fiber Structures, Flame Retardant Processed Polyester Synthetic Fiber Structures Flame Retardant Processed With Such Flame Retardant, Flame Retardant Finishing Agent Containing Such Flame Retardant, Such Flame Retardant Finishing Agent The present invention also relates to a flame retardant processing method for a polyester-based synthetic fiber structure using a flame retardant, and further to a flame-retardant processing polyester-based synthetic fiber structure obtained by such a flame retardant processing method.

  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, since cyclic phosphazene compounds having amino groups, phenoxy groups and / or methoxy groups in the molecule have a high phosphorus content, they have already been used as flame retardants for polyester-based synthetic fiber structures. Some have been proposed (see, for example, Patent Documents 4 and 5).

  Conventionally, however, certain cyclic aminophenoxyphosphazenes do not necessarily have good dispersibility. Therefore, it is necessary to disperse them in a solvent using a large amount of a surfactant to form a flame retardant, and as a result, cyclic aminophenoxy The polyester-based synthetic fiber structure subjected to flame retardant treatment with phosphazene has a problem that easily causes the above-described sticking (see, for example, Patent Document 4).

  Conventionally, cyclic aminophenoxyphosphazenes have been used as flame retardants as mixtures containing various isomers with different bonding positions of amino groups and phenoxy groups to the phosphazene skeleton. When the polyester-based synthetic fiber structure is flame-retardant processed, there is a problem that the polyester-based synthetic fiber structure subjected to the flame-retardant processing is partially colored by hydrolysis under wet heat to cause coloring.

  Furthermore, since cyclic (amino) phenoxyphosphazene having many phenoxy groups (together with amino groups) is highly hydrophobic, a large amount of surfactant is required to disperse it in a solvent to form a flame retardant. Therefore, the polyester-based synthetic fiber structure that has been flame-retarded with such a flame-retardant finish must be washed after the flame-retarding process in the same manner as the flame-retarding process using the phosphoric acid ester or phosphoric acid amide described above. However, when this is not performed, there is a problem that the flame-retardant processed polyester-based synthetic fiber structure is remarkably reduced in friction fastness.

  In addition, when the polyester-based synthetic fiber structure is flame-retarded with a flame retardant containing a cyclic aminophenoxyphosphazene 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 Japanese Patent Laid-Open No. 10-298188 JP 2002-105881 A

  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 developed various cyclic phosphazene compounds having an amino group, a phenoxy group and / or a methoxy group. As a result of extensive and detailed research on the production and flame retardant performance of certain products, certain aminophenoxycyclotriphosphazenes are difficult to hydrolyze, stable and easy to formulate into flame retardant processing agents. Disperse in a solvent in the presence of an activator to obtain a flame retardant, and use this flame retardant, for example, by performing flame retardant processing on a polyester synthetic fiber structure by a padding method. Even without subsequent cleaning, it is difficult to satisfy without deteriorating the physical properties of the polyester fiber structure, such as occurrence of sticking, chalk marks, and reduced friction fastness. Sex have found that it is possible to impart the polyester-based synthetic fiber structure, and have reached the present invention.

  According to the present invention, the following structural formula (1)

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

A flame retardant for a polyester-based synthetic fiber structure comprising at least one aminophenoxycyclotriphosphazene selected from 2,4-diamino-2,4,6,6-tetraphenoxycyclotriphosphazene represented by Is done.

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

  Furthermore, according to the present invention, there is provided a flame retardant polyester-based synthetic fiber structure that is flame retardant processed with the flame retardant.

  In addition, according to the present invention, a polyester-based synthetic fiber structure is flame-retardant processed with the above-mentioned flame-retardant processing agent. Provided is a flame-retardant processing method for a polyester-based synthetic fiber structure that is attached to a polyester-based synthetic fiber structure, dried, and then heat-treated at a temperature of 100 to 220 ° C.

  In addition to the above, according to the present invention, there is provided a flame retardant polyester-based synthetic fiber structure which is flame retardant processed by the above flame retardant processing method.

  By using a flame retardant processing agent containing a flame retardant according to the present invention, a polyester-based synthetic fiber structure is subjected to flame retardant processing, so that it is possible to satisfy satisfactory without causing occurrence of sticking and chalk marks and a decrease in friction fastness. Flammability 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.

  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. Further, the fabric such as the woven fabric and the nonwoven fabric may be a single layer or a laminate of two or more layers, or may be a composite made of yarn, cotton, a woven fabric, a nonwoven fabric or the like. Good.

  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, functional compounds such as flame retardants are added to polyesters. Copolymerized with polyester at the time of production, or a functional compound such as an antibacterial agent blended at the time of polymerization or spinning.

  The flame-retardant polyester-based synthetic fiber structure 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.

  The flame retardant for the polyester-based synthetic fiber structure according to the present invention has the following structural formula (1):

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

And at least one aminophenoxycyclotriphosphazene selected from 2,4-diamino-2,4,6,6-tetraphenoxycyclotriphosphazene represented by the formula:

  That is, according to the present invention, the 2,4,6-triamino-2,4,6-triphenoxycyclotriphosphazene can be used alone as a flame retardant, and 2,4-diamino-2 , 4,6,6-tetraphenoxycyclotriphosphazene alone can be used as a flame retardant, and 2,4,6-triamino-2,4,6-triphenoxycyclotriphosphazene and 2,4 -Diamino-2,4,6,6-tetraphenoxycyclotriphosphazene can be used in combination at an arbitrary ratio to form a flame retardant.

  The aminophenoxycyclotriphosphazene is obtained by, for example, reacting hexachlorocyclotriphosphazene with sodium phenoxide in an appropriate organic solvent to obtain a reaction mixture mainly composed of chlorophenoxycyclotriphosphazene, and then sealed in a pressure vessel. It can be obtained by reacting ammonia with the above mixture in an appropriate organic solvent under conditions, and removing by-products from the resulting reaction mixture.

  According to the present invention, the flame retardant comprising aminophenoxycyclotriphosphazene 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 flame retardant in a solvent in the presence of a surfactant. Here, the preferred dispersion medium for the flame retardant in the flame retardant processing agent is water.

  However, according to the present invention, the dispersion medium may be an organic solvent or a mixture of an organic solvent 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 can be preferably obtained by mixing the aminophenoxycyclotriphosphazene with water together with a surfactant, pulverizing it with a wet pulverizer, and making it into 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 to be used is more than 5.0 parts by weight with respect to 100 parts by weight of the aminophenoxycyclotriphosphazene, the friction fastness of the obtained flame-retardant processed polyester synthetic fiber structure May decrease, and there is a risk of occurrence of sticking. On the other hand, when the amount of the surfactant used is less than 0.9 parts by weight, the aminophenoxycyclotriphosphazene 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 include alcohols such as methanol and ethanol, aromatic hydrocarbons such as toluene, xylene, and alkylnaphthalene, acetone, Mention may be made of ketones such as 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 is applied to a polyester-based synthetic fiber structure and flame-retarded, the average particle size of the flame retardant has an important effect on the flame-retardant performance imparted to the polyester-based synthetic fiber structure by the processing. Effect. The flame retardant is more preferable as its average particle size is smaller because it can impart high flame retardancy to the polyester synthetic fiber structure. On the other hand, the larger the average particle size of the flame retardant, the worse the storage stability as the flame retardant, and the flame retardant precipitates in the flame retardant and clumps to form a so-called hard cake. Therefore, it is not preferable.

  Therefore, according to the present invention, when a flame retardant treatment is performed on a polyester synthetic fiber structure using the flame retardant processing agent, the flame retardant sufficiently diffuses and adheres to the inside of the polyester synthetic fiber structure. The aminophenoxycyclotriphosphazene is preferably used as a flame retardant 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 has durability, In particular, it is preferable to be dispersed in water as fine particles having an average particle diameter in the range of 0.3 to 1 μm.

  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 aminophenoxycyclotriphosphazene 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 aminophenoxycyclotriphosphazene to the polyester-based synthetic fiber structure is the target polyester type. Although it varies depending on the form and type of the synthetic fiber structure, it is usually in the range of 0.1 to 5% by weight, preferably 1 to 5% by weight in terms of the amount of flame retardant.

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

  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 a polyester synthetic fiber structure using the flame retardant according to the present invention, it may be by a method of kneading the flame retardant according to the present invention during spinning of the polyester synthetic fiber, as described above. Furthermore, it is preferable to use a flame retardant processing agent according to the present invention and a method of subjecting the polyester synthetic fiber structure to flame retardant processing as post-processing.

  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 aminophenoxycyclotriphosphazene according to the present invention to the inside of the fiber by 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, for example, after 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, the fabric is squeezed with a roller (mangle), and the flame retardant is used as described above. It is a method of adhering to a 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 aminophenoxycyclotriphosphazene is attached to the polyester-based synthetic fiber structure in this way, it is dried and, as described above, heat-treated at a temperature of 100 to 220 ° C. for 1 to 5 minutes. Thus, aminophenoxycyclotriphosphazene 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-bath treatment method in which a polyester-based synthetic fiber structure is immersed in a flame-retardant processing agent or a processing fluid diluted with the flame-retardant processing agent and treated in a bath at a temperature of 100 to 140 ° C. to exhaust the flame retardant into the fiber. 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. Furthermore, the flame retardant conventionally known may be included as needed.

  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.

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

  In the following, the non-volatile content in the flame retardant processing agent means the ratio of the flame retardant in the flame retardant processing agent, and the flame retardant processing agent together with the flame retardant contains a surfactant, an antifoaming agent and other auxiliary agents. When included, it refers to the ratio of the total amount of non-volatile components in the flame retardant, the surfactant, the antifoaming agent and the other auxiliaries.

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

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

The aminophenoxycyclotriphosphazene obtained in the following reference examples was prepared by measuring ¹ H-NMR spectrum and ³¹ P-NMR spectrum, analyzing chlorine element (residual chlorine) by potentiometric titration using silver nitrate, and LC / MS. Identification was based on the results of the analysis. Moreover, about these aminophenoxycyclotriphosphazenes, the melting temperature and the 5% weight loss temperature were measured by TG / DTA analysis.

A. Flame retardant production reference example 1
(Synthesis of 2,4,6-triamino-2,4,6-triphenoxycyclotriphosphazene)
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 tetrahydrofuran (THF) to 610 g (5.25 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 850 g of a chlorophenoxycyclotriphosphazene mixture. As a result of analyzing this mixture by HPLC using a sample prepared in advance, it was confirmed that it contained 2,4,6-trichloro-2,4,6-triphenoxycyclotriphosphazene.

  Put 849 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 221 g (13.0 mol) of ammonia, and seal at 50 ° C. Stir for 15 hours. Thereafter, the pressure vessel was opened, and the reaction product was diluted with 3500 mL of toluene and filtered. Methanol was added to the obtained filter cake, heated to dissolve, and cooled to room temperature. The precipitated solid was collected by filtration and dried to obtain 321 g of a white solid.

The analysis result of the white solid is shown below.
¹ H-NMR spectrum (300 MHz, DMSO-d ₆ , δ, ppm):
NH: 4.1 (6H),
C—H: 6.8 to 7.5 (15H),
³¹ P-NMR spectrum (121 MHz, DMSO-d ₆ , δ, ppm):
P- (NH ₂ ) (OPh): 17.3 to 17.7 (3P),
LC / MS (positive-ESI) m / z: 463 (M + H ⁺ ),
Hydrolyzed chlorine: 0.01% or less,
TG / DTA analysis:
Melting temperature: 213 ° C.
5% weight loss temperature: 278 ° C.

  From the above analysis results, it was confirmed that the white solid was 2,4,6-triamino-2,4,6-triphenoxycyclotriphosphazene. Yield 46.3%, HPLC purity 99.1% (area percentage).

Reference example 2
(Synthesis of 2,4-diamino-2,4,6,6-tetraphenoxycyclotriphosphazene)
Into a 5 L flask equipped with a stirrer, thermometer and reflux condenser, 521 g (1.50 mol) of hexachlorocyclotriphosphazene and 2000 mL of toluene were charged and stirred to dissolve hexachlorocyclotriphosphazene in toluene. A hexachlorocyclotriphosphazene solution was obtained.

  A solution obtained by dissolving 697 g (6.00 mol) of sodium phenoxide in 2700 mL of THF 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. Thereafter, the reaction was carried out for 8 hours under reflux while removing THF.

  After completion of the reaction, the resulting reaction mixture was washed with 2000 mL of 2% aqueous sodium hydroxide solution and then twice with 1000 mL of demineralized water. The obtained toluene layer was dehydrated, and then toluene was distilled off to obtain 688 g of a chlorophenoxycyclotriphosphazene mixture. As a result of quantification by HPLC using a sample prepared in advance, it was confirmed that 2,4-dichloro-2,4,6,6-tetraphenoxycyclotriphosphazene was contained.

  688 g of the above chlorophenoxycyclotriphosphazene mixture and 600 mL of toluene were put into a 2 L stainless steel pressure vessel, 134 g (7.85 mol) of ammonia was further added, and the mixture was reacted under stirring at 50 ° C. for 15 hours. Thereafter, the pressure vessel was opened and 4500 mL of toluene was added to the resulting reaction mixture to dissolve the reaction mixture, followed by washing twice with 1000 mL of diluted hydrochloric acid and demineralized water.

  By using a mixture of ethyl acetate and hexane as an eluent, aminopentaphenoxycyclotriphosphazene and triaminotriphenoxycyclotriphosphazene as by-products were separated by silica gel packed column chromatography.

  After concentrating the eluent under reduced pressure, the residue was allowed to stand overnight as an about 80% ethyl acetate solution, and the precipitated crystals were filtered and dried, and 2,4-diamino-2,4,6,6-tetraphenoxycyclo 484 g of triphosphazene was obtained as a white solid.

The analysis result of the white solid is shown below.
¹ H-NMR spectrum (300 MHz, CDCl ₃ , δ, ppm):
N-H 2.6, 2.8 (4H),
C-H 6.8-7.5 (20H),
³¹ P-NMR spectrum (121 MHz, CDCl ₃ , δ, ppm):
P- (OPh) ₂ 8.5 to 10.5 (1P),
P-NH ₂ (OPh) 18.0 to 20.0 (2P),
LC / MS (positive-ESI) m / z: 540 (M + H ⁺ ),
Hydrolyzed chlorine: 0.01% or less,
TG / DTA analysis:
Melting temperature: 97 ° C.
5% weight loss temperature: 298 ° C.

  From the above analysis results, it was confirmed that the white solid was 2,4-diamino-2,4,6,6-tetraphenoxycyclotriphosphazene. Yield 59.8%, HPLC purity 99.3% (area percentage).

Reference example 3
(Synthesis of 2,2,4-triamino-4,6,6-triphenoxycyclotriphosphazene)
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 2200 mL of THF to 540 g (4.65 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 765 g of a chlorophenoxycyclotriphosphazene mixture. As a result of analyzing this mixture by HPLC using a sample prepared in advance, it was confirmed that it contained 2,2,4-trichloro-4,6,6-triphenoxycyclotriphosphazene.

  Place 764 g of the chlorophenoxycyclotriphosphazene mixture and 300 mL of toluene in a 2 L stainless steel pressure vessel, then reduce the pressure in the pressure vessel to 400 hPa, add 251 g (14.8 mol) of ammonia, and seal at 50 ° C. Stir for 15 hours. Thereafter, the pressure vessel was opened, 3500 mL of toluene was added to the reaction, diluted, filtered, and the toluene layer of the filtrate was washed with demineralized water.

  The toluene layer was concentrated under reduced pressure to obtain 464 g of a yellowish brown viscous product. 28.1 g of this viscous product was taken and purified with a column packed with silica gel using ethyl acetate and hexane as eluents. The fraction containing the desired product was concentrated under reduced pressure and then cooled to room temperature to obtain 12.9 g of a white solid.

The analysis result of the white solid is shown below.
¹ H-NMR spectrum (300 MHz, CDCl ₃ , δ, ppm):
NH: 1.6-2.8 (6H),
C—H: 7.1-7.4 (15H),
³¹ P-NMR spectrum (121 MHz, CDCl ₃ , δ, ppm):
P- (OPh) ₂ : 9.9 to 11.3 (1P),
_{P- (NH 2) 2, P-} (NH 2) (OPh): 17.8~20.5 (2P),
LC / MS (positive-ESI) m / z: 463 (M + H ⁺ ),
Hydrolyzed chlorine: 0.01% or less,
TG / DTA analysis:
Melting temperature: 138 ° C,
5% weight loss temperature: 259 ° C.

  From the above analysis results, it was confirmed that the white solid was 2,2,4-triamino-4,6,6-triphenoxycyclotriphosphazene. Yield 30.8%, HPLC purity 99.4% (area percentage).

Reference example 4
(Synthesis of 2,2-diamino-4,4,6,6-tetraphenoxycyclotriphosphazene)
Into a 5 L flask equipped with a stirrer, a thermometer and a reflux condenser, 521 g (1.50 mol) of hexachlorocyclotriphosphazene and 2150 mL of diethyl ether were charged and stirred while cooling with a water bath to prepare hexachlorocyclotriphosphazene. Was dissolved in diethyl ether to obtain a hexachlorocyclotriphosphazene solution.

  While stirring the above solution, 766 g of 25% aqueous ammonia (11.3 mol as ammonia) was added dropwise thereto at an internal temperature of 25 ° C. or less, and then reacted at an internal temperature of 30 ° C. for 2 hours. The resulting reaction mixture was transferred to a separatory funnel, the aqueous layer was separated, and the diethyl ether layer was washed with demineralized water until neutral.

  After the obtained diethyl ether layer was dehydrated, diethyl ether was distilled off to obtain 276 g of 2,2-diamino-4,4,6,6-tetrachlorocyclotriphosphazene as a pale yellow solid. Yield 59.6%.

The analysis result of the pale yellow solid is shown below.
¹ H-NMR spectrum (300 MHz, acetone-d ₆ , δ, ppm):
NH 2.1 (m),
³¹ P-NMR spectrum (121 MHz, acetone-d ₆ , δ, ppm):
_{P- (NH 2) 2 10.0~12.0 (} 1P),
P-Cl 18.0-20.0 (2P),

  Next, 276 g (0.894 mol) of 2,2-diamino-4,4,6,6-tetrachlorocyclotriphosphazene was charged into a 5 L flask equipped with a stirrer, a thermometer and a reflux condenser. Further, 1,200 mL of THF was added and stirred, and 2,2-diamino-4,4,6,6-tetrachlorocyclotriphosphazene was dissolved in THF to give 2,2-diamino-4,4,6,6. -A solution of tetrachlorocyclotriphosphazene was obtained.

  622 g (5.36 mol) of sodium phenoxide is dissolved in 2500 mL of THF to obtain a solution. This solution is added to the above 2,2-diamino-4,4,6,6-tetrachlorocyclotriphosphazene solution at an internal temperature of 25 ° C. or less. After the addition, the mixture was refluxed for 15 hours. After completion of the reaction, THF was distilled off under reduced pressure. The obtained residue was dissolved in 2000 mL of diethyl ether, washed with 2000 mL of 2% aqueous sodium hydroxide, and then washed twice with 1000 mL of demineralized water.

  The obtained diethyl ether layer was dehydrated, the diethyl ether was distilled off, 660 mL of hexane was added to the obtained residue, and the mixture was stirred for 1 hour and then filtered. The obtained solid was dried at 60 ° C. under reduced pressure to obtain 433 g of 2,2-diamino-4,4,6,6-tetraphenoxycyclotriphosphazene as a white solid. Yield 53.5%.

The analysis result of the white solid is shown below.
¹ H-NMR spectrum (300 MHz, CDCl ₃ , δ, ppm):
NH 2.2 (4H),
C-H 7.0 to 7.5 (20H),
³¹ P-NMR spectrum (121 MHz, CDCl ₃ , δ, ppm):
P- (OPh) ₂ 10.0-11.5 (2P),
_{P- (NH 2) 2 18.5~20.5 (} 1P),
LC / MS (positive-ESI) m / z: 540 (M + H ⁺ ),
Hydrolyzed chlorine: 0.01% or less,
TG / DTA analysis Melting temperature: 107 ° C
5% weight loss temperature: 344 ° C.

Reference Example 5
(Synthesis of aminopentaphenoxycyclotriphosphazene)
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 3000 mL of THF to 784 g (6.75 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 obtained reaction mixture, and the mixture was stirred 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 892 g of a chlorophenoxycyclotriphosphazene mixture. As a result of analyzing this mixture by HPLC using a sample prepared in advance, it was confirmed that monochloropentaphenoxycyclotriphosphazene and dichlorotetraphenoxycyclotriphosphazene were the main components.

  Put 891 g of the above chlorophenoxycyclotriphosphazene mixture and 350 mL of toluene in a 2 L stainless steel pressure vessel, then depressurize the pressure vessel to 400 hPa, add 131 g (7.72 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, and the toluene layer was washed with demineralized water.

  The toluene layer was concentrated under reduced pressure to obtain 812 g of a yellowish brown viscous product. 123 g of this viscous product was taken and purified with a column packed with silica gel using ethyl acetate and hexane as eluents. The fraction containing the desired product was concentrated under reduced pressure and then cooled to room temperature to obtain 43.2 g of a white solid.

The analysis result of the white solid is shown below.
¹ H-NMR spectrum (300 MHz, CDCl ₃ , δ, ppm):
N—H: 2.6 (2H),
C—H: 6.8 to 7.5 (25H),
³¹ P-NMR spectrum (121 MHz, CDCl ₃ , δ, ppm):
P- (OPh) ₂ : 9.3 to 10.1 (2P),
P- (NH ₂ ) (OPh): 18.4 to 19.8 (1P),
LC / MS (positive-ESI) m / z: 617 (M + H ^< + ^> ),
Hydrolyzed chlorine: 0.01% or less,
TG / DTA analysis:
Melting temperature: 76 ° C.
5% weight loss temperature: 315 ° C.

  From the above analysis results, it was confirmed that the white solid was aminopentaphenoxycyclotriphosphazene. Yield 30.7%, HPLC purity 99.3% (area percentage).

B. Production Example 1 of Flame Retardant
(Production of flame retardant finishing agent A1)
100 parts by weight of 2,4,6-triamino-2,4,6-triphenoxycyclotriphosphazene, 5.0 parts by weight of ammonium salt of sulfate ester of tristyrenated phenol ethylene oxide 10 mol adduct and silicone-based antifoaming agent 0.1 part by weight was 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 to disperse the aminophenoxycyclotriphosphazene as fine particles having an average particle diameter of 0.477 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 30% by weight to obtain a flame retardant processing agent A1 according to the present invention.

Example 2
(Manufacture of flame retardant finishing agent B1)
100 parts by weight of 2,4-diamino-2,4,6,6-tetraphenoxycyclotriphosphazene, 5.0 parts by weight of ammonium sulfate ester of tristyrenated phenol ethylene oxide 10-mole adduct and silicone antifoaming agent 0.1 part by weight was 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 to disperse the aminophenoxycyclotriphosphazene as fine particles having an average particle diameter of 0.542 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 30% by weight to obtain a flame retardant processing agent B1 according to the present invention.

Example 3
(Production of flame retardant finishing agent B2)
100 parts by weight of 2,4-diamino-2,4,6,6-tetraphenoxycyclotriphosphazene, 5.0 parts by weight of sodium salt of sulfate ester of tristyrenated phenol ethylene oxide 10 mol adduct, and silicone-based antifoaming agent 0.1 part by weight 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 to disperse the aminophenoxycyclotriphosphazene as fine particles having an average particle diameter of 0.500 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 30% by weight to obtain a flame retardant processing agent B2 according to the present invention.

Example 4
(Production of flame retardant finishing agent B3)
100 parts by weight of 2,4-diamino-2,4,6,6-tetraphenoxycyclotriphosphazene, 5.0 parts by weight of sodium salt of sulfosuccinic acid ester of tristyrenated phenol ethylene oxide 15 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 to disperse the aminophenoxycyclotriphosphazene as fine particles having an average particle diameter of 0.569 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 30% by weight to obtain a flame retardant processing agent B3 according to the present invention.

Example 5
(Production of flame retardant finishing agent B4-1)
100 parts by weight of 2,4-diamino-2,4,6,6-tetraphenoxycyclotriphosphazene, 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 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 to disperse the aminophenoxycyclotriphosphazene as fine particles having an average particle diameter of 0.833 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 30% by weight to obtain the flame retardant processing agent B4-1 according to the present invention. It was.

Example 6
(Production of flame retardant finishing agent B4-2)
100 parts by weight of 2,4-diamino-2,4,6,6-tetraphenoxycyclotriphosphazene, 5.0 parts by weight of an adduct of 25 moles of tristyrenated phenol ethylene oxide and 0.1 parts by weight of a silicone antifoaming agent 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 aminophenoxycyclotriphosphazene as fine particles having an average particle diameter of 1.088 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 30% by weight to obtain the flame retardant processing agent B4-2 according to the present invention. It was.

Example 7
(Production of flame retardant finishing agent B5-1)
100 parts by weight of 2,4-diamino-2,4,6,6-tetraphenoxycyclotriphosphazene, 5.0 parts by weight of an adduct of 13 moles of distyrenated phenol ethylene oxide and 0.1 parts by weight of a silicone-based antifoaming agent Mixed to 130 parts by weight. 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 aminophenoxycyclotriphosphazene as fine particles having an average particle diameter of 0.823 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 30% by weight to obtain the flame retardant processing agent B5-1 according to the present invention. It was.

Example 8
(Production of flame retardant finishing agent B5-2)
100 parts by weight of 2,4-diamino-2,4,6,6-tetraphenoxycyclotriphosphazene, 5.0 parts by weight of an adduct of 20 moles of distyrenated phenol ethylene oxide and 0.1 parts by weight of a silicone-based antifoaming agent Mixed to 130 parts by weight. 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 aminophenoxycyclotriphosphazene as fine particles having an average particle diameter of 0.771 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 30% by weight to obtain the flame retardant processing agent B5-2 according to the present invention. It was.

Example 9
(Production of flame retardant finishing agent B5-3)
100 parts by weight of 2,4-diamino-2,4,6,6-tetraphenoxycyclotriphosphazene, 5.0 parts by weight of a 50 mol adduct of distyrenated phenol ethylene oxide and 0.1 part by weight of a silicone-based antifoaming agent Mixed to 130 parts by weight. This mixture was charged into a mill filled with glass beads having a diameter of 0.8 mm and pulverized for 4 hours to disperse the aminophenoxycyclotriphosphazene as fine particles having an average particle diameter of 1.167 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 30% by weight to obtain the flame retardant processing agent B5-3 according to the present invention. It was.

Example 10
(Manufacture of flame retardant finishing agent B6)
2,4-diamino-2,4,6,6-tetraphenoxycyclotriphosphazene (100 parts by weight), distyrenated methylphenol ethylene oxide (14 mol adduct) (5.0 parts by weight) and silicone antifoaming agent (0.1 part by weight) 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 aminophenoxycyclotriphosphazene as fine particles having an average particle diameter of 1.430 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 30% by weight to obtain a flame retardant processing agent B6 according to the present invention.

Example 11
(Manufacture of flame retardant finishing agent B7)
100 parts by weight of 2,4-diamino-2,4,6,6-tetraphenoxycyclotriphosphazene, 5.0 parts by weight of a 15-benzyl tribenzylated phenol ethylene oxide adduct and 0.1 parts by weight of a silicone antifoaming agent Mixed to 130 parts by weight. This mixture was charged into a mill filled with glass beads having a diameter of 0.8 mm and pulverized for 4 hours to disperse the aminophenoxycyclotriphosphazene as fine particles having an average particle diameter of 0.914 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 nonvolatile content concentration was 30% by weight to obtain a flame retardant processing agent B7 according to the present invention.

Example 12
(Manufacture of flame retardant finishing agent B8)
100 parts by weight of 2,4-diamino-2,4,6,6-tetraphenoxycyclotriphosphazene, 5.0 parts by weight of an adduct of 11 moles of cumylated phenol ethylene oxide and 0.1 part by weight of a silicone-based antifoaming agent Mixed to 130 parts by weight. 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 aminophenoxycyclotriphosphazene as fine particles having an average particle diameter of 0.500 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 nonvolatile content concentration was 30% by weight to obtain a flame retardant processing agent B8 according to the present invention.

Example 13
(Production of flame retardant finishing agent B9)
100 parts by weight of 2,4-diamino-2,4,6,6-tetraphenoxycyclotriphosphazene, 5.0 parts by weight of stearyltrimethylammonium chloride and 0.1 parts by weight of a silicone-based antifoaming agent are mixed with 130 parts by weight of water. did. 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 aminophenoxycyclotriphosphazene as fine particles having an average particle diameter of 1.575 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 30% by weight to obtain a flame retardant processing agent B9 according to the present invention.

Example 14
(Manufacture of flame retardant finishing agent B10)
100 parts by weight of 2,4-diamino-2,4,6,6-tetraphenoxycyclotriphosphazene, 5.0 parts by weight of sodium dioctyl sulfosuccinate and 0.1 parts by weight of a silicone-based antifoaming agent are added to 130 parts by weight of water. Mixed. 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 aminophenoxycyclotriphosphazene as fine particles having an average particle diameter of 1.564 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 30% by weight to obtain a flame retardant processing agent B10 according to the present invention.

Example 15
(Production of flame retardant finishing agent B11)
100 parts by weight of 2,4-diamino-2,4,6,6-tetraphenoxycyclotriphosphazene, 5.0 parts by weight of polyoxyethylene (20) sorbitan monostearate and 0.1 parts by weight of a silicone-based antifoaming agent 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 aminophenoxycyclotriphosphazene as fine particles having an average particle diameter of 1.615 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 30% by weight to obtain a flame retardant processing agent B11 according to the present invention.

Example 16
(Production of flame retardant finishing agent B12)
2,4-diamino-2,4,6,6-tetraphenoxycyclotriphosphazene 100 parts by weight, polyoxyethylene (15) tridecyl ether phosphate ester 5.0 parts by weight and silicone-based antifoaming agent 0.1 part by weight Parts 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 aminophenoxycyclotriphosphazene as fine particles having an average particle diameter of 1.350 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 nonvolatile content concentration was 30% by weight to obtain a flame retardant processing agent B12 according to the present invention.

Example 17
(Production of flame retardant finishing agent B13)
100 parts by weight of 2,4-diamino-2,4,6,6-tetraphenoxycyclotriphosphazene, 5.0 parts by weight of polyoxyethylene (40) hydrogenated castor oil and 0.1 part by weight of a silicone-based antifoaming agent are added to water. Mixed to 130 parts by weight. This mixture was charged into a mill filled with glass beads having a diameter of 0.8 mm and pulverized for 4 hours to disperse the aminophenoxycyclotriphosphazene as fine particles having an average particle diameter of 1.497 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 30% by weight to obtain a flame retardant processing agent B13 according to the present invention.

Example 18
(Manufacture of flame retardant finishing agent B14)
100 parts by weight of 2,4-diamino-2,4,6,6-tetraphenoxycyclotriphosphazene, 5.0 parts by weight of polyoxyethylene (8) stearylamine and 0.1 parts by weight of a silicone-based antifoaming agent are added to water 130. Mixed into parts by weight. 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 aminophenoxycyclotriphosphazene as fine particles having an average particle diameter of 1.791 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 nonvolatile content concentration was 30% by weight to obtain a flame retardant processing agent B14 according to the present invention.

Example 19
(Manufacture of flame retardant finishing agent C1)
80 parts by weight of 2,4,6-triamino-2,4,6-triphenoxycyclotriphosphazene, 20 parts by weight of 2,4-diamino-2,4,6,6-tetraphenoxycyclotriphosphazene, tristyrenated phenol 5.0 parts by weight of ammonium salt of sulfuric acid ester of 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 to disperse the aminophenoxycyclotriphosphazene as fine particles having an average particle diameter of 0.533 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 30% by weight to obtain a flame retardant processing agent C1 according to the present invention.

Example 20
(Production of flame retardant finishing agent D1)
2,4,6-triamino-2,4,6-triphenoxycyclotriphosphazene 50 parts by weight, 2,4-diamino-2,4,6,6-tetraphenoxycyclotriphosphazene 50 parts by weight, tristyrenated phenol 5.0 parts by weight of ammonium salt of sulfuric acid ester of 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 in a mill filled with glass beads having a diameter of 0.8 mm and pulverized for 4 hours to disperse the aminophenoxycyclotriphosphazene as fine particles having an average particle diameter of 0.598 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 30% by weight to obtain a flame retardant processing agent D1 according to the present invention.

Example 21
(Production of flame retardant E1)
2,4,6-triamino-2,4,6-triphenoxycyclotriphosphazene 10 parts by weight, 2,4-diamino-2,4,6,6-tetraphenoxycyclotriphosphazene 90 parts by weight, tristyrenated phenol 5.0 parts by weight of ammonium salt of sulfuric acid ester of 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 to disperse the aminophenoxycyclotriphosphazene as fine particles having an average particle diameter of 0.734 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 30% by weight to obtain a flame retardant processing agent E1 according to the present invention.

Example 22
(Production of flame retardant finish B1B5-2)
100 parts by weight of 2,4-diamino-2,4,6,6-tetraphenoxycyclotriphosphazene, 2.5 parts by weight of ammonium salt of sulfuric ester of tristyrenated phenol ethylene oxide 10 mol adduct, distyrenated phenol ethylene oxide 2.5 parts by weight of 20 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 to disperse the aminophenoxycyclotriphosphazene as fine particles having an average particle diameter of 0.715 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 30% by weight to obtain the flame retardant processing agent B1B5-2 according to the present invention. It was.

Example 23
(Production of flame retardant finishing agent B5-1A)
100 parts by weight of 2,4-diamino-2,4,6,6-tetraphenoxycyclotriphosphazene and 5.0 parts by weight of distyrenated phenol ethylene oxide 13 mol adduct 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 to disperse the aminophenoxycyclotriphosphazene as fine particles having an average particle diameter of 1.851 μm. 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.

Comparative Example 1
(Manufacture of flame retardant finishing agent F)
47 parts by weight of guanidine phosphate was dissolved in 53 parts by weight of water to obtain a flame retardant processing agent F according to a comparative example.

Comparative Example 2
(Manufacture of flame retardant finishing agent G)
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 nonvolatile content concentration was 40% by weight to obtain a flame retardant processing agent G according to a comparative example.

Comparative Example 3
(Manufacture of flame retardant finishing agent H)
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 nonvolatile content concentration when dried was 40% by weight to obtain a flame retardant finishing agent H according to a comparative example.

Comparative Example 4
(Production of flame retardant finishing agent I)
20 parts by weight of hexaaminocyclotriphosphazene was dissolved in 80 parts by weight of water to obtain a flame retardant finishing agent I according to a comparative example.

Comparative Example 5
(Manufacture of flame retardant finishing agent J)
100 parts by weight of 2,2,4-triamino-4,4,6-triphenoxycyclotriphosphazene, 5.0 parts by weight of ammonium sulfate ester of tristyrenated phenol ethylene oxide 10-mole adduct, and silicone antifoaming agent 0.1 part by weight 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 to disperse the aminophenoxycyclotriphosphazene as fine particles having an average particle diameter of 0.420 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 30% by weight to obtain a flame retardant processing agent J according to a comparative example.

Comparative Example 6
(Manufacture of flame retardant finishing agent K)
100 parts by weight of 2,2-diamino-4,4,6,6-tetraphenoxycyclotriphosphazene, 5.0 parts by weight of ammonium sulfate ester of tristyrenated phenol ethylene oxide 10-mole adduct and silicone antifoaming agent 0.1 part by weight 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 to disperse the aminophenoxycyclotriphosphazene as fine particles having an average particle diameter of 0.432 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 30% by weight to obtain a flame retardant processing agent K according to a comparative example.

Comparative Example 7
(Manufacture of flame retardant finishing agent L)
100 parts by weight of aminopentaphenoxycyclotriphosphazene, 10.0 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 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 to disperse the aminophenoxycyclotriphosphazene as fine particles having an average particle diameter of 0.620 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 nonvolatile content concentration was 30% by weight to obtain a flame retardant processing agent L according to a comparative example.

Comparative Example 8
(Manufacture of flame retardant finishing agent M)
Mixing 100 parts by weight of hexaphenoxycyclotriphosphazene, 10.0 parts by weight of sodium salt of sulfosuccinate of 15 mole adduct of tristyrenated phenol ethylene oxide and 0.1 parts by weight of silicone antifoaming agent in 130 parts by weight of water did. 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 hexaphenoxycyclotriphosphazene as fine particles having an average particle diameter of 0.642 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 nonvolatile content concentration was 40% by weight to obtain a flame retardant processing agent M according to a comparative example.

Comparative Example 9
(Production of flame retardant finishing agent N)
To 100 parts by weight of 2,4,6-triphenoxy-2,4,6-trimethoxycyclotriphosphazene, 12.5 parts by weight of ammonium salt of sulfate ester of tristyrenated phenol ethylene oxide 10 mol adduct was added, To this was added 137.5 parts by weight of hot water with stirring, emulsified and dispersed, and then cooled to obtain a milky white flame retardant finish N according to a comparative example. The average particle size of the flame retardant finishing agent N was 0.251 μm.

C. Flame Retardant Processing of Polyester-Based Synthetic Fiber Structure (1) Preparation of Fabric to be Treated Polyester knit (weighing weight 200 g / m2) is dispersed dye Dianix Black AM-SLR (manufactured by DyStar) 4% owf at 130 ° C for 30 minutes After dyeing in the bath, 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 25, the polyester knit dyed in black was flame-retardant processed as a fabric to be treated.

(2) In-bath dyeing simultaneous flame retardant treatment Example 24
In the polyester knit dyeing step, the flame retardant processing agent E1 according to the present invention is added to the polyester knit at 11% owf and disperse dye Dianix Black AM-SLR (made by DyStar) 4% owf at 130 ° C. for 30 minutes. After the flame retardant treatment at the same time as dyeing, it was subjected to reduction cleaning by a conventional method and dried to obtain a flame retardant polyester fabric dyed black.

  The amount of flame retardant attached in the above-mentioned simultaneous flame retardant treatment in the bath is calculated from the total weight decreased 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. Asked.

  The flame-retardant polyester fabric thus obtained was subjected to evaluation tests for friction fastness, stickiness, chalk mark, bleed out, light fastness and wet heat. Table 1 shows the results of these performance tests.

  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 processing example 25 and comparative example 10
As flame retardant processing agents according to the present invention, A1, B1, B2, B3, B4-1, B4-2, B5-1, B5-2, B5-3, B6, B7, B8, B9, B10, B11, B12 , B13, B14, C1, D1, E1, B1B5-2, B5-1A, and Comparative Example 10, blank, flame retardant F, G, H, I, J, K, L, M, N or these Each of the above-mentioned treated fabrics was flame-retardant processed using a processing solution diluted with water to obtain a flame-retardant processed polyester fabric according to the present invention and a polyester fabric as a comparative example. Tables 1 to 5 show the results of performance tests on these flame-retardant polyester fabrics.

  Moreover, although the flame retardant processing of the polyester fabric was carried out using each of the flame retardant processing agents A1 and B1, an example in which the flame retardant required to be satisfied by the polyester fabric could not be imparted due to the small amount of adhesion is shown in Table 4. This is shown as Comparative Example 10 in the middle.

  In the above-mentioned flame retardant processing with the flame retardant, the flame retardant adhesion amount from the weight difference of the polyester fabric before and after the flame retardant processing, the concentration of the flame retardant diluted with the solvent and the flame retardant content in the flame retardant Was calculated.

  The performance test of the flame-retardant polyester fabric in Example 25 and Comparative Example 10 was performed as follows. That is, the fabric to be treated was flame-retardant processed by the padding method using the flame retardant processing agent according to the present invention, dried at 100 ° C. for 5 minutes, and heat-treated at 130 ° C. for 1 minute. 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, with respect to friction fastness, stickiness, chalk mark, bleed out, light fastness and wet heat test.

  For flame retardancy, using a single bath containing 1.0% by weight of silicone resin and flame retardant, the flame retardant was attached to the treated fabric by the padding method, and then dried at 130 ° C. for 5 minutes. Then, heat-treated at 150 ° C. for 1 minute to obtain a flame-retardant 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.

Example 26
100 parts by weight of 2,4-diamino-2,4,6,6-tetraphenoxycyclotriphosphazene, 5.0 parts by weight of ammonium sulfate ester of tristyrenated phenol ethylene oxide 10-mole adduct and silicone antifoaming agent 0.1 part by weight and 25 parts by weight of a polyester-based urethane resin emulsion (non-volatile content 50%, glass transition temperature (Tg) is −42 ° C.) were mixed with 105 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 to disperse the aminophenoxycyclotriphosphazene 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, 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 finish O according to the present invention. The non-volatile content of this flame retardant finishing agent O was 35.7% by weight.

Example 27
Using the flame retardant processing agent O obtained in Example 26, the treated fabric was flame retardant processed in the same manner as in Example 25 to obtain a flame retardant polyester fabric according to the present invention. A performance test was conducted on this flame-retardant polyester fabric in the same manner as in Example 25. The results are shown in Table 4.

D. Flame retardant performance test (fastness to friction)
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.

(Intensity)
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.

  Tables 1 to 5 show the test results of the flame retardancy.

  As shown in Examples 24 and 25 of Tables 1 to 4, the polyester fabrics that are flame-retardant processed using the flame-retardant processing agent according to the present invention are excellent in flame retardancy, friction fastness, and light fastness. In addition, there is no sticking or chalk marks without cleaning the flame-retardant processed textiles, and bleeding out is also suppressed.

  The test result about the to-be-processed fabric itself before a flame-retardant process is shown in the comparative example 10 of Table 4 as a blank. Even in comparison with this blank, in particular, the flame retardant processing agents A1 and B1 in Table 1 are inferior in stickiness and friction fastness by using a small amount of flame retardant.

  In Example 27, a polyester-based urethane emulsion was used for the purpose of improving the friction fastness of the flame-retardant-treated polyester fabric, and a flame-retardant processing agent containing a paraffin wax emulsion was used for the purpose of improving sewing properties. The treated fabric was subjected to flame retardant processing, and the obtained polyester fabric was evaluated for performance.

  As a result, the obtained flame-retardant processed polyester fabric is excellent in flame retardancy, friction fastness and light fastness as in Example 24 and Example 25, and there is no washing of the flame-retardant processed fiber product. In addition, no sticking or chalk marks were generated, and bleeding out was also suppressed.

  Comparative Examples 1 to 3 use, as flame retardants, crystalline powders of guanidine phosphate, anilinodiphenyl phosphate and tetra (2,6-dimethylphenyl) -m-phenylene phosphate, respectively, and flame retardants F and G, respectively. As shown in Comparative Example 10 of Table 4 to Table 5, when any flame retardant was used, the flame-retardant polyester fabric was noticeable. . Further, as shown in Comparative Example 10 of Table 5, the flame retardant finishing agents G and H were inferior in both friction fastness and light fastness, and bleed out was also remarkable.

  In Comparative Example 4, water-soluble hexaaminocyclotriphosphazene was dissolved in water to obtain a flame retardant finishing agent I. In Table 5, as shown in Comparative Example 10, there was a sticking. It was.

  In Comparative Examples 5 and 6, 2,2,4-triamino-4,4,6-triphenoxycyclotriphosphazene having a geminal-diamino group in which two amino groups are bonded to one phosphorus atom and 2 , 2-Diamino-4,4,6,6-tetraphenoxycyclotriphosphazene is used to obtain flame retardants J and K, respectively. Since these geminal-diamino groups possessed by the flame retardant easily hydrolyze in a wet heat environment, these flame retardant processing agents show significant discoloration in the wet heat test. It was.

  Comparative Examples 7 and 8 were obtained by dispersing aminopentaphenoxycyclotriphosphazene and hexaphenoxycyclotriphosphazene in water as flame retardants, respectively, to obtain flame retardant processing agents L and M, respectively. Since the polyester fabric subjected to the flame retardant processing using these flame retardant processing agents contains a large amount of surfactant, in Table 5, as shown in Comparative Example 10, in addition to the stickiness, the friction fastness It was inferior.

  In Comparative Example 9, 2,4,6-triphenoxy-2,4,6-trimethoxycyclotriphosphazene was emulsified and dispersed to obtain flame retardant processing agent N. As shown in FIG. 10, in addition to the fact that there was a sticking, it was inferior in friction fastness and bleed out property.

As described above, the flame retardant processing agents A1 and B1 in Comparative Example 10 of Table 4 have poor flame retardant performance of the resulting flame retardant processed polyester fabric as a result of too little flame retardant adhesion to the polyester fabric. It was enough.

Claims (7)

The following structural formula (1)

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

A flame retardant for a polyester-based synthetic fiber structure comprising at least one aminophenoxycyclotriphosphazene selected from 2,4-diamino-2,4,6,6-tetraphenoxycyclotriphosphazene represented by the formula:   A flame retardant processing agent for a polyester-based synthetic fiber structure obtained by dispersing the flame retardant according to claim 1 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 flame-retardant 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 flame retardant polyester-based synthetic fiber structure which is flame retardant processed by the flame retardant processing method according to claim 5.