WO2017110785A1 - Traitement ignifuge de structures de fibre synthétique à base de polyester - Google Patents

Traitement ignifuge de structures de fibre synthétique à base de polyester Download PDF

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WO2017110785A1
WO2017110785A1 PCT/JP2016/087896 JP2016087896W WO2017110785A1 WO 2017110785 A1 WO2017110785 A1 WO 2017110785A1 JP 2016087896 W JP2016087896 W JP 2016087896W WO 2017110785 A1 WO2017110785 A1 WO 2017110785A1
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Prior art keywords
flame retardant
weight
polyester
flame
parts
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PCT/JP2016/087896
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English (en)
Japanese (ja)
Inventor
将大 和田
輝文 岩城
重人 小山
多田　祐二
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大京化学株式会社
株式会社伏見製薬所
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Priority to JP2017558143A priority Critical patent/JP6818327B2/ja
Publication of WO2017110785A1 publication Critical patent/WO2017110785A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K21/00—Fireproofing materials
    • C09K21/06—Organic materials
    • C09K21/12—Organic materials containing phosphorus
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
    • D06M13/44—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen containing nitrogen and phosphorus

Definitions

  • 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.
  • 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.
  • polyester-based synthetic fibers by padding method using water-soluble salts such as guanidine phosphate and carbamate phosphate as flame retardant processing agents.
  • water-soluble salts such as guanidine phosphate and carbamate phosphate
  • 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.
  • 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).
  • 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).
  • HBCD 1,2,5,6,9,10-hexabromocyclododecane
  • phosphate esters and phosphate 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.
  • 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
  • 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.
  • 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.
  • 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.
  • this 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.
  • polyester-based synthetic fiber structure is flame-retardant processed with a flame retardant containing a cyclic aminophenoxyphosphazene as a flame retardant, and at the same time dyed in a deep color using 3 to 5% owf
  • 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-A-10-298188 JP 2002-105881 A
  • 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.
  • a flame retardant processing agent for a polyester-based synthetic fiber structure obtained by dispersing the above flame retardant in a solvent in the presence of a surfactant.
  • thermoplastic polyester-based synthetic fiber structure which is flame retardant processed with the above flame retardant.
  • a polyester-based synthetic fiber structure is flame-retardant processed with the above-mentioned flame-retardant processing agent.
  • a flame-retardant processing method for a polyester-based synthetic fiber structure which is attached to a polyester-based synthetic fiber structure, dried, and then heat-treated at a temperature of 100 to 220 ° C.
  • 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.
  • 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.
  • 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, L-lactic acid and aliphatic hydroxycarboxylic acid copolymer, polycaprolactone such as poly- ⁇ -caprolactone (PCL), polymalic acid, polyhydroxycarboxylic butyric acid, polyhydroxyvaleric acid ⁇ -hydroxybutyric acid (3HB) -3-hydroxyvale
  • PCL
  • the flame retardant polyester synthetic fiber structure according to the present invention is suitably used for, for example, seat sheets, seat covers, curtains, wallpaper, ceiling cloths, carpets, notebooks, architectural curing sheets, tents, canvases, and the like.
  • the flame retardant of the polyester-based synthetic fiber structure according to the present invention has the following structural formula (1)
  • At least one aminophenoxycyclotriphosphazene selected from 2,4-diamino-2,4,6,6-tetraphenoxycyclotriphosphazene.
  • 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.
  • the flame retardant comprising aminophenoxycyclotriphosphazene is suitably used as a flame retardant processing agent dispersed in an appropriate solvent.
  • the flame retardant for a polyester 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.
  • the preferred dispersion medium for the flame retardant in the flame retardant processing agent is water.
  • 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.
  • the flame retardant processing agent according to the present invention can be preferably obtained by mixing the aminophenoxycyclotriphosphazene with water with a surfactant and pulverizing it with a wet pulverizer to make it into fine particles.
  • any of an anionic surfactant, a nonionic surfactant, and a cationic surfactant can be used.
  • 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 an ammonium ion) Is shown.
  • 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 an ammonium ion
  • M ′ represents an alkali metal ion or an ammonium ion
  • a and c each independently represent an average of 1 to 3
  • b and d each independently represent an average of 5 to 30.
  • M or M When 'is an alkali metal ion, specifically, it is preferably a sodium ion or a potassium ion.
  • the amount of the surfactant to be used 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.
  • the amount of the surfactant used when the amount of the surfactant used is less than 0.9 parts by weight, the aminophenoxycyclotriphosphazene may not be dispersed in water.
  • 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.
  • 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.
  • the other anionic surfactants and nonions Surfactants and cationic surfactants may be used singly or in combination of two or more as required.
  • 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.
  • 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, sul
  • 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.
  • 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.
  • 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.
  • the flame retardant 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 ⁇ m 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 ⁇ m.
  • the flame retardant processing agent is usually diluted with water and used as a processing liquid.
  • a working fluid preferably contains the aminophenoxycyclotriphosphazene according to the present invention in a range of usually 0.5 to 5% by weight.
  • 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.
  • the amount of the flame retardant attached to the polyester-based synthetic fiber structure does not limit the amount of the flame retardant attached 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.
  • the flame retardant according to the present invention 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.
  • a flame-retardant processing agent is attached to the polyester-based synthetic fiber structure.
  • An example is a method in which the aminophenoxycyclotriphosphazene according to the present invention is exhausted into the fiber by heat treatment at a temperature of 100 to 220 ° C. for 1 to 5 minutes after drying.
  • 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.
  • 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.
  • aminophenoxycyclotriphosphazene is adhered to the polyester-based synthetic fiber structure in this way, and then dried and heat-treated at a temperature of 100 to 220 ° C. for 1 to 5 minutes as described above.
  • 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.
  • 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 solution diluted with the flame retardant and treated in a bath at a temperature of 100 to 140 ° C. to exhaust the flame retardant into the fiber. Can be mentioned.
  • 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 finish according to the present invention may contain a surfactant other than those described above as a dispersant, if necessary, within a range where the performance is not hindered.
  • 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.
  • the flame retardant conventionally known may be included as needed.
  • 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.
  • 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.
  • 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.
  • fiber finishing agents include softeners, antistatic agents, water and oil repellents, hard finishes, and texture modifiers.
  • 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 the 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.
  • % 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.
  • THF tetrahydrofuran
  • the reaction mixture thus obtained was washed with 2000 mL of 2% aqueous sodium hydroxide solution, and then washed 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. This mixture was analyzed by HPLC using a sample prepared in advance, and it was confirmed that 2,4,6-trichloro-2,4,6-triphenoxycyclotriphosphazene was contained.
  • the obtained reaction mixture was washed with 2000 mL of 2% aqueous sodium hydroxide solution and then washed 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.
  • aminopentaphenoxycyclotriphosphazene and triaminotriphenoxycyclotriphosphazene as by-products were separated by silica gel packed column chromatography.
  • the reaction mixture thus obtained was washed with 2000 mL of 2% aqueous sodium hydroxide solution, and then washed 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.
  • the mixture was analyzed by HPLC using a sample prepared in advance, and as a result, it was confirmed that it contained 2,2,4-trichloro-4,6,6-triphenoxycyclotriphosphazene.
  • 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 obtained diethyl ether layer was dehydrated, diethyl ether was distilled off, 660 mL of hexane was added to the obtained residue, and the mixture was stirred for 1 hour, followed by filtration.
  • 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 reaction mixture thus obtained was washed with 2000 mL of 2% aqueous sodium hydroxide solution, and then washed 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.
  • 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.
  • 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 salt of sulfuric ester of tristyrenated phenol ethylene oxide 10 mol 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 ⁇ m. 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 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 ⁇ m. 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 ⁇ m. 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 Manufacture 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 ⁇ m. 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 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 25 mol adduct of tristyrenated phenol ethylene oxide and 0.1 parts by weight of 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 ⁇ m. 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 the flame retardant processing agent B4-2 according to the present invention. It was.
  • Example 7 Manufacture of flame retardant finish 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 ⁇ m. 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 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 20 mol of distyrenated phenol ethylene oxide adduct and 0.1 parts by weight of silicone 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 ⁇ m. 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 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 parts 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 ⁇ m. 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 100 parts by weight of 2,4-diamino-2,4,6,6-tetraphenoxycyclotriphosphazene, 5.0 parts by weight of an adduct of 14 moles of distyrenated methylphenol 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 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 ⁇ m. 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-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 0.914 ⁇ m. 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 parts by weight of a silicone 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 ⁇ m. 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 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 aminophenoxycyclotriphosphazene as fine particles having an average particle diameter of 1.575 ⁇ m. 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 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 ⁇ m. 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 ⁇ m. 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) 100 parts by weight of 2,4-diamino-2,4,6,6-tetraphenoxycyclotriphosphazene, 5.0 parts by weight of polyoxyethylene (15) tridecyl ether phosphate ester and 0.1 parts by weight of a silicone-based antifoaming agent 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 ⁇ m. 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 ⁇ m. 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 were added to 130 parts of water. 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 ⁇ m. 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 ⁇ m.
  • 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 ⁇ m. 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 ⁇ m. 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 Manufacture 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 sulfate 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 ⁇ m. 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 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 13 moles of distyrenated phenol ethylene oxide 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 ⁇ m. 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 concentration of the nonvolatile content 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 ⁇ m. 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 a 10-mole ethylene oxide adduct of octylphenol and 0.1 parts by weight of a 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 ⁇ m or less.
  • 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 ⁇ m, 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 salt of sulfuric ester of tristyrenated phenol ethylene oxide 10 mol 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 ⁇ m. 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 salt of sulfate ester of tristyrenated phenol ethylene oxide 10 mol 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 ⁇ m. 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 ⁇ m. 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 ⁇ m.
  • 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 ⁇ m.
  • 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.
  • Example 24 In-bath dyeing simultaneous flame retardant treatment
  • the flame retardant finish E1 according to the present invention is added to the polyester knit at 11% owf and disperse dye Dianic Black AM-SLR (manufactured by DyStar) 4% owf at 130 ° C. for 30 minutes
  • 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 processed 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.
  • silicone resin 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.
  • 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 polyester fabric fire-treated 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.
  • 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 salt of sulfuric ester of tristyrenated phenol ethylene oxide 10 mol 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): ⁇ 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 ⁇ m.
  • Tg glass transition temperature
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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 crystalline powders of guanidine phosphate, anilinodiphenyl phosphate, and tetra (2,6-dimethylphenyl) -m-phenylene phosphate as flame retardants.
  • Comparative Example 10 of Table 4 to Table 5 when any flame retardant was used, the flame-retardant polyester fabric was noticeable. .
  • 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.
  • Comparative Example 4 water-soluble hexaaminocyclotriphosphazene was dissolved in water to obtain a flame retardant finishing agent I.
  • Table 5 as shown in Comparative Example 10, there was a sticking. It was.
  • Comparative Examples 7 and 8 are 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.
  • Comparative Example 9 2,4,6-triphenoxy-2,4,6-trimethoxycyclotriphosphazene was emulsified and dispersed to obtain flame retardant processing agent N.
  • Table 5 Comparative Example 9 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.
  • 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.

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Abstract

La présente invention concerne : un produit ignifuge pour des structures de fibre synthétique à base de polyester, comprenant au moins un aminophénoxy cyclotriphosphazène choisi parmi 2,4,6-triamino-2,4,6-triphénoxy cyclotriphosphazène et 2,4-diamino-2,4,6,6-tétraphénoxy cyclotriphosphazène; et un agent de traitement ignifuge pour structures de fibre synthétique à base de polyester, qui est obtenu par dispersion du produit ignifuge dans un solvant en présence d'un tensioactif. La présente invention concerne en outre un procédé de traitement ignifuge pour structures de fibre synthétique à base de polyester, le procédé impliquant le traitement ignifuge d'une structure de fibre synthétique à base de polyester par utilisation de l'agent de traitement ignifuge.
PCT/JP2016/087896 2015-12-22 2016-12-20 Traitement ignifuge de structures de fibre synthétique à base de polyester WO2017110785A1 (fr)

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WO2018235756A1 (fr) * 2017-06-22 2018-12-27 大京化学株式会社 Traitement ignifuge de structure en fibre synthétique à base de polyester

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CN114773681B (zh) * 2022-03-12 2023-06-06 郑州大学 一种具有微胶囊核壳结构的环三磷腈类阻燃剂及制备方法

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US3240728A (en) * 1961-11-23 1966-03-15 Albright & Wilson Mfg Ltd Polyurethanes containing cyclic phosphonitrilamidates
JPH08291467A (ja) * 1995-04-14 1996-11-05 Toray Ind Inc 難燃性ポリエステル繊維およびその製造方法
JP2001316454A (ja) * 2000-02-29 2001-11-13 Otsuka Chem Co Ltd 難燃性エポキシ樹脂組成物及び電子部品

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018235756A1 (fr) * 2017-06-22 2018-12-27 大京化学株式会社 Traitement ignifuge de structure en fibre synthétique à base de polyester
JPWO2018235756A1 (ja) * 2017-06-22 2020-04-30 大京化学株式会社 ポリエステル系合成繊維構造物の難燃加工
JP7176698B2 (ja) 2017-06-22 2022-11-22 大京化学株式会社 ポリエステル系合成繊維構造物の難燃加工

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