JP2001262466A - Flame-retardant fiber product and flameproofing agent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a flame-retardant fiber product capable of suitably being used or textiles, bedding, wall papers, building materials and interor materials of automobiles, ariplanes, railways, ships, etc., especially sheet covers, floor mats, carpets, etc. SOLUTION: This flame-retardant fiber product is obtained by adding an ammonium polyphosphorate-containing substance covered with a thermoplastic resin in an amount of 3-50 wt.% based on total weight, expressed in terms of dried weight to a fiber product.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a flame-retardant textile product exhibiting a high degree of flame retardancy, and a flameproofing agent comprising a synthetic resin emulsion in which an ammonium polyphosphate-containing substance coated with a thermoplastic resin is dispersed. About. More specifically, a flame-retardant fiber obtained by dispersing an ammonium polyphosphate-containing substance coated with a thermoplastic resin in a synthetic resin emulsion, and applying, impregnating, or backing the fiber product with the emulsion. The present invention relates to a product and a flameproofing agent in which an ammonium polyphosphate-containing substance coated with a predetermined amount of a thermoplastic resin is dispersed in a synthetic resin emulsion.

[0002]

2. Description of the Related Art Conventionally, many textile products have been used for clothing, bedding, wallpaper, and interior materials of automobiles, aircraft, railways, ships, and the like. With the expansion and diversification of these uses, fireproof, flameproof, fireproof or flame retardant applications are required for uses using fibers, and the performance thereof is becoming stricter year by year.

Further, products using a halogen compound or a halogenated organophosphorus compound, which is the mainstream of the conventional flame-retarding technology, may generate halogen-based gas during combustion, or use such a halogen compound to make the flame-retardant. The processed textile products
The fiber product is dissolved or swelled in an organic solvent used at the time of dry cleaning, so that the fiber product becomes sticky, which deteriorates the texture and lowers the flame retardancy.

[0004] Examples of using a water-soluble inorganic salt such as an ammonium phosphate monomer, a borate, or ammonium sulfamate as a flameproofing agent that does not generate halogen gas are known. However, there was a drawback that the textile product was inferior in water-washing resistance due to its property.

[0005] In order to meet these demands, studies have been made on the use of sparingly soluble salts such as ammonium polyphosphate. For example, Japanese Patent Publication No. 46200/1976 discloses that a fiber or a fiber product is prepared by adding a phosphorus compound such as ammonium polyphosphate and a formaldehyde condensation polymer of a guanidine salt or a guanylurea salt, or a cocondensation product of these with another compound. A method for flame retarding fibers or textiles to which reaction products have been attached is disclosed. However, the flame-retardant textile product obtained by the method disclosed in this publication has a problem in that the ammonium polyphosphate used in the product has insufficient water resistance, and a large amount of guanidine salt or guanylurea salt is liberated from the formaldehyde polycondensate. Formalin sometimes occurred.

Further, Japanese Patent Application Laid-Open Nos. 4-214471 and 4-228676 disclose a partially water-soluble ammonium polyphosphate, a surfactant, a heat-curable resin, and a fabric containing water. Compositions for combusting are disclosed. However, in some cases, ammonium polyphosphate, one component of the composition disclosed in the publication, is poor in water resistance, especially in relatively high temperatures, due to its water solubility.

As apparent from the above description, an object of the present invention is to provide a flame-retardant fiber product excellent in water resistance and flame retardancy, and a flameproofing agent for making the fiber product flame-retardant. That is.

The present invention has the following configuration. (1) A flame-retardant fiber product in which a fiber-containing product contains an ammonium polyphosphate-containing substance coated with a thermoplastic resin in an amount of 3 to 50% by dry weight of the total weight.

(2) A treatment liquid in which an ammonium polyphosphate-containing substance coated with a thermoplastic resin is dispersed in a ratio of 10 to 100 parts by weight with respect to 100 parts by weight of a synthetic resin emulsion is obtained by treating a fiber product. Flame retardant textile products.

(3) The synthetic resin emulsion is selected from the group consisting of acrylic ester emulsions, urethane emulsions, epoxy emulsions, vinyl acetate emulsions, vinyl chloride emulsions, vinylidene chloride emulsions, and polyvinyl alcohol emulsions. 3. The flame-retardant fiber product according to the above item 2, which is at least one kind.

(4) The thermoplastic resin is a homopolymer of a monomer represented by the following formula (1) having 2 to 5 active groups capable of polymerizing in one molecule or a copolymer thereof, or polymerized in one molecule: At least one selected from monomers represented by the following formula 1 having 2 to 5 possible active groups and a monomer represented by the following formula 2 having one polymerizable active group per molecule 4. The flame-retardant fiber product according to any one of the above items 1 to 3, which is a copolymer with at least one selected from the group consisting of:

Embedded image

Embedded image (In the formula, R ₁ , R _2, and R ₃ are the same or different groups, and each represents a hydrogen atom, a halogen atom, a cyano group, a cyanoalkyl group having 2 to 8 carbon atoms, a carboxyl group, An alkyl group having 10 to 10 carbon atoms, an alkyl ether group having 1 to 15 carbon atoms, an aminoalkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkynyl group having 2 to 12 carbon atoms, and 1 to 18 carbon atoms Wherein R ₄ is one of the groups represented by the following general formulas 27 and 28, provided that R ₁ , R ₂ and When any one of the groups represented by R ₃ is a carboxyl group or an alkyl ester group having 1 to 18 carbon atoms, the other groups are each different from the functional group, and R ₈ , R _9, R ₁₀ and R ₁₁ are the same or different groups There are a hydrogen atom, a halogen atom, a cyano group, a cyanoalkyl group having 2 to 8 carbon atoms, a carboxyl group, an alkyl group having 1 to 10 carbon atoms, an alkyl ether group having 1 to 15 carbon atoms, and a It is one kind selected from a functional group consisting of an aminoalkyl group, an aromatic group having 6 to 32 carbon atoms, and an alkyl ester group having 1 to 18 carbon atoms, provided that R ₈ , R ₉ , R ₁₀ and R _{11 are used.}
In the case where one of the groups is a carboxyl group or an alkyl ester group having 1 to 18 carbon atoms, the other groups are each different from the functional group).

Embedded image

Embedded image Here, R ₅ is a group selected from the groups represented by the following general formulas 29, 30, 31 and 32, and R ₁ , R ₂ and R ₃ have the same meanings as those of the formula 25.

Embedded image

Embedded image

Embedded image

Embedded image (However, R ₆ and R _{7 in} Chemical formulas 29 and 30 may be the same or different groups, and include a hydrogen atom, a halogen atom, a cyano group, a cyanoalkyl group having 2 to 8 carbon atoms, a carbon atom of 1 10 to 10 aminoalkyl group, an aromatic group having 6 to 32 carbon atoms, one group selected from the group represented by the above formula 27 or the group represented by the above formula 28, p is an integer of 1 to 12 Ar in Chemical Formula 7 is a divalent aromatic residue having 6 to 32 carbon atoms, and R _{4 in} Chemical Formula 32 is a group represented by Chemical Formula 27 or a group represented by Chemical Formula 28. Is).

(5) The method according to any one of (1) to (4), wherein the amount of the thermoplastic resin is 1 to 40 parts by weight based on 100 parts by weight of the ammonium polyphosphate-containing substance. Flammable textile products.

(6) The material containing ammonium polyphosphate is coated with at least one resin selected from the group consisting of melamine resin, epoxy resin, phenol resin, urethane resin, urea resin and silicone resin, or melamine monomer, Item 6. The flame-retardant fiber product according to any one of Items 1 to 5, which is an encapsulated or denatured ammonium polyphosphate.

(7) A flame retardant in which an ammonium polyphosphate-containing material coated with a thermoplastic resin is dispersed in a ratio of 10 to 100 parts by weight in 100 parts by weight of a synthetic resin emulsion.

(8) The thermoplastic resin is a homopolymer of a monomer represented by the following formula (1) having 2 to 5 active groups capable of polymerizing in one molecule or a copolymer thereof, or polymerized in one molecule: At least one selected from monomers represented by the following formula having 2 to 5 possible active groups and a monomer selected from the following formula represented by the following formula having one polymerizable active group in one molecule The flameproofing treatment according to claim 7, which is a copolymer with at least one selected from the group consisting of:

Embedded image

Embedded image (In the formula, R ₁ , R _2, and R ₃ are the same or different groups, and each represents a hydrogen atom, a halogen atom, a cyano group, a cyanoalkyl group having 2 to 8 carbon atoms, a carboxyl group, An alkyl group having 10 to 10 carbon atoms, an alkyl ether group having 1 to 15 carbon atoms, an aminoalkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkynyl group having 2 to 12 carbon atoms, and 1 to 18 carbon atoms Wherein R ₄ is one of the groups represented by the following general formulas 35 and 36, provided that R ₁ , R ₂ and When any one of the groups represented by R ₃ is a carboxyl group or an alkyl ester group having 1 to 18 carbon atoms, the other groups are each different from the functional group, and R ₈ , R _9, R ₁₀ and R ₁₁ are the same or different groups There are a hydrogen atom, a halogen atom, a cyano group, a cyanoalkyl group having 2 to 8 carbon atoms, a carboxyl group, an alkyl group having 1 to 10 carbon atoms, an alkyl ether group having 1 to 15 carbon atoms, and a It is one kind selected from a functional group consisting of an aminoalkyl group, an aromatic group having 6 to 32 carbon atoms, and an alkyl ester group having 1 to 18 carbon atoms, provided that R ₈ , R ₉ , R ₁₀ and R _{11 are used.}
In the case where one of the groups is a carboxyl group or an alkyl ester group having 1 to 18 carbon atoms, the other groups are each different from the functional group).

Embedded image

Embedded image Here, R ₅ is a group selected from the groups represented by the following general formulas (37), (38), (39) and (40), and R ₁ , R ₂ and R ₃ have the same meanings as those of the formula (33).

Embedded image

Embedded image

Embedded image

Embedded image (However, R ₆ and R _{7 in} Chemical Formulas 37 and 38 may be the same or different groups, and include a hydrogen atom, a halogen atom, a cyano group, a cyanoalkyl group having 2 to 8 carbon atoms, 10 to 10 are selected from an aminoalkyl group, an aromatic group having 6 to 32 carbon atoms, a group represented by Formula 35 or a group represented by Formula 36, and p is an integer of 1 to 12. Ar in Chemical Formula 39 is a divalent aromatic residue having 6 to 32 carbon atoms, and R _{4 in} Chemical Formula 40 is a group represented by Chemical Formula 35 or a group represented by Chemical Formula 36. Is).

(9) The flameproofing treatment according to the above (7) or (8), wherein the amount of the thermoplastic resin is 1 to 40 parts by weight based on 100 parts by weight of the ammonium polyphosphate-containing substance.

(10) The material containing ammonium polyphosphate is coated with at least one resin selected from the group consisting of a melamine resin, an epoxy resin, a phenol resin, a urethane resin, a urea resin, and a silicone resin, or a melamine monomer. 10. The flameproofing treatment according to any one of the above items 7 to 9, which is an encapsulated or denatured ammonium polyphosphate.

[0018]

BEST MODE FOR CARRYING OUT THE INVENTION The ammonium polyphosphate-containing substance coated with the thermoplastic resin according to the present invention may be used for improving the water solubility of ammonium polyphosphate or in the subsequent step of coating with the thermoplastic resin. In addition, an auxiliary component used for improving the adhesion to the coating film can be contained. Such an auxiliary component may be formed inside or on the surface of the ammonium polyphosphate, by a reaction product with the ammonium polyphosphate, a coating, a microencapsulated substance, a mixture,
It is a water-insoluble component, a poorly water-soluble component, a hydrophobic component or a water-repellent component existing in the form of an adhered or adsorbed substance.

Specific examples of the ammonium polyphosphate-containing substance include a substance containing a triazine derivative such as a melamine monomer and a melamine phosphate in ammonium polyphosphate, a substance coated with ammonium triphosphate with the triazine derivative, and a polyphosphoric acid. Poorly water-soluble ammonium polyphosphate such as a partial reaction product formed by partial reaction of ammonium acid and the triazine derivative, water-insoluble ammonium polyphosphate in which ammonium polyphosphate is coated with a thermosetting resin or microencapsulated, A hydrophobic or water-repellent ammonium polyphosphate in which a surface treatment agent, a surfactant, or a coupling agent is attached or adsorbed on the surface of ammonium polyphosphate.

In the present invention, these substances are collectively referred to as ammonium polyphosphate-containing substances, and the amounts of these triazine derivatives, thermosetting resins, surface treatment agents, surfactants or coupling agents, and other minor components are polyphosphoric acid. It is about 2 to 40% by weight, preferably 3 to 37% by weight, based on the whole ammonium-containing material. Here, the content ratio of ammonium polyphosphate contained in the ammonium polyphosphate-containing substance is preferably such that the proportion of phosphorus in the whole substance in terms of phosphorus concentration is 20 to 31% by weight, more preferably 25 to 31% by weight. 30% by weight (provided that the pure ammonium polyphosphate has a phosphorus concentration of about 32% by weight).

The thermosetting resin used for producing the coated ammonium polyphosphate, which is one of the ammonium polyphosphate-containing substances, includes melamine resin, modified melamine resin, guanamine resin, epoxy resin, phenol resin, urethane resin, urea resin, And silicone resins. The ammonium polyphosphate-containing substance used in the present invention coated or microencapsulated with a thermosetting resin can be obtained, for example, by the following method. That is, untreated ammonium polyphosphate and unmelted melamine resin, modified melamine resin, guanamine resin, epoxy resin, phenolic resin, urethane resin, urea resin, and silicone resin or a mixture thereof in a reaction apparatus, and if necessary, The catalyst can be obtained by an in-liquid curing method in which a catalyst is charged and heated and cured in water, an organic solvent, or a mixed solvent thereof.

In addition, the polymerization conditions are set so that the thermosetting resin generated on the surface of the ammonium polyphosphate particles uniformly surrounds the ammonium polyphosphate, and the raw materials ammonium polyphosphate and ammonium polyphosphate are used. The so-called in-
An in-situ polymerization method, an interfacial polymerization method in which two kinds of reaction components are respectively dissolved in two kinds of solvents which are not mixed with each other to form a thermosetting resin at an interface between both liquid phases,
Coacervation method utilizing the phenomenon of separation of a solvent rich in thermosetting resin in a resin-good solvent-non-solvent system (liquid-liquid phase separation), spraying a thermosetting resin liquid to coat the surface of ammonium polyphosphate After encapsulation with a thermosetting resin, this is brought into contact with hot air to cure the resin and dry the volatile components, and a spray drying method, giving mechanical thermal energy mainly to impact force to the raw material resin,
It can also be obtained by a known method such as a hybridization method of immobilizing or encapsulating on the surface of ammonium polyphosphate particles.

The surface treating agent not only imparts hydrophobicity and water repellency to the ammonium polyphosphate, but also introduces a functional group on the surface of the ammonium polyphosphate particles, so that in the subsequent step of coating the thermoplastic resin, It is a compound that has the effect of strengthening the interaction between the core material, ammonium polyphosphate, and the coating, and providing adhesion. Preferred examples of the surface treatment agent include higher fatty acids,
Coupling agents and surfactants are mentioned, and as the higher fatty acids, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, behenic acid and the like are mentioned.

The coupling agents are represented by the general formula X
_q Silane coupling agent represented by SiY _4-q (however,
q is 1 or 2, and X is a hydrolyzable group such as CH ₃ O
—, C ₂ H ₅ O—, CH ₃ OCH ₂ CH ₂ O—, Cl—, Y represents an alkyl group having 1 to 20 carbon atoms, a vinyl group, an aminoalkyl group having 3 to 6 carbon atoms, and 5 carbon atoms. Glycidoxyalkyl group having 5 to 9 carbon atoms, methacryloxyalkyl group having 5 to 10 carbon atoms, vinylbenzyl group-containing group, chloroalkyl group having 2 to 6 carbon atoms, epoxycyclohexylethyl group, and a combination of these groups. ).

Also, 4-6 coordination titanate coupling agents such as isopropyl triisostearoyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, isopropyl tri (N-aminoethylaminoethyl) titanate, tetraoctyl bis (di -Tridecyl phosphite) titanate, tetra (2,
2-diallyloxymethyl-1-butyl) bis (di-tridecyl) phosphite titanate, bis (dioctylpyrophosphate) oxyacetate titanate, bis (dioxytylpyrophosphate) ethylene titanate,
Isopropyl trioctanoyl titanate, isopropyl dimethacryl isostearyl titanate,

Isopropyl tridodecylbenzenesulfonyl titanate, isopropyl isostearoyl diacryl titanate, isopropyl tri (dioctyl phosphate) titanate, isopropyl tricumyl phenyl titanate, tetraisopropyl bis (dioctyl phosphite) titanate, etc. can also be suitably used in the present invention.
In addition, aluminate-based coupling agents such as acetoalkoxyaluminum diisopropylate, zircoaluminate-based coupling agents, and phosphate-based coupling agents can be suitably used in the present invention.

In the present invention, the above-mentioned surface treating agents can be used in combination in any amount. In the surface treatment method using the surface treatment agent, the surface treatment agent is water,
A wet method of preparing a solution diluted with acetic acid water or a mixed solvent of water and alcohol, and impregnating the surface-treated material with the solution, spraying the surface-treating agent or a solution thereof into the stirred surface-treated material, etc. A publicly known method such as a dry method for adding the above can be used. In the case of a coupling agent, a primer method using a primer obtained by polymerizing the coupling agent alone or reacting with another prepolymer can be used.

Examples of the surfactant include anionic surfactants, cationic surfactants, nonionic surfactants, amphoteric surfactants and fluorine surfactants, and all known surfactants are used. it can. For example, as anionic surfactants, saturated fatty acid salts having 10 to 32 carbon atoms, laurate, myristate, baltimate,
Higher carboxylates such as stearates and oleates, N-acyl-N-methylglycine, N-acyl-N
-Methyl-β-alanine, condensates of higher fatty acids such as N-acylglutamic acid and amino acids and salts thereof, alkyl ether carboxylate, acylated peptide, alkylbenzene sulfonate, alkylnaphthalene sulfonate, naphthalene sulfone Acid salt-formaldehyde polycondensate, dialkyl sulfosuccinate, alkyl sulfoacetate,

Α-olefin sulfonate, N-acylmethyl taurine, funnel oil, higher alcohol sulfate, secondary alcohol sulfate, alkyl ether sulfate, secondary alcohol ethoxy sulfate, polyoxyethylene alkylphenyl Ether sulfate, monoglycol sulfate, fatty acid alkylol amide sulfate, alkyl ether phosphate monoester, alkyl ether phosphate diester, alkyl ether phosphate triester, alkyl phosphate monoester, alkyl phosphate diester Salts, and alkyl phosphate triesters.

As the cationic surfactant, primary, secondary and
Aliphatic amine salts obtained by neutralizing primary and tertiary higher alkylamines having 12 to 54 carbon atoms with inorganic acids such as hydrochloric acid and sulfuric acid or organic acids such as acetic acid, lactic acid and citric acid; Quaternary ammonium salts, bersalkonium salts, benzethonium chloride, alkylpyridinium salts, imidazolinium salts and the like. Examples of the amphoteric surfactant include alkyldimethyl betaine, aminocarboxylate, imidazolinium betaine, and lecithin.

The nonionic surfactants include those having 1 carbon atom
Polyoxyethylene alkyl ether, polyoxyethylene secondary alcohol ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene sterol ether, polyoxyethylene produced by addition polymerization of 2 to 22 aliphatic primary alcohols and ethylene oxide Lanolin derivative, ethylene oxide derivative of alkylphenol formalin condensate, polyoxyethylene polyoxypropylene block polymer,

Polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene glycerin aliphatic ester, polyoxyethylene castor oil, hydrogenated castor oil, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, polyethylene glycol fatty acid ester, fatty acid Monoglyceride, polyglycerin fatty acid ester, sorbitan fatty acid ester, propylene glycol fatty acid ester, sucrose fatty acid ester, fatty acid alkanolamide, polyoxyethylene fatty acid amide, polyoxyethylene alkylamine, alkylamine oxide and the like can be mentioned.

The fluorine-based surfactant is a surfactant having a fluorocarbon or perfluorocarbon in a hydrophobic group, for example, a fluoroalkylcarboxylic acid having an alkyl group having 2 to 10 carbon atoms, N-perfluorooctane. Disodium sulfonylglutamate,
3- (fluoroalkyl (C ₆ -C ₁₁₎ oxy) -1-
Alkyl (C ₃ ~C ₅₎ - sulfonate, sodium 3-
(Ω-fluoroalkanoyl (C ₆ -C ₈ ) -N-ethylamino) -1-propanesulfonic acid sodium salt, N-
[3- (perfluorooctane sulfonamide) propyl] -N, N-dimethyl -N- carboxymethylene ammonium betaine, fluoroalkyl (C ₁₁ -C ₂₀₎ carboxylic acids,

Perfluoroalkyl (C ₇ -C ₁₃ ) carboxylic acid, perfluorooctanesulfonic acid diethanolamide, perfluoroalkyl (C ₄ -C ₁₂ ) sulfonic acid salt, N-propyl-N- (2-hydroxyethyl) perfluorooctane sulfonamide, perfluoroalkyl (C ₆ ~C ₁₀₎ sulfonamide propyl trimethyl ammonium salts, perfluoroalkyl (C ₆ ~C ₁₀₎
-N-ethylsulfonylglycine salt, bisphosphate (N-
Perfluorooctylsulfonyl-N-ethylaminoethyl) and monoperfluoroalkyl (C _6-
C ₁₆ ) ethyl phosphate and the like.

As the ammonium polyphosphate-containing substance used in the present invention, a substance obtained by a production method in a known literature or the like can be used, and a commercially available product can also be used. Examples of the commercially available product include Hostaflam AP-
462 (trade name, manufactured by Hoechst), Sumisafe-PM
(Trade name, manufactured by Sumitomo Chemical Co., Ltd.), Terage (T
ERRAJU) -C30 (trade name, manufactured by Chisso Corporation), Terage (TERRAJU) -C40 (trade name, manufactured by Chisso Corporation), Terage (TERRAJ)
U) -C60 (trade name, manufactured by Chisso Corporation), Terage (TERRAJU) -C70 (trade name, manufactured by Chisso Corporation), and Terage (TERRAJU) -C80
(Trade name, manufactured by Chisso Corporation) or the like may be used.

The thermoplastic resin for coating the ammonium polyphosphate-containing substance used in the present invention is one or more monomers represented by the above formula having 2 to 5 polymerizable active groups in one molecule. Or a monomer having a plurality of the active groups, and a monomer represented by the above formula having one polymerizable active group in one molecule.
It is a copolymer with one or more kinds of monomers. The polymerization reaction or copolymerization reaction is carried out using a polymerization initiator used for a usual radical polymerization reaction. A polymer or copolymer obtained from a monomer containing a monomer having a plurality of the active groups is hardly soluble or almost insoluble in a common organic solvent because it is cross-linked two-dimensionally or three-dimensionally. The ammonium polyphosphate-containing substance coated with the resin has excellent organic solvent resistance.

The monomers having 2 to 5 active groups include 1,2-divinylbenzene, 1,3-divinylbenzene, 1,4-divinylbenzene, 1,2-diallylphthalate, and 1,2-diallylphthalate. 1,4-diallylphthalate, divinyl ether, allyl vinyl ether, propenyl pinyl ether, allyl-α-methyl vinyl ether, butadiene, chloroprene, fluoroprene, cyanoprene, bromoprene, 1,4-pentadiene, 1,5-hexadiene, 1,6 -Heptadiene,
1,7-octadiene, 1,8-nonadiene, 1,9-
Decadien,

1,10-Undecadiene, 1,11-Dodecadiene, 1,12-Oridecadiene, 1,13-Tetradecadiene, 1,17-Octadecadiene, 1,2
1-docosadiene, allene, allene derivative, 2,5-dimethyl-1,5-hexadiene, cis-1,5,9-decatriene, trans-1,3,7-octatriene,
1-vinyl-3-methylenecyclopentane, 2,5-diphenyl-1,5-hexadiene, 2-phenyl-1,
5-hexadiene, 3-methyl-1,5-hexadiene, 3-phenyl-1,5-hexadiene,

3-methyl-4-phenyl-1,5-hexadiene, 3-vinyl-1,5-hexadiene, 2,6
-Diphenyl-1,6-heptadiene, 2,7-diphenyl-1,7-octadiene, 3-phenyl-1,5-
Heptadiene, 2,6-dicarbethoxy-1,6-heptadiene, 2,6-dicarboxy-1,6-heptadiene, 2,6-dicyano-1,6-heptadiene, 4,4
Dicarbethoxy-1,6-heptadiene, 4-acetyl-4-carbethoxy-1,6-heptadiene, 4-carboxy-1,6-heptadiene, 4-acetyl-1,
6-heptadiene,

4,4-diacetyl-1,6-heptadiene, 4-cyano-4-carbethoxy-1,6-heptadiene, 4-cyano-4-carboxy-1,6-heptadiene, 4-cyano-1,6 -Heptadiene, 2,6-dichloro-4,4-dicarbethoxy-1,6-heptadiene, 2,6-dichloro-3-carbethoxy-1,6-heptadiene, 4-allyl-4-hydroxy-1,6-heptadiene , 4-allyl-4-acetoxy-1,6-heptadiene, trans-1,2-divinylcyclobutane, cis-1,2-divinylcyclobutane, trans-
1,2-dimethyl-1,2-divinylcyclobutane, trans-1-isopropenyl-2-vinylcyclobutane, trans-1,2-diisopropenylcyclobutane,

Cis-1,2-divinylcyclopentane,
Cis-1,3-divinylcyclopentane, trans-
1,3-divinylcyclopentane, cis-1,2-divinylcyclohexane, trans-1,2-divinylcyclohexane, cis-1,3-divinylcyclohexane,
Trans-1,3-divinylcyclohexane, trivinylcyclohexane, 1,2,4-trimethylenecyclohexane, 1,3,5-trimethylenecyclohexane,
1,3,5,7-tetramethylenecyclooctane, 1,
4-dimethylenecyclohexane, 1-methylene-4-vinylcyclohexane, divinyl ketone, divinyl acetylene, triallyl isocyanurate,

Triallyl cyanurate, triacryl formal, trimethallyl isocyanurate, diglycidyl bisphenol A diacrylate, dipentaerythryl monohydroxy acrylate, trimethylolpropane triacrylate, neobentyl glycol hydroxypivalate diester Acrylate, 1,4-butanediol diacrylate, 2-pronoic acid [2- [1,1-dimethyl-2-[(1-oxo-2-
Propenyl) oxy] ethyl] -5-ethyl-1,3-
Dioxan-5-yl] methyl ester, pentaerythritol triacrylate,

Trimethylolpropane trimethacrylate, ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, allyl methacrylate, N, N'-methylenebis ( Acrylamide), triallyl trimellitate, 3,9-divinyl-2,4,8,10-tetraoxaspiro [5,5] undecane, and the like.
A combination of two or more types is also possible.

The monomer having one functional group per molecule includes ethylene, propylene, 1-butene,
Isobutylene, 3-methyl-1-butene, 4-methyl-
1-pentene, 1-hexene, 1-octene, 1-decene, styrene, α-methylstyrene, vinyltoluene,
Chlorostyrene, cyanostyrene, aminostyrene, hydroxystyrene, vinylnaphthalene, vinylanthracene, 2-vinylphenanthrene, 3-vinylphenanthrene, acrylonitrile, methacrylonitrile, acrylic acid, methacrylic acid, acrylic ester, methacrylic acid Esters, cyclohexyl methacrylate, benzyl methacrylate, 2-hydroxyethyl methacrylate,

2-hydroxypropyl methacrylate, methylaminoethyl methacrylate, diethylaminoethyl methacrylate, glycidyl methacrylate, tetrahydrofurfuryl methacrylate, α-cyanoacrylate, α-halogenoacrylate, acrylamide, methacrylamide, Diacetone acrylamide,
Allyl chloride, allyl alcohol, allyl amine, allyl acetone, allyl aldehyde, allyl ester, allyl methyl ether, allyl ethyl ether, allyl carbamide, allyl glycerin, allyl acetic acid, allyl thio alcohol, allyl thiocarbamide, allyl thiocarbimide, allyl thiourea , Allyl urea, vinyl chloride, vinylidene chloride, vinyl bromide, vinyl fluoride, fuvinylidene, fluorostyrene, vinyl acetate, vinyl laurate, vinyl salicylate,

Methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, n-hexyl vinyl ether, n-octyl vinyl ether, phenyl vinyl ether, o-cresyl vinyl ether, p-cresyl vinyl ether,
p-chlorophenyl vinyl ether, α-naphthyl vinyl ether, β-naphthyl vinyl ether, 1-buten-3-one, acrylophenone, 2-vinylpyridine,
And 4-vinylpyridine, 2-methyl-5-vinylpyridine and the like, and two or more of them can be used in combination.

In the present invention, the coating ratio of the thermoplastic resin obtained from the monomer to the ammonium polyphosphate-containing material is 10%.
The ratio is 1 to 40 parts by weight, preferably 5 to 20 parts by weight with respect to 0 parts by weight.

The method for producing the thermoplastic polyammonium-containing material used in the present invention will be described in detail below. In a reaction vessel having a function of heating and stirring or kneading, 100 to 100 parts by weight of an ammonium polyphosphate-containing substance, 0.1 to 40 parts by weight of a monomer having 2 to 5 functional groups represented by the above formula in one molecule Parts, optionally 0.1 to 39.9 parts by weight of a monomer having one functional group represented by the above formula in one molecule, and 0.1 part of a polymerization initiator.
1 to 10 parts by weight are charged and mixed. At this time, the solvent is 1
The solvent may be used in an amount of 0 to 500 parts by weight, and a single solvent or a mixed solvent composed of water or an organic solvent can be used as the solvent.

The polymerization initiator used is generally an organic peroxide such as benzoyl peroxide, acetyl peroxide, t-butyl hydroperoxide, cumene hydroperoxide, di-t-butyl peroxide, Lauroyl peroxide, dimethyl α, α'-azodiisobutyrate, succinic peroxide, dicumene peroxide, dichlorobenzoyl peroxide, and inorganic peroxides such as potassium persulfate, ammonium persulfate, hydrogen peroxide, and perboric acid Examples include sodium and the like, and azo compounds such as α, α'-azodiisobutyronitrile, azodicyclohexylcarbonitrile, and phenylazotriphenylmethane, and all commercially available products can be used.

Next, the mixture in the reaction vessel was heated to a temperature of 20-200.
A polymer cross-linked to the particle surface of a substance containing ammonium polyphosphate as a main component by heating and stirring at 150 ° C., preferably 50 to 100 ° C., and allowing the reaction to complete for a period of time, for example, 0.5 to 50 hours. Is formed, and an ammonium polyphosphate-containing substance coated with the thermoplastic resin used in the present invention is obtained.

The textile products used in the present invention include cotton,
Natural organic fibers such as cotton, kapok, flax, ramie, jute, green hemp, hemp, bow hemp, manila hemp, sisal hemp, mage, malaon, wool, and silk; viscose fibers such as rayon, strong rayon, polynosic, Cellulose semi-synthetic fiber such as acetate, polyester fiber,
Synthetic fibers such as polypropylene fiber, polyethylene fiber, nylon fiber, acrylic fiber, vinylon fiber, and polyclar fiber, para-aramid fiber, meta-aramid fiber, heat-resistant synthetic pulp, wholly aromatic polyester fiber, polyvinyl alcohol fiber, and polyacrylonitrile fiber , Phenol fiber, polyphenylsulfone fiber (P
PS) fibers and high-performance fibers such as polyimide fibers, and further, a fiber product called a fabric, a base fabric, a nonwoven fabric, a felt, or a fabric produced alone or in combination of a plurality thereof.

In the present invention, there is no particular limitation on the method for obtaining a fiber product called fabric, base fabric, nonwoven fabric, felt, or fabric, which is produced by using the above-mentioned fibers alone or in combination of a plurality thereof. A known method such as a water needle method, a stitch bond method, a resin bonded nonwoven fabric method, a spun bond method, a resin mixed felt method, and a melt blow method can be applied.

The synthetic resin of the synthetic resin emulsion used in the present invention is mainly composed of 2-ethylhexyl acrylate, butyl acrylate, methyl acrylate and methyl methacrylate, and is copolymerized with acrylic acid, methacrylic acid, acrylonitrile, styrene and the like. Methylol acrylamide, glycidyl methacrylate, allylaminodichlorotriazine, acrylate-based resin with a cross-linking group such as monochlorovinyl acetate,
Mixtures of polyols such as polyether polyols, polyester polyols, polymer polyols and / or polyamines are used as the first component and an average of 2
A urethane-based resin obtained by reaction-curing a polyisocyanate containing two or more terminal isocyanate groups as a second component, polyvinyl acetate, vinyl acetate-ethylene copolymer, vinyl acetate-vinyl propionate copolymer,
Vinyl acetate-based resin obtained by polymerizing vinyl acetate-acrylate copolymer, and aliphatic, aromatic, cyclic,
In addition to commonly used epoxy resins such as acyclic, alicyclic and heterocyclic resins, vinyl chloride resins, vinylidene chloride resins and polyvinyl alcohol resins can be suitably used.

The synthetic resin emulsion contains water and the above-mentioned synthetic resin, and the above-mentioned synthetic resin in the synthetic resin emulsion is 5 to 60% by weight in terms of solid content, preferably 10 to 5% by weight.
0% by weight, and 0.1 to 5% by weight, preferably 1 to 3% by weight of an emulsifier, to which an arbitrary amount of a surfactant such as a cationic, anionic or nonionic surfactant, a softening agent, an antistatic agent, Polishing agents, antibacterial agents, water / oil repellents, defoamers,
It is prepared by appropriately mixing a dye, a pigment and the like. For 100 parts by weight of the solid content of the synthetic resin emulsion, an ammonium polyphosphate-containing substance 10-2 coated with a thermoplastic resin.
00 parts by weight, preferably 50 to 150 parts by weight, are mixed and dispersed to obtain a flameproofing agent. At this time, in order to further improve the flame retardancy, known flame retardants, for example, phosphate esters,
Chlorinated phosphate, condensed phosphate, red phosphorus,
Coated red phosphorus, aluminum hydroxide, magnesium hydroxide,
Alternatively, expandable graphite or the like can be appropriately blended.

As a method for obtaining a flame-retardant fiber product according to the present invention, a flame-retardant treating agent in which an ammonium polyphosphate-containing substance coated with a thermoplastic resin is dispersed in a synthetic resin emulsion is applied to the above-mentioned fiber product. , Spraying, impregnation, backing and the like, and drying and / or curing. At this time, the amount of-proof flame treatment agent 10 to 500 parts per said textile 1 m ^2, preferably 50 to 200
Department.

[0056]

The present invention will be described in more detail with reference to the following Examples and Comparative Examples, which by no means limit the scope of the present invention. The evaluation in Examples and Comparative Examples was performed by the following method. (1) Flame retardancy test Based on JIS D1201. The size of the test piece is length 3
It was 50 mm x 100 mm in width, and the thickness was used as it was. Those having a burning rate (mm / min) of more than 100 were regarded as flammable, those having a burning rate of 100 or less as slow burning, and those extinguished before the test piece burned out were regarded as self-extinguishing. (2) Flame retardancy test after water resistance test The test pieces obtained in each of Examples and Comparative Examples were immersed in boiling water for 5 minutes, dried at 80 ° C for 2 hours, and then left in a desiccator at room temperature for 12 hours. Then, the flame retardancy test (1) was performed.

Further, the ammonium polyphosphate-containing material coated with the thermoplastic resin used in each of the examples and comparative examples of the present invention was produced as follows. In a 500 ml reactor equipped with a stirrer, thermometer, reflux condenser and inlet, 100 parts by weight of ammonium polyphosphate microencapsulated with melamine resin, 7 parts by weight of styrene monomer, 3 parts by weight of divinylbenzene, 2 parts by weight of potassium persulfate, 200 parts by weight of water and 50 parts by weight of methanol were charged and mixed at room temperature. Then temperature 80
C., and reacted at the same temperature for 6 hours. After cooling the reaction solution, filtration, washing with water and drying were performed to obtain 110 parts by weight of the coated ammonium polyphosphate.

Here, ammonium polyphosphate microencapsulated with the melamine resin was obtained as follows. In a 5-liter flask having a heating and stirring function and a reflux function, water of 1000 g of melamine monomer-coated ammonium polyphosphate and 12% methanol concentration was added.
2000 g of methanol solution, 35% formalin concentration 12
2 g was added, heated, and reacted at a reflux temperature for 1 hour. Then, the mixture was rapidly cooled to 30 to 40 ° C., filtered, washed repeatedly with a 12% aqueous methanol solution, and dried in an oven set at 100 ° C. to obtain 990 g of ammonium polyphosphate microencapsulated with a melamine resin.

Here, the melamine monomer-coated ammonium polyphosphate was treated using the following procedure. A powdered ammonium polyphosphate 200 was placed in a biaxial tabletop kneader having a volume of 5 L, which was previously heated to 280 to 320 ° C.
0 parts were charged, and nitrogen gas or inert gas was ventilated.
The mixture was heated and mixed for a period of time to remove ammonia from ammonium polyphosphate. Then melamine 11 into the kneader
0 part was added, the upper lid of the kneader was closed, the inside of the reactor was sealed, and the mixture was heated and stirred at 260 to 300 ° C. for 5 hours.
Thus, 2100 parts of melamine monomer-coated ammonium polyphosphate was obtained.

[0060]

Example 1 As a synthetic resin emulsion, a solid content of 47% by weight containing an anionic surfactant and a viscosity of 3000 were used.
cps acrylic emulsion AA-80 (trade name,
100 parts by weight of Kanebo NS Co., Ltd.) was mixed well with 50 parts by weight of an ammonium polyphosphate-containing substance coated with a thermoplastic resin to obtain a flameproofing agent. After using a 100% polyester cloth for a textile product as a base material and applying the flameproofing agent with a spatula, squeeze with a roll linear pressure of 25 kg / cm ² using a roll squeezing machine.
After drying at 80 ° C. for 3 hours, a flame-retardant fiber product was obtained. The flame-retardant fiber product was cut into a predetermined size and subjected to various tests. The results are shown in Table 1.

[0061]

Example 2 As a synthetic resin emulsion, a solid content concentration of 33% by weight containing an anionic surfactant and a viscosity of 500 c
100 parts by weight of a urethane emulsion GC-52 (trade name, manufactured by Kanebo NS Co., Ltd.), 30 parts by weight of an ammonium polyphosphate-containing substance coated with a thermoplastic resin, and a phosphate ester (CR-733S,
3 parts by weight of Daihachi Chemical Co., Ltd.) and 1 part by weight of a sodium acrylate thickener were mixed well to obtain a flameproofing agent. A 100% acrylic cloth is used for a textile product as a base material, and the cloth is sufficiently immersed in the flameproofing agent contained in an appropriate container.
cm ² and dried at 80 ° C. for 3 hours to obtain a flame-retardant fiber product. The flame-retardant fiber product was cut into a predetermined size and subjected to various tests. The results are shown in Table 1.

[0062]

Example 3 A flame-retardant fiber product was obtained in the same manner as in Example 1 except that 100% rayon cloth was used as the base fabric. The flame-retardant fiber product was cut into a predetermined size and subjected to various tests. The results are shown in Table 1.

[0063]

Embodiment 4 The warp yarn is 100% cotton as the base fabric.
%, Weft 40% acrylic, 25% polyester, cotton 2
A flame-retardant fiber product was obtained according to Example 2, except that a blended fabric of 0% and 15% of nylon was used. The flame-retardant fiber product was cut into a predetermined size and subjected to various tests. The results are shown in Table 1.

[0064]

[Comparative Example 1] Instead of an ammonium polyphosphate-containing substance coated with a thermoplastic resin, Hostafram AP422, which is an ammonium polyphosphate not coated, was used.
Example 1 except that (trade name, manufactured by Clariant) was used.
A flame-retardant fiber product was obtained according to. The flame-retardant fiber product was cut into a predetermined size and subjected to various tests. The results are shown in Table 1.

[0065]

Comparative Example 2 In accordance with Example 2, except that Sumisafe PM (trade name, manufactured by Sumitomo Chemical Co., Ltd.), which is a melamine-modified ammonium polyphosphate, was used instead of the ammonium polyphosphate-containing substance coated with the thermoplastic resin. As a result, a flame-retardant fiber product was obtained. The flame-retardant fiber product was cut into a predetermined size and subjected to various tests. The results are shown in Table 1.

[0066]

[Table 1]

[0067]

Comparative Example 3 A flame-retardant fiber product was obtained according to Example 1, except that 20 parts by weight of trisdichloropropylphosphate was used instead of the ammonium polyphosphate-containing substance coated with the thermoplastic resin. The fabric was cut into a predetermined size and subjected to various tests.

[0068]

The flame-retardant fiber product of the present invention has high flame retardancy and exhibits excellent water resistance. Therefore, clothing,
It can be suitably used for bedding, wallpaper, building materials, and interior materials such as automobiles, aircraft, railways and ships, especially for seat covers, floor mats, and carpets.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI theme coat ゛ (Reference) C08L 31/04 C08L 31/04 A 33/08 33/08 63/00 63/00 C 75/04 75 / 04 101/00 101/00 C09C 3/10 C09C 3/10 C09K 21/04 C09K 21/04 D06M 11/71 D06M 13/313 13/313 11/08 F term (reference) 4H028 AA07 AB02 BA04 4J002 BD041 BD101 BE021 BF021 BF031 BG041 CD001 CK021 DH056 EU187 FB266 FB286 FD310 GK02 HA07 4J037 AA08 CB19 CC11 CC12 CC13 CC14 CC15 CC16 CC17 CC22 CC23 CC26 CC28 CC29 EE03 FF30 4L031 BA18 CA11 DA16 4L033 AC05 CA59 CA18 CA05 CA59 CA18 CA05 CA29

Claims (10)

[Claims] (1) A flame-retardant fiber product comprising a fiber product containing an ammonium polyphosphate-containing substance coated with a thermoplastic resin in an amount of 3 to 50% by weight of the total weight on a dry weight basis. 2. A fiber product obtained by treating a synthetic resin emulsion with 100 parts by weight of a thermoplastic resin-coated ammonium polyphosphate-containing material dispersed in a proportion of 10 to 100 parts by weight. Flame retardant textile products. 3. The synthetic resin emulsion is one selected from the group consisting of acrylic ester emulsions, urethane emulsions, epoxy emulsions, vinyl acetate emulsions, vinyl chloride emulsions, vinylidene chloride emulsions, and polyvinyl alcohol emulsions. The flame-retardant fiber product according to claim 2, which is the above. 4. The thermoplastic resin according to claim 1, wherein the thermoplastic resin has 2 to 5 polymerizable active groups in one molecule, a homopolymer or a copolymer thereof, or a polymerizable monomer in one molecule. At least one selected from monomers represented by the following formula 1 having 2 to 5 active groups, and a monomer represented by the following formula 2 having one polymerizable active group in one molecule. The flame-retardant fiber product according to any one of claims 1 to 3, which is a copolymer with at least one of the above. Embedded image Embedded image (Wherein R ₁ , R ₂ and R ₃ are the same or different groups, and each represents a hydrogen atom, a halogen atom, a cyano group,
C2-C8 cyanoalkyl group, carboxyl group, C1-C10 alkyl group, C1-C15 alkyl ether group, C1-C10 aminoalkyl group, C2-C12 alkenyl group Wherein R ₄ is one selected from the group consisting of a functional group consisting of an alkynyl group having 2 to 12 carbon atoms and an alkyl ester group having 1 to 18 carbon atoms; One of the groups. However, when any one of the groups R ₁ , R ₂ and R ₃ is a carboxyl group or an alkyl ester group having 1 to 18 carbon atoms, the other groups are different from the functional groups, respectively. In the formula 2, R ₈ , R ₉ , R ₁₀ and R ₁₁ are the same or different groups, and each is a hydrogen atom, a halogen atom, a cyano group, a cyanoalkyl group having 2 to 8 carbon atoms, a carboxyl group, a carbon number. An alkyl group having 1 to 10 carbon atoms, an alkyl ether group having 1 to 15 carbon atoms, an aminoalkyl group having 1 to 10 carbon atoms, an aromatic group having 6 to 32 carbon atoms, and 1 to 18 carbon atoms
1 selected from a group of functional groups consisting of an alkyl ester group of
Is a seed. However, when any one of the groups R ₈ , R ₉ , R ₁₀ and R ₁₁ is a carboxyl group or an alkyl ester group having 1 to 18 carbon atoms, each of the other groups is different from the functional group. is there). Embedded image Embedded image Here, R ₅ is represented by the following general formula 5, 6, 7 or 8
Wherein R ₁ , R ₂ and R ₃ have the same meanings as in the group of formula 1. Embedded image Embedded image Embedded image Embedded image (However, R ₆ and R _{7 in} Chemical Formulas 5 and 6 may be the same or different groups, and include a hydrogen atom, a halogen atom,
Cyano group, cyanoalkyl group having 2 to 8 carbon atoms, 1 carbon atom
10 to 10 aminoalkyl group, an aromatic group having 6 to 32 carbon atoms, one group selected from the group represented by the above formula 3 or the group represented by the above formula 4, and p is an integer of 1 to 12 is there. Ar in Chemical Formula 7 is a divalent aromatic residue having 6 to 32 carbon atoms, and R _{4 in} Chemical Formula 8 is a group represented by Chemical Formula 3 or a group represented by Chemical Formula 4. ). 5. The flame-retardant fiber product according to claim 1, wherein the amount of the thermoplastic resin is 1 to 40 parts by weight based on 100 parts by weight of the ammonium polyphosphate-containing substance. . 6. A microcapsule comprising an ammonium polyphosphate-containing substance coated with at least one resin selected from the group consisting of a melamine resin, an epoxy resin, a phenol resin, a urethane resin, a urea resin, and a silicone resin, or a melamine monomer. The flame-retardant fiber product according to any one of claims 1 to 5, which is a modified or modified ammonium polyphosphate. 7. A flameproofing agent comprising an ammonium polyphosphate-containing substance coated with a thermoplastic resin dispersed in a proportion of 10 to 100 parts by weight in 100 parts by weight of a synthetic resin emulsion. 8. The thermoplastic resin is a homopolymer or a copolymer of a monomer represented by the following formula (1) having 2 to 5 active groups capable of polymerizing in one molecule, or polymerizable in one molecule. At least one selected from monomers represented by the following formula 9 having 2 to 5 active groups, and a monomer represented by the following formula 10 having one polymerizable active group in one molecule. The flameproofing treatment according to claim 7, which is a copolymer with at least one of the above. Embedded image Embedded image (Wherein R ₁ , R ₂ and R ₃ are the same or different groups, and each represents a hydrogen atom, a halogen atom, a cyano group,
C2-C8 cyanoalkyl group, carboxyl group, C1-C10 alkyl group, C1-C15 alkyl ether group, C1-C10 aminoalkyl group, C2-C12 alkenyl group , An alkyl alkynyl group having 2 to 12 carbon atoms, and an alkyl ester group having 1 to 18 carbon atoms, wherein R ₄ is a group represented by the following general formula 11 or 12 One of the groups. However, when any one of the groups R ₁ , R ₂ and R ₃ is a carboxyl group or an alkyl ester group having 1 to 18 carbon atoms, the other groups are different from the functional groups, respectively. In the formula (10), R ₈ , R ₉ , R ₁₀ and R ₁₁ are the same or different groups, and each is a hydrogen atom, a halogen atom, a cyano group, a cyanoalkyl group having 2 to 8 carbon atoms, a carboxyl group, a carbon number. 1 to 10 alkyl groups, 1 to 1 carbon atoms
An alkyl ether group having 15 carbon atoms, an aminoalkyl group having 1 to 10 carbon atoms, an aromatic group having 6 to 32 carbon atoms, and 1
It is one kind selected from a functional group consisting of -18 alkyl ester groups. However, any one of the groups R ₈ , R ₉ , R ₁₀ and R ₁₁ is a carboxyl group or a group having 1 to 18 carbon atoms.
In the case of the alkyl ester group, the other groups are each different from the functional group). Embedded image Embedded image Here, R ₅ is a group selected from the groups represented by the following general formulas 13, 14, 15, and 16, and R ₁ , R _2, and R ₃ have the same meanings as those of the formula 1. Embedded image Embedded image Embedded image Embedded image (However, R ₆ and R _{7 in} Chemical Formulas 13 and 14 may be the same or different groups, and may be a hydrogen atom, a halogen atom, a cyano group, a cyanoalkyl group having 2 to 8 carbon atoms, 10 to an aminoalkyl group, an aromatic group having 6 to 32 carbon atoms, one selected from the group represented by the above formula 11 or the group represented by the above formula 12, and p is an integer of 1 to 12. Ar in Chemical Formula 15 is a divalent aromatic residue having 6 to 32 carbon atoms, and R _{4 in} Chemical Formula 16 is a group represented by Chemical Formula 11 or a group represented by Chemical Formula 12. Is). 9. The flameproofing treatment according to claim 7, wherein the amount of the thermoplastic resin is 1 to 40 parts by weight based on 100 parts by weight of the ammonium polyphosphate-containing substance. 10. A microcapsule, wherein the substance containing ammonium polyphosphate is coated with at least one resin selected from the group consisting of melamine resin, epoxy resin, phenol resin, urethane resin, urea resin and silicone resin, or melamine monomer. The flameproofing treatment according to any one of claims 7 to 9, which is a modified or modified ammonium polyphosphate.