JP2014141598A - Flame-retardant coating agents, and method of producing flame-retardant sheet materials - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide flame-retardant coating agents which can provide flame-retardant sheet materials excellent in flame retardancy and feeling and reduced in strike-through and hot water spot generation, without using halogen compounds or antimony compounds; and a method of producing flame-retardant sheet materials.SOLUTION: A flame-retardant coating agent comprises: at least one compound (A) selected from the group consisting of cyclic and linear phosphazene compounds represented by the specified general formula (1); a phosphorus compound (B); an alkali thickening acrylic resin (C); a self-emulsifying aqueous polyurethane resin (D) having an anionic group; and water (E).

Description

  The present invention relates to a flame retardant coating agent and a method for producing a flame retardant sheet material treated with the coating agent.

  Conventionally, vehicle seat materials such as automobile seat materials and railcar seat materials; furniture and interior seat materials such as chair upholstery materials; flame retardants for industrial materials such as wall materials and building seat materials such as tents As metal oxides such as halogen flame retardants and antimony oxide are treated with resin compounds. However, these sheet materials generate dioxins, dioxin analogues, and formaldehyde during incineration, which may adversely affect the environment.

  In order to solve such a problem, in Japanese Patent Application Laid-Open No. 2006-233152 (Patent Document 1), an acrylic copolymer resin containing no methylol group in an acrylic monomer on one surface of a fabric, an ammonium polyphosphate salt A flame retardant fabric having a back coating layer composed of a back coating agent containing a phosphate ester and a thickener in a specific ratio and having a formaldehyde generation amount of 0.1 ppm or less is disclosed.

  Japanese Patent Application Laid-Open No. 2007-016357 (Patent Document 2) is excellent in flame retardancy, light resistance, and abrasion resistance, has no occurrence of stickiness, and has a flame retardant suede tone treated with a non-halogen flame retardant. As artificial leather, a phosphoric acid compound A having a solubility in water of 1% or less on one side of a thermoplastic synthetic fiber fabric made of a woven fabric, a knitted fabric or a nonwoven fabric having raised or raised surfaces and impregnated with a polyurethane resin, and at the time of combustion A suede-like artificial leather excellent in flame retardancy, to which a flame retardant processing agent comprising a composition containing a vinyl group-containing resin C capable of forming a carbonized skeleton and a water-insoluble thickener D, is disclosed.

  However, the polyphosphate ammonium salt used in Patent Document 1 and the condensed ammonium phosphate that is a phosphoric acid compound used in Patent Document 2 have increased solubility in water as the water temperature increases. It is difficult to suppress the occurrence of cracks in water, particularly hot water of 80 ° C. or higher. Furthermore, there is a problem that ammonium polyphosphate salt or condensed ammonium phosphate dissolved in water decomposes with time and causes pH change of the coating agent. In addition, the acrylic copolymer resin used in Patent Document 1 and the vinyl group-containing resin used in Patent Document 2 have a drawback in that the flame retardance is greatly inhibited.

  In Japanese Patent Application Laid-Open No. 2005-226212 (Patent Document 3), a flame retardant comprising a mixture in which a phosphorus compound, a metal hydroxide, a phosphate ester and a thermoplastic resin are blended at a specific ratio on at least one surface of a metal-coated fabric. By forming a protective coating, it is highly flexible and flexible without significantly degrading the original conductivity of the metal and the electromagnetic shielding properties inherent to the metal-coated fabric, without using a halogen compound or an antimony compound. It is disclosed that a flame-retardant metal-coated cloth (electromagnetic wave shielding material) having a texture can be obtained.

  However, in the method described in Patent Document 3, since an organic solvent is used as a solvent for dissolving or dispersing various raw materials, a back-through occurs, and a flame-retardant coating agent is used for the purpose of preventing the back-through. It is necessary to perform a sealing process before coating, and the processing process becomes complicated. Moreover, since it is a solvent system, there is a risk of adversely affecting the environment.

  In JP2007-297757A (Patent Document 4), 5 or 300 parts by weight of one or more specific phosphinic acid salts having little solubility in water and not containing VOC such as formaldehyde are used. A processing method is disclosed that can solve problems such as tightness, slippage, washing resistance, and VOC by using 100 parts by weight of a synthetic resin emulsion or solution containing no halogen or VOC.

  However, although the phosphinic acid salt described in Patent Document 4 exhibits good flame retardancy, it has a large decrease in texture and poor compatibility with the resin component, so that it is stable when blended with a coating agent. There is also the problem of getting worse.

JP 2006-233152 A JP 2007-016357 A JP-A-2005-226212 JP 2007-297757 A

  The present invention has been made in view of such a current situation, and is excellent in flame retardancy and texture without using a halogen compound or an antimony compound, and suppresses the occurrence of cracking through and cracking of hot water. A flame retardant sheet material is provided.

  In particular, the present invention is used for industrial flame retardant materials such as vehicle seat materials, furniture / interior sheet materials, and architectural sheet materials, and in particular halogen-based flame retardants such as bromine and chlorine, which are of concern for the natural environment. A flame retardant coating agent that can provide a flame retardant sheet material that is excellent in flame retardancy and texture, and that suppresses the occurrence of back-through and sticking to hot water, and is treated with this coating agent. The present invention relates to a method for producing a flame retardant sheet material.

  Here, the back-through is a phenomenon in which, when a coating agent is processed on one surface of a sheet material, the sheet material penetrates to the other surface and deteriorates the quality of the sheet material.

  The tightness is a phenomenon in which when water or steam adheres to the processed sheet material and then dried, the part to which water or steam adheres becomes a spot or ring stain. As the temperature of adhering water or steam rises, the solubility of the components contained in the sheet material in water tends to increase, and the stickiness tends to deteriorate.

  As a result of intensive studies to solve the above problems, the present inventors have found that a flame retardant coating agent containing a specific phosphazene compound, a specific phosphorus compound, a specific thickener, and a specific urethane resin, By treating one side of the material and then drying to form a flame retardant coating on the treated surface of the sheet material and / or in the sheet material, it is excellent in flame retardancy and texture, through-through and heat The present inventors have found that a flame-retardant sheet material in which the occurrence of sticking to water is suppressed is obtained, and the present invention has been completed based on this finding.

  Therefore, the present invention is represented by at least one compound (A) selected from the group consisting of phosphazene compounds represented by the following general formulas (1) and (2), and the following general formulas (3) to (6). At least one compound (B) selected from the group consisting of phosphorus compounds, an alkali-thickened acrylic resin (C), a self-emulsifiable aqueous polyurethane resin (D) having an anionic group, and water (E And a flame retardant coating agent.

(In the above formula, X ¹ and X ² each independently have an alkyloxy group having 1 to 18 carbon atoms, an alkenyloxy group having 2 to 18 carbon atoms, or an alkyl group having 1 to 4 carbon atoms. Represents an aryloxy group having 6 to 14 carbon atoms, and m represents an integer of 3 to 25)

(In the above formula, X ¹ and X ² each independently have an alkyloxy group having 1 to 18 carbon atoms, an alkenyloxy group having 2 to 18 carbon atoms, or an alkyl group having 1 to 4 carbon atoms. Represents an aryloxy group having 6 to 14 carbon atoms, Y represents an (X ¹ or X ² ) ₃ P═N— group, or an (X ¹ or X ² ) (O) P═N— group, and Z Represents (X ¹ or X ² ) ₄ P-group or (X ¹ or X ² ) ₂ (O) P- group, and n represents an integer of 3 to 1000)

(In the above formula, R ¹ and R ² may each independently have a phenyl group optionally having an alkyl group having 1 to 4 carbon atoms, or an alkyl group having 1 to 4 carbon atoms. Represents a naphthyl group, E represents a direct bond, —O— or —N (H) —, a represents 1 or 2, and b represents 0 or 1.

(In the above formula, R ³ represents a benzyl group, a methylbenzyl group, a phenethyl group, a naphthylmethyl group, or a group represented by the following formula (7)).

(In the above formula, R ⁴ represents an alkyl group having 1 to 10 carbon atoms, a phenyl group, or a benzyl group)

(In the above formula, R ^{5 to} R ⁸ each independently represent a phenyl group having an alkyl group having 1 to 4 carbon atoms, R ⁹ represents an arylene group which may have a substituent, and c represents Represents an integer of 1 to 5)

(In the above formula, R ¹⁰ and R ¹¹ each independently represents an alkyl group having 1 to 4 carbon atoms,
R ¹² represents a biphenyl group or a naphthyl group)

  In the flame-retardant coating agent of the present invention, the alkali thickening acrylic resin (C) includes a monomer composition containing at least one monomer selected from the group consisting of a carboxyl group-containing monomer and a (meth) acrylic acid ester monomer. It is preferable that it is a polymer of a product.

  The self-emulsifiable aqueous polyurethane resin (D) having an anionic group reacts with (a) a polyisocyanate, (b) a polyol, and (c) a compound having an anionic group and two or more active hydrogens. The resulting isocyanate group-terminated prepolymer neutralized product having an anionic group is emulsified and dispersed in water by self-emulsification, and (d) chain extension using a polyamine compound having two or more amino groups and / or imino groups. An aqueous polyurethane resin having an anionic group obtained by reacting is preferable.

  The blending ratio (A) :( B) of the phosphazene compound (A), phosphorus compound (B), alkali-thickened acrylic resin (C) and self-emulsifiable aqueous polyurethane resin (D) having an anionic group: (C) :( D) is preferably in a mass ratio of 20-200: 10-250: 0.5-25: 100.

  In the present invention, the flame retardant coating agent of the present invention is treated on one side of the sheet material and then dried, so that the phosphazene compound (A) is added to the treated surface of the sheet material and / or in the sheet material. A flame retardant sheet material is obtained by forming a flame retardant film containing a phosphorus compound (B), an alkali-thickened acrylic resin (C) and a self-emulsifiable aqueous polyurethane resin (D) having an anionic group A method for producing a flame-retardant sheet material is provided.

  According to the present invention, there is provided a flame retardant sheet material that is excellent in flame retardancy and texture without using a halogen compound or an antimony compound, and that suppresses occurrence of cracking through and cracking against hot water. be able to.

Hereinafter, the present invention will be described in detail.
Phosphazene compound (A)
The phosphazene compound (A) used in the present invention is a conventionally known linear or cyclic phosphazene compound that can be used as a flame retardant. The general formulas (1) and (2) And at least one selected from the group consisting of compounds represented by:
These phosphazene compounds can be used singly or in combination of two or more.

In the general formulas (1) and (2), X ¹ and X ² are alkyloxy having 4 to 18 carbon atoms from the viewpoint of flame retardancy, tightness, haze, and fastness of the obtained flame retardant sheet material. Group or an aryloxy group having 6 to 14 carbon atoms which may have an alkyl group having 1 to 4 carbon atoms, and more preferably a phenyloxy group. m is preferably 3 to 10 in view of ease of production of the phosphazene compound. Moreover, n is preferably 3 to 100 in view of the ease of producing the phosphazene compound.

Phosphorus compound (B)
The phosphorus compound (B) used in the present invention can give the flame retardancy and flexibility improvement effect of the formed flame retardant coating by using in combination with the phosphazene compound (A). And at least one selected from the compounds represented by the general formulas (3) to (6).
These phosphorus compounds can be used individually by 1 type or in combination of 2 or more types.

Examples of the phosphorus compound represented by the general formula (3) include triphenyl phosphate, 1-naphthyl diphenyl phosphate, 2-naphthyl diphenyl phosphate, di (1-naphthyl) phenyl phosphate, di (2-naphthyl) phenyl phosphate, 1-naphthyl-2-naphthylphenyl phosphate, trinaphthyl phosphate, triparacresyl phosphate, tri-2,6-xylenyl phosphate, phenoxyethyl diphenyl phosphate, di (phenoxyethyl) phenyl phosphate, phenoxyethyl dinaphthyl phosphate, di (Phenoxyethyl) naphthyl phosphate, naphthoxyethyl diphenyl phosphate, di (naphthoxyethyl) phenyl phosphate, naphthoxyethyl dinaphthyl phosphate, di (naphth Kishiechiru) naphthyl phosphate, anilino diphenyl phosphate, dianilinopyrimidine phenyl phosphate, trianilino phosphate, and the like triphenyl phosphine oxide. These compounds can be used alone or in combination of two or more.
Among these, it is preferable to use phenoxyethyl diphenyl phosphate from the viewpoint of flame retardancy.

Examples of the phosphorus compound represented by the general formula (4) include 10-benzyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (4-methylbenzyl) -9. , 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-phenethyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (1-naphthylmethyl) ) -9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (2-naphthylmethyl) -9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide , Butyl [3- (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide-1 -Yl) methyl] succinimide, phenyl [3- (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide-10-yl) methyl] succinimide, benzyl [3- (9,10-dihydro -9-oxa-10-phosphaphenanthrene-10-oxide-10-yl) methyl] succinimide and the like. These compounds can be used alone or in combination of two or more.
Among these, it is preferable to use 10-benzyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide from the viewpoint of flame retardancy.

In the general formula (5), the arylene group represented by R ⁹ may have a substituent, and examples of the substituent include an alkyl group having 1 to 4 carbon atoms and a hydroxy group. Examples of the arylene group include a phenylene group, a biphenylene group, a methylene bisphenylene group, a dimethylmethylene bisphenylene group, and a sulfone bisphenylene group.

Examples of the phosphorus compound represented by the general formula (5) include resorcinol di-2,6-xylenyl phosphate, hydroquinone di-2,6-xylenyl phosphate, 4,4′-biphenol di-2, Examples include 6-xylenyl phosphate. These compounds can be used alone or in combination of two or more.
Among these, it is preferable to use resorcinol di-2,6-xylenyl phosphate from the viewpoint of flame retardancy.

Examples of the phosphorus compound represented by the general formula (6) include 5,5-dimethyl-2- (2′-phenylphenoxy) -1,3,2-dioxaphosphorinane-2-oxide, 5,5 -Dimethyl-2- (4'-phenylphenoxy) -1,3,2-dioxaphosphorinane-2-oxide, 5-butyl-5-ethyl-2- (4'-phenylphenoxy) -1,3 Examples include 2-dioxaphosphorinane-2-oxide and 5,5-dimethyl-2- (2′-naphthyloxy) -1,3,2-dioxaphosphorinane-2-oxide. These compounds can be used alone or in combination of two or more.
Among these, it is preferable to use 5,5-dimethyl-2- (2′-phenylphenoxy) -1,3,2-dioxaphosphorinane-2-oxide from the viewpoint of flame retardancy.

Alkali thickened acrylic resin (C)
The alkali-thickened acrylic resin (C) used in the present invention adjusts the viscosity and viscosity of the flame-retardant coating agent and adjusts the coating properties for the sheet material. One type of resin can be used alone or in combination of two or more types.

  The alkali-thickening acrylic resin (C) is preferably a polymer of a monomer composition containing at least one monomer selected from the group consisting of a carboxyl group-containing monomer and a (meth) acrylic acid ester monomer.

  Among such alkali-thickening acrylic resins, a monomer composition containing at least one monomer selected from the group consisting of a carboxyl group-containing monomer and a (meth) acrylic acid ester monomer, a polymerization initiator, a surfactant, and If necessary, it is preferably obtained by emulsion polymerization in the presence of a chain transfer agent, a crosslinking agent or the like. The polymerization temperature is 5 to 100 ° C., preferably 50 to 80 ° C., and other conditions and methods may be carried out according to general polymerization conditions and methods. Examples of the addition method include a batch addition method, a continuous addition method, a divided addition method, and the like, and these may be adopted.

  Examples of the carboxyl group-containing monomer that is a constituent of the alkali-thickening acrylic resin include monocarboxylic acid monomers such as (meth) acrylic acid, crotonic acid, cinnamic acid, and atropic acid; itaconic acid, maleic acid, and fumaric acid. Examples thereof include dicarboxylic acid monomers such as acids, citraconic acid, and mesaconic acid and acid anhydrides thereof; and dicarboxylic acid monoalkyl ester monomers. Among these, acrylic acid and methacrylic acid are preferable, and methacrylic acid is particularly preferable.

  Examples of (meth) acrylic acid ester monomers include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, ( Sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, decyl (meth) acrylate, ( (Meth) acrylic acid dodecyl, (meth) acrylic acid tetradecyl, (meth) acrylic acid hexadecyl, (meth) acrylic acid octadecyl, (meth) acrylic acid icosyl, (meth) acrylic acid henicosyl, (meth) acrylic acid docosyl, (meta ) Octadecenyl acrylate, cyclopentyl (meth) acrylate, Examples thereof include cyclohexyl (meth) acrylate, benzyl (meth) acrylate, etc., preferably ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, butyl methacrylate, and particularly preferably ethyl acrylate. is there.

  In addition to at least one monomer selected from the group consisting of a carboxyl group-containing monomer and a (meth) acrylic acid ester monomer, the alkali thickening acrylic resin (C) can be copolymerized therewith as a constituent component. Monomers can be used. Examples of such copolymerizable monomers include vinyl carboxylate monomers, styrene monomers, hydroxyl group-containing monomers, amide group-containing monomers, and cyano group-containing monomers.

  Examples of vinyl carboxylate monomers include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl valerate, vinyl pavillate, vinyl caproate, vinyl octoate, vinyl nonanoate, vinyl decanoate, vinyl undecanoate, vinyl laurate, Examples thereof include vinyl tridecanoate, vinyl myristate, vinyl palmitate, vinyl stearate, vinyl monochloroacetate, vinyl benzoate and the like, preferably vinyl acetate and vinyl propionate. Styrene monomers include styrene, α-methyl styrene, o-methyl styrene, m-methyl styrene, p-methyl styrene, o-ethyl styrene, m-ethyl styrene, p-ethyl styrene, o-isopropyl styrene, m- Examples thereof include isopropyl styrene, p-isopropyl styrene, o-tert-butyl styrene, m-tert-butyl styrene, and p-tert-butyl styrene, with styrene being preferred. Hydroxyl group-containing monomers include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, polyoxyethylene mono (meth) acrylate, polyoxypropylene mono (meth) acrylate, polyoxybutylene Mono (meth) acrylate, polyoxydecylene mono (meth) acrylate, polyoxidedecylene mono (meth) acrylate, polyoxytetradecylene mono (meth) acrylate, polyoxyhexadecylene mono (meth) acrylate, polyoxy Octadecylene mono (meth) acrylate, polyoxyicosylene mono (meth) acrylate, polyoxytriacontylene mono (meth) acrylate, polyoxyethylene polyoxypropylene (Meth) acrylate, glycerin mono (meth) acrylate, pentaerythritol mono (meth) acrylate, (meth) allyl alcohol, glycerol mono (meth) allyl ether. Examples of amide group-containing monomers include (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-butyl (meth) acrylamide, and N-methylol (meth). Acrylamide, N-ethylol (meth) acrylamide, N-hydroxypropyl (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-ethoxymethyl (meth) acrylamide, N-propoxymethyl (meth) acrylamide, N-butoxymethyl (Meth) acrylamide, diacetone (meth) acrylamide, maleic acid amide, maleic acid imide and the like can be mentioned. Examples of the cyano group-containing monomer include (meth) acrylonitrile, α-chloroacrylonitrile, α-ethylacrylonitrile and the like. In the above, (meth) acryl means either acryl or methacryl, and (meth) acrylonitrile means either acrylonitrile or methacrylonitrile.

  Polymerization initiators that can be used during the production of the alkali-thickened acrylic resin include hydrogen peroxide, ammonium persulfate, potassium persulfate, redox initiators (hydrogen peroxide-ferrous chloride, ammonium persulfate-acidic sodium sulfite, Ascorbic acid (salt), Rongalite, etc.), 1,1-di-t-butylperoxy-2-methylcyclohexane, 2,2-bis (4,4-di-t-butylperoxycyclohexyl) propane, water-soluble Examples include radical donors such as azo initiators. Further, radicals may be generated by photopolymerization with ultraviolet rays, electron beams, radiation, or the like. In this case, a photosensitizer or the like may be used.

  As the surfactant that can be used in the production of the alkali thickening acrylic resin, the same surfactant as that which can be used when emulsifying and dispersing the phosphazene compound (A) and / or the phosphorus compound (B) described later is used. Things can be used. In the present invention, in addition to these surfactants, a reactive group called a polymerizable group such as a vinyl group or an allyl group and a hydrophilic group such as a sulfonate group or a polyoxyethylene group are included. Compounds can also be used effectively. These surfactants can be used alone or in admixture of two or more. It is preferable to use the surfactant in an amount of 0.1 to 10% by mass based on the total amount of monomers. When the addition amount is less than 0.1% by mass, the polymerization reaction becomes poor and the intended alkali-thickened acrylic resin tends not to be obtained. When it exceeds 10 mass%, there is little effect which makes a polymerization reaction further favorable, and it exists in the tendency for the flame retardance of a flame-retardant sheet material and a tightness to fall.

  Examples of chain transfer agents that can be used in the production of the alkali-thickening acrylic resin include mercaptans such as n-hexyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, n-stearyl mercaptan, and tetraethyl. Those that can be used in usual emulsion polymerization such as thiunium sulfide, pentaphenylethane, terpinolene, α-methylstyrene dimer, etc. can be used alone or in combination of two or more. In addition, as a method of use, any method of batch addition, divided addition or continuous addition may be used. The amount of chain transfer agent used is preferably 2% by mass or less, more preferably 0.5% by mass or less, based on the total amount of monomers. If the addition amount exceeds 2% by mass, the alkali-thickening acrylic resin has a low molecular weight, so that there is a tendency that sufficient viscosity and viscosity cannot be obtained.

  The crosslinking agent that can be used in the production of the alkali-thickening acrylic resin is not particularly limited as long as it is a compound having two or more radically polymerizable double bonds. ) Acrylate, propylene glycol di (meth) acrylate, glycerin di (meth) acrylate, glycerin tri (meth) acrylate, diethylene glycol di (meth) acrylate, diallyl phthalate, diallyl malate, diallyl fumarate, allyl (meth) acrylate, N , N′-methylenebis (meth) acrylamide, divinylbenzene and the like, and can be used as necessary.

  In addition, a pH buffering agent, a chelating agent and the like may be used during the polymerization. Examples of the pH buffering agent include sodium bicarbonate, sodium carbonate, sodium dihydrogen phosphate, sodium phosphate, sodium acetate, and potassium acetate. Examples of the chelating agent include sodium ethylenediaminetetraacetate and sodium nitrilotriacetate. .

  Such an alkali-thickened acrylic resin is usually obtained as an emulsified dispersion of resin and is distributed in the market. The alkali thickening acrylic resin is preferably used in such a state of being emulsified and dispersed. Commercially available products can be used as the alkali-thickening acrylic resin (C). For example, Nicazole VT-253A (manufactured by Nippon Carbide Industries Co., Ltd.), Aron A-20P, Aron A-7150, Aron A- 7070, Aron B-300, Aron B-300K, Aron B-500 (manufactured by Toagosei Co., Ltd.), Jurimer AC-10LHP, Jurimer AC-10SHP, Rheojic 250H, Rheojic 835H, Junron PW-110, Junron PW- 150 (above made by Nippon Pure Chemicals Co., Ltd.), Primal ASE-60, Primal TT-615, Primal RM-5 (above made by Rohm and Haas Japan), SN thickener A-818, SN thickener A -850 (manufactured by San Nopco), Paragum 500 (Para-Chem Saza) Co., Ltd.), Rheolate 430 made (Elementary Chartis Japan Co., Ltd.), Oh sticker V-500 (Nicca Chemical Co., Ltd.), and the like.

  Moreover, in this invention, in order to adjust the applicability | paintability of a flame retardant coating agent, a urethane resin can be used together with an alkali thickening acrylic resin (C). Such a urethane resin can be used in an amount of 0.3 to 1% by mass relative to the flame retardant coating agent.

Examples of urethane resins that can be used in combination with the alkali thickening acrylic resin (C) include nonionic polyether polyol urethane polymers.
As the polyether polyol-based urethane polymer, commercially available products can be used. For example, Adecanol UH-420, Adecanol UH-450, Adecanol UH-540, Adecanol UH-752 (manufactured by Asahi Denka Kogyo Co., Ltd.) SN thickener 601, SN thickener 612, SN thickener 621N, SN thickener 623N (manufactured by San Nopco), Leorate 244, Leorate 278, Leorate 300 (manufactured by Elementis Japan Co., Ltd.), DK thickener SCT-275 (Daiichi Kogyo Seiyaku Co., Ltd.).

  The self-emulsifiable aqueous polyurethane resin (D) having an anionic group used in the present invention is a binder resin used for fixing the phosphazene compound (A) and the phosphorus compound (B) to a sheet material, A good texture can be given to the sheet material. In addition, when used in combination with the phosphazene compound (A) and the phosphorus compound (B), the sheet material can have good flame retardancy and the effect of suppressing the occurrence of sticking to hot water.

  In the present invention, the water-based polyurethane resin refers to a polyurethane resin in which separation or sedimentation is not observed even when an aqueous emulsion dispersion having a polyurethane resin concentration in water of 40% by mass is left at 20 ° C. for 12 hours.

Examples of the anionic group include a carboxyl group (—COOH), a carboxylate group (—COO ⁻ ), a sulfo group (—SO ₃ H), a sulfonate group (—SO ₃ ^— ), and the like. Among them, from the viewpoint that the emulsion dispersion stability of the self-emulsifiable aqueous polyurethane resin (D) having an anionic group tends to be excellent, and the flame retardancy of the flame retardant sheet material tends to decrease less. It is preferably a group and / or a carboxylate group.

  The content of the anionic group in the self-emulsifiable aqueous polyurethane resin (D) having an anionic group is preferably 0.1 to 5.0% by mass, and preferably 0.2 to 4.0% by mass. Is more preferable, and it is still more preferable that it is 0.5-2.5 mass%.

  When the content of the anionic group is less than the lower limit, it is difficult to emulsify and disperse the aqueous polyurethane resin, and the stability of the aqueous polyurethane resin water-emulsified dispersion tends to be poor. Tend to decrease. When the above upper limit is exceeded, the component (D) becomes difficult to sharply heat-sensitive coagulate, and there is a tendency for show-through.

Examples of the aqueous polyurethane resin include (a) an organic polyisocyanate, (b) a polyol, and (c) an isocyanate group-terminated prepolymer having an anionic group obtained by reacting a compound having an anionic group and two or more active hydrogens. An aqueous solution having an anionic group obtained by emulsifying and dispersing a polymer neutralized product in water by self-emulsification and (d) a chain extension reaction using a polyamine compound having two or more amino groups and / or imino groups. A polyurethane resin can be suitably used.
The self-emulsifiable aqueous polyurethane resin (D) having an anionic group can be used alone or in combination of two or more.

(A) Organic polyisocyanate The (a) organic polyisocyanate used in producing the self-emulsifiable aqueous polyurethane resin (D) having an anionic group useful in the present invention is not particularly limited, and for example, a diisocyanate compound A modified polyisocyanate compound such as a triisocyanate compound, a tetraisocyanate and a compound, a dimer or a trimer of a diisocyanate compound can be used.

  Examples of the diisocyanate compound include aliphatic diisocyanate compounds such as tetramethylene diisocyanate, hexamethylene diisocyanate, dodecamethylene diisocyanate, and trimethylhexamethylene diisocyanate; isophorone diisocyanate, hydrogenated xylylene diisocyanate, dicyclohexylmethane diisocyanate, norbornane diisocyanate, 1,3- Alicyclic diisocyanate compounds such as bis (isocyanatomethyl) cyclohexane and 3,3′-dimethyl-4,4′-dicyclohexylmethane diisocyanate; phenylene diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, 3,3′-dimethyl-4, 4'-biphenylene diisocyanate, 3,3'-dichloro-4,4'- Phenylene diisocyanate, naphthalene diisocyanate, tolidine diisocyanate, xylylene diisocyanate, aromatic diisocyanate compounds such as tetramethyl xylylene diisocyanate.

  Examples of the triisocyanate compound, tetraisocyanate and compound include triphenylmethane triisocyanate, dimethyltriphenylmethane tetraisocyanate, and tris (isocyanatophenyl) -thiophosphate.

The modified polyisocyanate compound derived from the diisocyanate compound is not particularly limited as long as it has two or more isocyanate groups. For example, biuret structure, isocyanurate structure, urethane structure, uretdione structure, allophanate structure, trimer Examples thereof include polyisocyanates having a body structure, etc., adducts of aliphatic isocyanates of trimethylolpropane, and polymeric MDI (MDI = diphenylmethane diisocyanate).
These polyisocyanate compounds may be used alone or in combination of two or more.

  Among these polyisocyanate compounds, aliphatic polyisocyanates and alicyclic polyisocyanates can be suitably used because the flame-retardant sheet material tends to be non-yellowing.

(B) Polyol As the polyol (b) used in producing the self-emulsifiable aqueous polyurethane resin (D) having an anionic group useful in the present invention, particularly if it has two or more hydroxyl groups. Without being limited, polyester polyol, polycarbonate polyol, polyether polyol, dimer diol and the like can be used.

  Examples of the polyester polyol include polyethylene adipate diol, polybutylene adipate diol, polyethylene butylene adipate diol, polyhexamethylene isophthalate adipate diol, polyethylene succinate diol, polybutylene succinate diol, polyethylene sebacate diol, and polybutylene sebacate. Diol, poly-ω-capololactone diol, poly (3-methyl-1,5-pentylene) adipate diol, polycondensate of 1,6-hexanediol and dimer acid, 1,6-hexanediol and adipic acid Examples thereof include a copolycondensate of dimer acid, a polycondensate of nonanediol and dimer acid, a copolycondensate of ethylene glycol, adipic acid and dimer acid, and the like.

  Examples of the polycarbonate polyol include polycarbonate polyols obtained by reaction of glycols such as 1,4-butanediol, 1,6-hexanediol, and diethylene glycol with diphenyl carbonate, phosgene, and the like. Examples of such a polycarbonate polyol include polytetramethylene carbonate diol, polyhexamethylene carbonate diol, 3-methyl-1,5-pentanediol carbonate diol, poly-1,4-cyclohexanedimethylene carbonate diol, 1,6 -A hexanediol polycarbonate polyol etc. can be mentioned.

  Examples of the polyether polyol include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, trimethylene glycol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6- Hexanediol, neopentyl glycol, glycerin, trimethylolethane, trimethylolpropane, sorbitol, sucrose, bisphenol A, bisphenol S, hydrogenated bisphenol A, aconitic acid, trimellitic acid, hemimellitic acid, phosphoric acid, ethylenediamine, diethylenetriamine, Triisopropanolamine, pyrogallol, dihydroxybenzoic acid, hydroxyphthalic acid, 1,2,3-propanetrithiol, monoethanolamine, diethano To compounds having at least two active hydrogens such as amine and triethanolamine, monomers such as ethylene oxide, propylene oxide, butylene oxide, styrene oxide, trimethylene oxide, tetramethylene oxide, epichlorohydrin, tetrahydrofuran, cyclohexylene, etc. Examples thereof include polymers obtained by addition polymerization of one kind or two or more kinds by a conventional method. In this case, the addition polymerization method may be any of homopolymerization, block copolymerization, and random copolymerization.

  Examples of the dimer diol include those mainly composed of a diol obtained by reducing a polymerized fatty acid. Examples of such polymerized fatty acids include Diels-Alder type bimolecular polymerization of unsaturated fatty acids having 18 carbon atoms such as oleic acid and linoleic acid, dry oil fatty acids, semi-dry oil fatty acids, and lower monoalcohol esters of these fatty acids. What reacted is mentioned.

  These polyols may be used alone or in combination of two or more. Moreover, as a weight average molecular weight of such a polyol, it is preferable that it is 500-5,000, and it is more preferable that it is 1,000-3,000.

  Among these polyols, at least one selected from the group consisting of polycarbonate polyols and polyether polyols is preferable from the viewpoint of less deterioration in strength over time of the flame-retardant sheet material due to hydrolysis.

(C) Compound having an anionic group and two or more active hydrogens (c) Anionic group used in producing a self-emulsifiable aqueous polyurethane resin (D) having an anionic group useful in the present invention The compound having two or more active hydrogens is not particularly limited, and examples thereof include carboxyl group-containing low molecular diols such as 2,2-dimethylolpropionic acid and 2,2-dimethylolbutanoic acid, 2-sulfo- Sulfone group-containing low molecular diols such as 1,3-propanediol and 2-sulfo-1,4-butanediol, and ammonium salts of these carboxyl group-containing low molecular diols or sulfone group-containing low molecular diols, trimethylamine, triethylamine, Tri-n-propylamine, tributylamine, triethanolamine, N, N-dimethyldiethanol Examples include amines, organic amine salts such as N, N-diethylethanolamine, and alkali metal salts such as sodium and potassium. These may be used alone or in combination of two or more.

(D) Polyamine compound having two or more amino groups and / or imino groups (d) Used in producing the aqueous polyurethane resin (D) useful in the present invention (d) Having two or more amino groups and / or imino groups The polyamine compound is not particularly limited. For example, ethylenediamine, propylenediamine, tetramethylenediamine, hexamethylenediamine, diaminocyclohexylmethane, piperazine, hydrazine, 2-methylpiperazine, isophoronediamine, norbornanediamine, diaminodiphenylmethane, tolylenediamine Diamines such as xylylenediamine; polyamines such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine, iminobispropylamine, tris (2-aminoethyl) amine; diprimary amines And amidoamines derived from monocarboxylic acids; water-soluble amine derivatives such as monoketimines of diprimary amines; And hydrazine derivatives such as fumaric acid dihydrazide, itaconic acid dihydrazide, 1,1′-ethylenedihydrazine, 1,1′-trimethylenedihydrazine, 1,1 ′-(1,4-butylene) dihydrazine, and the like. it can. These polyamine compounds having two or more amino groups and / or imino groups can be used singly or in combination of two or more.

  The polyurethane resin having an anionic group can be obtained as an emulsified dispersion of the polyurethane resin by the emulsification dispersion in water and the chain extension reaction by the self-emulsification of the neutralized product of the isocyanate group-terminated prepolymer having an anionic group. .

  The neutralized product of the isocyanate group-terminated prepolymer having an anionic group is an isocyanate having a group obtained by neutralizing an anionic group derived from the compound (c) having an anionic group and two or more active hydrogens. It is a group terminal prepolymer neutralized product, and is obtained by reacting (a) organic polyisocyanate, (b) polyol and (c) a compound having an anionic group and two or more active hydrogens.

  A specific method for obtaining such a neutralized isocyanate group-terminated prepolymer having an anionic group is not particularly limited, and for example, a conventionally known one-stage so-called one-shot method, multi-stage isocyanate weight It can be produced by an addition reaction method or the like. The reaction temperature at this time is preferably 40 to 150 ° C.

  In such a reaction, a low molecular weight chain extender having two or more active hydrogen atoms can be used as necessary. Such a low molecular weight chain extender preferably has a molecular weight of 400 or less, particularly preferably 300 or less. Examples of the low molecular weight chain extender include, for example, low molecular weight high molecular weights such as ethylene glycol, propylene glycol, neopentyl glycol, 1,4-butanediol, 1,6-hexanediol, trimethylolpropane, pentaerythritol, and sorbitol. Examples thereof include low-molecular-weight polyamines such as ethylene diamine, propylene diamine, hexamethylene diamine, diaminocyclohexyl methane, piperazine, 2-methylpiperazine, isophorone diamine, diethylene triamine, and triethylene tetramine. These low molecular weight chain extenders may be used alone or in combination of two or more.

  Furthermore, a reaction catalyst such as dibutyltin dilaurate, stannous octoate, dibutyltin-2-ethylhexanoate, triethylamine, triethylenediamine, or N-methylmorpholine may be added as necessary during the reaction. Can do. Moreover, the organic solvent which does not react with an isocyanate group can be added at the time of reaction or after completion | finish of reaction. As such an organic solvent, for example, acetone, methyl ethyl ketone, toluene, tetrahydrofuran, dioxane, dimethylformamide, N-methylpyrrolidone, ethyl acetate, methyl isobutyl ketone and the like can be used.

  The neutralization of the anionic group derived from the compound having the (c) anionic group and two or more active hydrogens may be performed simultaneously with the preparation of the isocyanate group-terminated prepolymer, or before the preparation. It may be after preparation. Such neutralization can be appropriately performed using a known method, and the compound used for such neutralization is not particularly limited, and examples thereof include trimethylamine, triethylamine, tri-n-propylamine, and tributylamine. , N-methyl-diethanolamine, N, N-dimethylmonoethanolamine, N, N-diethylmonoethanolamine, amines such as triethanolamine; potassium hydroxide; sodium hydroxide; sodium carbonate; ammonia and the like. Among these, tertiary amines such as trimethylamine, triethylamine, tri-n-propylamine and tributylamine are particularly preferable.

  The method for emulsifying and dispersing the neutralized isocyanate group-terminated prepolymer having an anionic group in water is not particularly limited, and examples thereof include a method using an emulsifying and dispersing device such as a homomixer, a homogenizer, and a disper. Moreover, when the isocyanate group-terminated prepolymer neutralized product having an anionic group is emulsified and dispersed in water, the prepolymer neutralized product is self-emulsified in a temperature range of 5 to 40 ° C. without using an emulsifier. Is preferably emulsified and dispersed in water to suppress the reaction between the isocyanate group and water as much as possible. When an emulsifier is used, the flame retardancy and wrinkle tend to decrease.

  Further, when emulsifying and dispersing in this manner, a reaction control agent such as phosphoric acid, sodium dihydrogen phosphate, disodium hydrogen phosphate, paratoluenesulfonic acid, adipic acid, benzoyl chloride is added as necessary. be able to.

  The chain elongation reaction of the neutralized isocyanate group-terminated prepolymer having an anionic group is carried out by adding two amino groups and / or imino groups to the neutralized isocyanate group-terminated prepolymer having the anionic group. The polyamine compound having the above is added, or the (d) neutralized isocyanate group-terminated prepolymer having an anionic group is added to the polyamine compound having two or more amino groups and / or imino groups. be able to. Such chain extension reaction is preferably performed at a reaction temperature of 20 to 40 ° C. Usually it is completed in 30 to 120 minutes.

  In the method for producing a polyurethane resin having an anionic group, the emulsification dispersion and the chain extension reaction may be performed simultaneously, after emulsifying and dispersing the isocyanate group-terminated prepolymer neutralized product having the anionic group. The chain may be elongated or emulsified and dispersed after the chain is elongated. Moreover, when the above-mentioned organic solvent is used when producing an isocyanate group-terminated prepolymer neutralized product having an anionic group, for example, the organic solvent is removed by distillation under reduced pressure or the like after a chain extension reaction or emulsification dispersion. It is preferable.

  Such an aqueous polyurethane resin is usually obtained as an emulsified dispersion of the resin and is distributed in the market. The aqueous polyurethane resin is preferably used in a state of being emulsified and dispersed in water as described above, and the concentration thereof is not particularly limited. However, the coating agent according to the present invention tends to be easily obtained in a uniform state. In consideration of the performance of the flame retardant sheet material, it is preferably 15 to 60% by mass.

Water (E)
When the water (E) is mixed with the phosphazene compound (A), the phosphorus compound (B), the alkali thickening acrylic resin (C), and the self-emulsifiable aqueous polyurethane resin (D) having an anionic group, It has a role as a solvent, and ion-exchanged water or distilled water can be suitably used.

  An organic solvent can be used in combination with the flame retardant coating agent of the present invention as a solvent. Examples of such an organic solvent include glycols such as ethylene glycol, diethylene glycol, butyl glycol, and butyl diglycol; alcohols such as methanol, ethanol, and isopropanol. From the viewpoints of tightness, cost, hazardous materials, fastness, viscosity, and penetration, the amount of the organic solvent is preferably 10% by mass or less, and most preferably 0% by mass with respect to water (E). preferable.

  In the flame-retardant coating agent of the present invention, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, ammonia, hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, acetic acid and the like can be used as a pH adjuster. .

  In the flame-retardant coating agent of the present invention, the blending amount of the phosphazene compound (A) is preferably 20 to 200 parts by mass, and 30 to 150 parts by mass with respect to 100 parts by mass of the aqueous polyurethane resin (D). It is more preferable. When the blending amount of the phosphazene compound (A) is less than 20 parts by mass with respect to 100 parts by mass of the aqueous polyurethane resin (D), the flame retardancy and texture of the flame retardant sheet material tend to decrease, and 200 parts by mass. Exceeding, there is a tendency that the phosphazene compound (A) powders on the surface of the flame retardant sheet material, various fastnesses and strengths of the flame retardant sheet material are lowered, and the texture is cured.

  It is preferable that the compounding quantity of a phosphorus compound (B) is 10-250 mass parts with respect to 100 mass parts of water-based polyurethane resin (D), and it is more preferable that it is 20-100 mass parts. When the blending amount of the phosphorus compound (B) is less than 10 parts by mass with respect to 100 parts by mass of the water-based polyurethane resin (D), the effect of plasticizing the flame-retardant coating is insufficient, and the texture is cured. There is a tendency to decrease, and if it exceeds 250 parts by mass, the phosphorous compound (B) powders on the surface of the flame retardant sheet material, and the various fastnesses of the flame retardant sheet material decrease, the flame retardant sheet There is a tendency for the material to become sticky.

  In the flame retardant coating agent of the present invention, the phosphazene compound (A) and the phosphorus compound (B) are blended in amounts (mass basis) phosphazene compound (A): phosphorus compound (B) = 50: 50 to 95: 5. It is preferable that

  The blending amount of the alkali-thickening acrylic resin (C) is 0.5 to 25 parts by mass with respect to 100 parts by mass of the aqueous polyurethane resin (D) from the viewpoint of product stability and coating properties of the flame retardant coating agent. It is preferable that it is 1.0-10 mass parts. When the blending amount of the thickener (C) is less than 0.5 parts by mass with respect to 100 parts by mass of the aqueous polyurethane resin (D), the product stability of the flame retardant coating agent is lowered, and the flame retardancy to the sheet material There is a tendency to overcoating the coating agent and see-through, and if it exceeds 25 parts by mass, the flame retardant coating agent will become difficult to handle due to thickening and solidification, and to the sheet material due to faintness There is a tendency that a uniform process becomes difficult.

The flame retardant coating agent of the present invention can be used in combination with a metal hydroxide (F) from the viewpoint of improving flame retardancy by cooling when the flame retardant sheet material is combusted.
Examples of such metal hydroxide (F) include aluminum hydroxide and magnesium hydroxide, and these may be used in combination of two or more. Among these, aluminum hydroxide having a large endothermic amount is preferably used.

  Although the compounding quantity of a metal hydroxide (F) does not have a restriction | limiting in particular, It is preferable that it is less than 100 mass parts with respect to 100 mass parts of water-based polyurethane resin (D). When the amount is 100 parts by mass or more, the film formation of the water-based polyurethane resin (D) is affected, the adhesiveness between the flame-retardant film and the sheet material is lowered, and sufficient fabric strength tends not to be obtained.

  In the flame-retardant coating agent of the present invention, a phosphazene compound, a phosphorus compound, a thickener, a thermoplastic resin, a deodorant, a foaming agent, etc. other than those used in the present invention are used within the range not impairing the effects of the present invention. Can be blended.

In the present invention, when a polyurethane resin having a carboxy group is used as the aqueous polyurethane resin (D), the processability is imparted to the obtained flame-retardant sheet material within a range not impairing the effects of the present invention. For the purpose, a crosslinking agent that reacts with the carboxy group may be further added. Examples of such crosslinking agents include oxazoline crosslinking agents, epoxy crosslinking agents, isocyanate crosslinking agents, carbodiimide crosslinking agents, aziridine crosslinking agents, blocked isocyanate crosslinking agents, water-dispersed isocyanate crosslinking agents, and melamine crosslinking agents. Etc. As the crosslinking agent, one kind may be used alone, or two or more kinds may be used in combination.
Among these crosslinking agents, a carbodiimide-based crosslinking agent is preferable from the viewpoint of the tightness, strength, and fastness of the flame-retardant sheet material, and the blending amount thereof is set to 0. 0 with respect to the aqueous polyurethane resin (D). It is preferable that it is 5-10 mass%.

  The method for obtaining the flame retardant coating agent of the present invention is not particularly limited, and a known method can be used as appropriate. The order and method of blending the components (A) to (E) can be appropriately changed. In general, however, an aqueous emulsion dispersion containing a phosphazene compound (A) and a phosphorus compound (B) is prepared, and then an alkali-thickened acrylic resin (C) and an aqueous polyurethane resin (D) are blended. , Stirring and mixing, and adjusting the viscosity, pH, solid content and the like to obtain a flame retardant coating agent.

  As a method of stirring and mixing after blending the components (A) to (E), a conventionally known stirring device or emulsifying dispersion device can be used. Conventionally known agitators and emulsifiers / dispersers are not particularly limited, and include propellers, kneaders, rollers, colloid mills, bead mills, milders, homogenizers, ultrasonic homogenizers, homomixers, homodispers, nanomizers, optimizers, starbursts, etc. And an emulsifier / disperser. One type of these devices may be used, or two or more types may be used in combination.

The water-emulsified dispersion containing the phosphazene compound (A) and the phosphorus compound (B) can be obtained by, for example, emulsifying and dispersing the phosphazene compound (A) and the phosphorus compound (B) in water (E), or the phosphazene compound ( It can be obtained by blending the aqueous emulsion dispersion of A) and the aqueous emulsion dispersion of the phosphorus compound (B).
As a method for emulsifying and dispersing the phosphazene compound (A) and / or the phosphorus compound (B), a conventionally known stirring device and emulsifying dispersion device similar to those described above can be used.

When emulsifying and dispersing the phosphazene compound (A) and / or the phosphorus compound (B), a surfactant can be used. By using the surfactant, the phosphazene compound (A) and / or the phosphorus compound (B) can be stably emulsified and dispersed, and the alkali-thickened acrylic resin (C) and the aqueous polyurethane resin (D) It becomes easy to mix and it becomes easy to manufacture a flame-retardant coating agent.
Such a surfactant is not particularly limited, and at least one of known nonionic surfactants and anionic surfactants can be used.

  Nonionic surfactants include, for example, linear or branched C8-24 alcohols or alkenols, alkylene oxide adducts, polycyclic phenols alkylene oxide adducts, linear or branched carbons. Alkylene oxide adduct of aliphatic amine having 8 to 44, linear or branched alkylene oxide adduct of fatty acid amide having 8 to 44 carbon atoms, alkylene oxide of linear or branched fatty acid having 8 to 24 carbon atoms Nonionic surfactants such as adducts, reaction products of polyhydric alcohols with linear or branched fatty acids having 8 to 24 carbon atoms and alkylene oxides, and alkylene oxide adducts of fats and oils. These nonionic surfactants may be used individually by 1 type, and may be used in combination of 2 or more type.

  Examples of the anionic surfactant include sulfate ester salts, phosphate ester salts, carboxylate salts and sulfosuccinic acid type anionic surfactants of the above-mentioned nonionic surfactants, sulfate esters and phosphate ester salts of higher alcohols, and fats and oils. Sulfonated products, alkylbenzene sulfonates, alkyl naphthalene sulfonates, and formalin condensates of naphthalene sulfonates. These anionic surfactants may be used individually by 1 type, and may be used in combination of 2 or more type.

  Among these, from the viewpoints of emulsifying dispersibility and stability, it is composed of an alkylene oxide adduct of linear or branched alcohols having 8 to 24 carbon atoms, an alkylene oxide adduct of polycyclic phenols, and an anionized product thereof. It is preferably at least one selected from the group.

  As polycyclic phenols, (3-8 mol) styrene adduct, (3-8 mol) α-methylstyrene adduct of phenol, 4-cumylphenol, 4-phenylphenol, or 2-naphthol, or A (3-8 mol) benzyl chloride reactant is preferred.

  The amount of the surfactant in the flame retardant coating agent of the present invention is 100 mass in total of the component (A), the component (B), the component (C), the component (D), and, in some cases, the component (F). It is preferable that it is 0.1-3 mass parts with respect to a part. When the amount is less than 0.1 parts by mass, the product stability of the flame retardant coating agent tends to decrease and the flame resistance of the flame retardant sheet material tends to decrease. When the amount exceeds 3 parts by mass, the flame retardant sheet material There is a tendency to decrease the tightness, fastness, and flame retardancy.

  The flame retardant coating agent of the present invention has an average particle diameter d (50) of 0.5 to 30 μm, a maximum particle diameter d (max) of preferably 200 μm or less, and an average particle diameter d (50) of More preferably, it is 0.5 to 20 μm, and the maximum particle diameter d (max) is 100 μm or less.

  When the average particle diameter d (50) exceeds 30 μm, or when the maximum particle diameter d (max) exceeds 200 μm, the product stability of the flame retardant coating agent tends to decrease, and the flame retardancy of the flame retardant sheet material There is a tendency for the (A) component and / or the (B) component to powder on the surface of the flame retardant sheet material. When the average particle diameter d (50) is less than 0.5 μm, a great deal of time and cost are required to reduce the particle diameter, which tends to be unfavorable industrially.

  For the particle size, the cumulative volume particle size distribution is measured using a laser diffraction / scattering particle size distribution measuring device, and the particle size (median particle size) at which the integrated volume is 50% is defined as the average particle size d (50). The particle diameter (maximum particle diameter) at which 100% is 100% can be determined as the maximum particle diameter d (max).

  In the flame-retardant coating agent of this invention, it is preferable to adjust pH to 6.0-10.0, and it is more preferable to adjust to 7.0-9.0. When the pH is less than 6.0, the viscosity of the flame retardant coating agent decreases, the product stability of the flame retardant coating agent decreases, the amount of the flame retardant coating agent applied to the sheet material is excessive, and there is a tendency to show through. is there. When it exceeds 10.0, there exists a tendency for the flame retardance fall by the hydrolysis of a flame-retardant component, and cloth | dye deterioration.

  The flame retardant coating agent of the present invention comprises a total of the phosphazene compound (A), the phosphorus compound (B), the alkali thickening acrylic resin (C), the aqueous polyurethane resin (D), and in some cases the compound (F). It is preferable that it is 20-60 mass%. When the total is less than 20% by mass, the amount applied to the sheet material is insufficient, and the flame retardancy tends to be reduced. When it exceeds 60%, the coating amount becomes excessive, and further improvement in flame retardancy is reduced, and various fastnesses tend to be lowered.

  The viscosity of the flame retardant coating agent of the present invention is preferably 3,000 to 30,000 mPa · s, and more preferably 8,000 to 20,000 mPa · s. When the viscosity is less than 3,000 mPa · s, there is a tendency to show through, and when the viscosity exceeds 30,000 mPa · s, blurring tends to occur.

When the flame retardant coating agent of the present invention is foam-coated on a sheet material, the flame retardant coating agent preferably has a viscosity of 500 to 10,000 mPa · s. If it is less than 500 mPa · s, the product stability of the flame-retardant coating agent tends to be poor, and if it exceeds 10,000 mPa · s, foaming tends to be poor and good foam coating tends to be impossible.
When foaming coating is performed, it is necessary to appropriately use a foaming agent such as N, N-dimethyldodecylamine oxide or sodium dodecyl diphenyl ether disulfonate.

  In the present invention, the viscosity (unit: mPa · s) of the flame retardant coating agent is 200 ml of the flame retardant coating agent in a glass bottle having an inner diameter of 50 mm, and a B type viscometer (high viscosity type; BH type, rotor NO. 5). , 20 rpm, measurement temperature 20 ° C.).

  In the flame-retardant coating agent of the present invention, good coatability can be obtained by setting not only the viscosity but also the viscosity within a specific range. The viscosity can be determined by measuring the PVI value.

  The flame retardant coating agent of the present invention preferably has a PVI value of 0.10 to 0.30, and more preferably 0.15 to 0.25. When the PVI value is less than 0.10, there is a tendency of excessive application amount or show-through, and when it exceeds 0.30, there is a tendency that blurring or a sufficient application amount cannot be provided.

The PVI value is a printing viscosity index, which is a value calculated from the following formula by measuring a flame retardant coating agent under the above viscosity measurement conditions at rotation speeds of 20 rpm and 2 rpm.
PVI value = Measured value at 20 rpm / Measured value at 2 rpm

  The flame retardant coating agent of the present invention is treated on one side of the sheet material and then dried, and the phosphazene compound (A), phosphorus compound (B) is incorporated into the treated side of the sheet material and / or in the sheet material. ), A flame-retardant sheet material can be obtained by forming a flame-retardant film containing an alkali-thickened acrylic resin (C) and an aqueous polyurethane resin (D).

When the flame retardant coating agent of the present invention is processed into a sheet material, the flame retardant coating agent of the present invention may be used as it is, or may be diluted as appropriate.
Examples of the method for treating the flame retardant coating agent of the present invention into a sheet material include coating methods such as gravure coater, knife coater, roll coater, slit coater, comma coater, air knife coater, flow coater, brush, and foam. be able to.
After the flame retardant coating agent is processed into a sheet material, the obtained flame retardant sheet material can be laminated or bonded.

  The method of drying the flame retardant coating agent of the present invention after treating it on one side of the sheet material is not particularly limited, and is, for example, dry drying using hot air; Hiten Pulcher Steamer (HTS ), Wet drying using a high pressure steamer (HPS); a microwave irradiation dryer or the like can be used. These drying methods can be used individually by 1 type, or can also be used in combination of 2 or more type. The drying temperature is preferably 80 ° C. to 180 ° C., and the drying time is preferably 1 minute to 30 minutes. In particular, a drying temperature of 80 ° C. to 130 ° C. and a drying time of 2 minutes to 10 minutes are more preferable. By performing such drying, a flame retardant coating can be formed on the treated surface of the sheet material and / or in the sheet material.

  As the amount (DRY) of the flame retardant coating agent applied to the sheet material, the phosphazene compound (A), the phosphorus compound (B), the alkali thickening acrylic resin (C), and the aqueous polyurethane resin (D) may be used depending on circumstances. Is preferably 10 to 100% by mass, and more preferably 15 to 50% by mass with respect to the sheet material. When the applied amount (DRY) is less than 10% by mass, the flame retardancy tends to decrease, and when it exceeds 100% by mass, the flexibility of the flame retardant sheet material tends to deteriorate, and further flame retardancy There is a tendency for the improvement in sex to be small.

The sheet material that can be treated with the flame retardant coating agent of the present invention is not particularly limited. For example, natural fibers such as cotton, hemp, silk, and wool, regenerated fibers such as rayon, and semi-synthetic materials such as acetate. Synthetic fibers such as fibers, polyamide fibers, polyvinyl chloride fibers, polyacrylonitrile fibers, polyester fibers, polyurethane fibers, polyethylene fibers, polypropylene fibers, woven fabrics made of these composite fibers, blended fibers, etc. A knitted fabric and a nonwoven fabric can be mentioned.
Such a sheet material may be subjected to a dyeing process or a soaping process.

EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated in more detail, this invention is not limited at all by the following examples.
The performance of the obtained flame retardant coating agent and flame retardant sheet material was evaluated by the following method.

(1) Viscosity 200 ml of a flame retardant coating agent was placed in a glass bottle with an inner diameter of 50 mm, and measured using a B-type viscometer (high viscosity type; BH type, rotor No. 5, 20 rpm, measurement temperature 20 ° C.).

(2) PVI value The flame retardant coating agent was measured under the above viscosity measurement conditions at rotation speeds of 20 rpm and 2 rpm, and calculated from the following formula.
PVI value = Measured value at 20 rpm / Measured value at 2 rpm

(3) pH
Measured with Horiba (F-52S).

(4) Flame retardance In the flame retardancy test, the combustion speed was measured 10 times in accordance with the test method of US automobile safety standard FMVSS302. The case where the combustion speed was less than 80 mm / min was determined to be acceptable, and the more the number of times of acceptance, the better the flame retardancy.

(5) Hot water tightness The flame-retardant sheet material is cut into a 20 cm square, and 5 cc of boiling distilled water is dropped onto the coated surface. After standing at room temperature for 24 hours, evaluation was performed according to the following criteria. Evaluation was similarly performed on the surface not subjected to the coating treatment.
S: No tightness A: Slight tightness B: Strongness C: Extremely strong

(6) Strikethrough The degree of breakthrough after the treatment with the flame retardant coating agent was evaluated according to the following criteria.
A: No show-through B: There is a show-through (especially Bx if the show-through is severe)

(7) Friction fastness (dry type)
About the flame-retardant sheet material obtained in each Example and Comparative Example, the friction fastness test is performed by the same method as the dyeing fastness test method for friction described in JIS L 0849 (2004), and the series is determined. did. In addition, this time, the friction tester type II (Gakushoku type) described in JIS L 0849 (2004) 5.1b) was used, and only the dry test described in JIS L 0849 (2004) 7.1 b) was performed. It was.

(8) Flexibility According to JIS L 1096 A method (45 ° cantilever method).
The smaller the value, the more flexible the texture.

(9) Haze value (glass haze)
Using a windscreen fogging tester (manufactured by Suga Test Instruments), a flame retardant sheet material of 5.0 cm × 5.0 cm is heated at 80 ° C. for 20 hours, and the sublimate from the flame retardant sheet material is glass plate on the upper part of the container Adhered to.
Using an integrating sphere type measuring device, the light transmittance (%) of the glass plate was measured, and 100−transmittance = haze value (glass haze). The smaller the numerical value, the better the haze (brightness).

(10) Prevention of seam fatigue Two test cloths having a length of 10 cm and a width of 10 cm are collected from the flame-retardant sheet material.
The uncoated surfaces of the two sheets are put together and overlapped, and a test piece to be tested in the horizontal direction is manufactured by sewing a position 1 cm from the end of one side in the vertical direction. The test piece is opened, one side of the test piece is attached to a seam fatigue tester (manufactured by Yamaguchi Kagaku Sangyo Co., Ltd.), the other side is loaded (3 kg weight), and the seam fatigue test is repeated 2500 times. Thereafter, with the load applied, the distance between one fabric at the seam portion and the other fabric is measured in units of 0.1 mm.
Similarly, the test is also performed in the vertical direction, and the values in the vertical direction and the horizontal direction are averaged. The smaller the average value, the better the anti-seam fatigue resistance.

Production Example 1
50 parts by mass of phenoxyphosphazene, 1 part by mass of an ethylene oxide 20 mol adduct of tristyrenated phenol (hereinafter abbreviated as TSP20E) and 49 parts by mass of water are subjected to bead mill treatment to obtain an emulsified dispersion of phosphazene compound (A) (average particle) Diameter 20 μm, phenoxyphosphazene non-volatile content 50 mass%, TSP20E non-volatile content 1 mass%).

Production Example 2
The same procedure as in Production Example 1 was carried out except that 1 part by mass of TSP20E was changed to 2 parts by mass and 49 parts by mass of water was changed to 48 parts by mass, and an emulsified dispersion of phosphazene compound (A) (average particle size 1 μm, Phenoxyphosphazene non-volatile content 50 mass%, TSP20E non-volatile content 2.0 mass%).

Production Example 3
50 parts by mass of methoxyphosphazene, 1 part by mass of TSP20E and 49 parts by mass of water were subjected to a homomixer treatment to give an emulsified dispersion of the phosphazene compound (A) (average particle size 5 μm, methoxyphosphazene nonvolatile content 50% by mass, TSP20E nonvolatile content 1% by mass. )

Production Example 4
The same procedure as in Production Example 3 was followed except that isopropoxyphosphazene was used instead of methoxyphosphazene, and an emulsified dispersion of phosphazene compound (A) (average particle size 5 μm, isopropoxyphosphazene nonvolatile content 50 mass%, TSP20E Non-volatile content 1% by mass) was obtained.

Production Example 5
Except for using resorcinol bis-dixylenyl phosphate instead of phenoxy phosphazene, the same procedure as in Production Example 1 was followed to obtain an emulsified dispersion of phosphorous compound (B) (average particle size 20 μm, resorcinol bis-dioxy). Silenyl phosphate non-volatile content 50 mass%, TSP20E non-volatile content 1 mass%).

Production Example 6
Except for using resorcinol bisdixylenyl phosphate in place of phenoxyphosphazene, the same operation as in Production Example 2 was carried out to obtain an emulsified dispersion of phosphorous compound (B) (average particle size 1 μm, resorcinol bisdikis). Silenyl phosphate non-volatile content 50 mass%, TSP20E non-volatile content 2.0 mass%).

Production Example 7
Except that phenoxyethyl diphenyl phosphate was used instead of phenoxy phosphazene, the same operation as in Production Example 1 was carried out to prepare an emulsified dispersion of phosphorous compound (B) (average particle size 20 μm, phenoxyethyl diphenyl phosphate non-volatile content 50 mass) %, TSP20E nonvolatile content 1% by mass).

Production Example 8
The phosphorus compound (B) was prepared in the same manner as in Production Example 1 except that 10-benzyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide was used instead of phenoxyphosphazene. Emulsion (average particle size 20 μm, 10-benzyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide nonvolatile content 50 mass%, TSP20E nonvolatile content 1 mass%) was obtained.

Production Example 9
The same procedure as in Production Example 1 was performed except that 5,5-dimethyl-2- (2′-phenylphenoxy) -1,3,2-dioxaphosphorinane-2-oxide was used instead of phenoxyphosphazene. An emulsified dispersion of phosphorus compound (B) (average particle size 20 μm, 5,5-dimethyl-2- (2′-phenylphenoxy) -1,3,2-dioxaphosphorinane-2-oxide nonvolatile content 50 Mass%, TSP20E nonvolatile content 1 mass%).

Comparative production example 1
Except for using ammonium polyphosphate (degree of polymerization 1000 or more, average particle size 18 μm) instead of phenoxyphosphazene, the same procedure as in Production Example 1 was carried out to prepare an emulsified dispersion of ammonium polyphosphate (average particle size 20 μm, polyphosphorus). Ammonium acid non-volatile content 50 mass%, TSP20E non-volatile content 1 mass%) were obtained.

Comparative production example 2
Except for using resorcinol bisdiphenyl phosphate instead of methoxyphosphazene, the same operation as in Production Example 3 was carried out to prepare an emulsified dispersion of resorcinol bisdiphenyl phosphate (average particle size 5 μm, resorcinol bisdiphenyl phosphate nonvolatile content 50% by mass, TSP20E nonvolatile content 1% by mass) was obtained.

Comparative production example 3
Except for using 50 parts by mass of aluminum ethylmethylphosphinate (average particle diameter 6 μm), 4.2 parts by mass of TSP20E, and 45.8 parts by mass of water, the same operation as in Production Example 1 was carried out. An emulsified dispersion (average particle diameter: 3 μm, non-volatile content of aluminum ethylmethylphosphinate 50 mass%, non-volatile content of TSP20E 4.2 mass%) was obtained.

Synthesis example 1 (polycarbonate urethane resin (anionic self-emulsifying type))
In a four-necked flask equipped with a stirrer, reflux condenser, thermometer, and nitrogen blowing tube, 97.5 g of polyhexamethylene carbonate diol (average molecular weight 2000), 7.2 g of dimethylolbutanoic acid, 1,4-butanediol 1 0.5 g, 0.005 g of dibutyltin dilaurate and 61.0 g of methyl ethyl ketone, and after uniform mixing, add 36.1 g of isophorone diisocyanate and react at 180 ° C. for 180 minutes to have a free isocyanate group content of 2.9% relative to the non-volatile content. A methyl ethyl ketone solution of a urethane prepolymer was obtained. This solution was neutralized with 4.8 g of triethylamine, transferred to another container, and emulsified and dispersed using a disper blade while gradually adding 362 g of water at 30 ° C. or lower. To this, 14.5 g of a 20% by mass aqueous solution of ethylenediamine was added and reacted for 90 minutes. Next, the obtained polyurethane resin dispersion was desolvated at 50 ° C. under reduced pressure to obtain an aqueous polyurethane resin emulsion dispersion having a nonvolatile content of 30% by mass of the polyurethane resin.

Synthesis example 2 (polyether urethane resin (anionic self-emulsifying type))
In a reactor similar to that used in Synthesis Example 1, 95.4 g of polypropylene glycol (average molecular weight 2000), 7.1 g of dimethylolbutanoic acid, 0.005 g of dibutyltin dilaurate and 59.2 g of methyl ethyl ketone were taken and mixed uniformly. Then, 35.7 g of dicyclohexylmethane diisocyanate was added and reacted at 80 ° C. for 200 minutes to obtain a methyl ethyl ketone solution of urethane prepolymer having a free isocyanate group content of 2.5% based on the nonvolatile content. This solution was neutralized with 4.8 g of triethylamine and then transferred to another container, and emulsified and dispersed using a disper blade while gradually adding 356 g of water at 30 ° C. or lower. To this was added 23.2 g of a 30% by weight aqueous solution of isophorone diamine and allowed to react for 90 minutes. Next, the obtained polyurethane resin dispersion was subjected to solvent removal at 50 ° C. under reduced pressure to obtain a polyurethane resin aqueous dispersion having a polyurethane resin nonvolatile content of 30% by mass.

Comparative synthesis example 1 (polycarbonate urethane resin (non-ion forced emulsification type))
In a reactor similar to that used in Synthesis Example 1, 195 g of polyhexamethylene carbonate diol (average molecular weight 2000), 1.5 g of 1,4-butanediol, 0.005 g of dibutyltin dilaurate and 61.0 g of methyl ethyl ketone were taken. After uniform mixing, 36.1 g of isophorone diisocyanate was added and reacted at 80 ° C. for 60 minutes to obtain a methyl ethyl ketone solution of a urethane prepolymer having a free isocyanate group content of 1.8% based on the nonvolatile content. This solution was transferred to a separate container, charged with 19.6 g of TSP20E at 30 ° C. or lower, and emulsified and dispersed using a disper blade while gradually adding 501 g of water after homogenization. To this, 14.5 g of a 20% by mass aqueous solution of ethylenediamine was added and reacted for 90 minutes. Next, the obtained polyurethane resin dispersion was desolvated at 50 ° C. under reduced pressure to obtain a polyurethane resin aqueous emulsion dispersion having a nonvolatile content of 32.5% by mass (a polyurethane resin having a nonvolatile content of 30% by mass). .

Comparative synthesis example 2 (polyester urethane resin (solvent type))
170 parts by mass of polycaprolactone diol (average molecular weight 2000), 0.3 parts by mass of butyl phosphate ester and 43,2 parts by mass of dimethylformamide were added to the same reactor as that used in Synthesis Example 1, and melted by heating and mixed. Uniform. At 30 ° C. or less, 100.7 parts by mass of diphenylmethane diisocyanate and 43.2 parts by mass of dimethylformamide were added to obtain a uniform mixture. At 30 ° C. or less, 21.1 parts by mass of ethylene glycol and 87 parts by mass of dimethylformamide were added to make the mixture uniform, and the reaction was carried out at 85 ± 5 ° C. for 1 hour. At 30 ° C. or lower, 2.7 parts by mass of diphenylmethane diisocyanate and 174 parts by mass of dimethylformamide were added and reacted at 85 ± 5 ° C. for 1 hour. Then, 2.7 parts by mass of diphenylmethane diisocyanate and 174 parts by mass of dimethylformamide were added at 30 ° C. or less, and the reaction was allowed to proceed at 85 ± 5 ° C. for 1 hour, and was further performed twice.
4.7 parts by mass of MEK oxime was added and cooled to obtain a polyurethane resin solution having a nonvolatile content of 30% by mass of the polyurethane resin.

Example 1
As component (A), 2.4 parts by mass of the emulsified dispersion of Production Example 1 (1.2 parts by mass as phenoxyphosphazene), and as component (B), 37.6 parts by mass of the emulsified dispersion of Production Example 5 (Resocinol bis 18.8 parts by mass as dixylenyl phosphate), 1 part by mass of Neo sticker V-500 (manufactured by Nikka Chemical Co., Ltd.) as component (C) (0.3 parts by mass as alkali thickening acrylic resin), As the component (D), 40 parts by mass of the polycarbonate-based polyurethane resin water-emulsified dispersion obtained in Synthesis Example 1 (12 parts by mass as the polyurethane resin), 0.1 part by mass of 25% ammonia water, and 18.9% of the water as the component (E). The flame retardant coating agent was obtained by putting the mass part in a mixing kettle and mixing and stirring to make it uniform. The flame retardant coating agent had a viscosity of 16,000 mPa · s, a PVI value of 0.20, an average particle size of 20 μm, and a pH of 8.0.

Next, the applied amount (DRY) is applied to one surface of a plain woven fabric (dyed and soaped) having a warp density of 60 yarns / 吋 and a weft density of 60 yarns / 吋 made of polyester multifilament yarn 167dtex36f and a basis weight of 280 g / m ^2. The flame retardant coating agent was treated with a knife coater so as to be 65 ± 5 g / m ² and dried at 150 ° C. for 3 minutes to produce a flame retardant sheet material. The applied amount was determined by calculating from (mass of flame retardant sheet material−mass of sheet material) ÷ dough area.
About the obtained flame retardant sheet material, flame retardancy, hot water wrinkle (treated surface), hot water wrinkle (opposite surface), back-through, friction fastness (dry type), bending resistance, haze (glass) Table 1 shows the results of evaluation of the degree of seam fatigue and the resistance to seam fatigue.

Examples 2-32 and Comparative Examples 1-3
The component (A), component (B), component (C), component (D), component (E) and 25% aqueous ammonia were changed to the compositions shown in Tables 1 to 4, and component (F) was used in some cases. Except for the above, the same operation as in Example 1 was carried out to obtain flame retardant sheet materials of Examples 2-32 and Comparative Examples 1-3. The values of the components (A), (B), (C), (D), and (F) in the table are blending ratios of the respective components in terms of nonvolatile content. About these flame retardant sheet materials, flame retardancy, hot water wrinkle (treated surface), hot water wrinkle (opposite surface), back-through, friction fastness (dry type), bending resistance, haze (glass haze) Tables 1 to 4 show the results of the evaluation of seam fatigue resistance.

Comparative Examples 4-13
(A) component, (B) component, (C) component, (D) component, (E) component, (F) component, and 25% ammonia water are changed into the composition shown in Table 4, and also the other described in Table 4 Except having used this compound, operation was performed in the same manner as in Example 1 to obtain flame retardant sheet materials of Comparative Examples 4 to 13. About this flame retardant sheet material, flame retardancy, hot water wrinkle (treated surface), hot water wrinkle (opposite surface), back-through, friction fastness (dry), bending resistance, haze (glass haze) Table 4 shows the results of evaluation of the anti-seam fatigue resistance.

Comparative Example 14
40 parts by mass of ammonium polyphosphate, 5 parts by mass of tricresyl phosphate, 0.37 parts by mass of neo sticker N (0.11 parts by mass as urethane-modified activator), 20 parts by mass of acrylic resin aqueous solution (10 parts by mass as acrylic resin) ) And 34.63 parts by weight of water were placed in a mixing kettle and mixed and stirred to obtain a flame retardant coating agent. Using this flame retardant coating agent, the same operation as in Example 1 was performed to obtain a flame retardant sheet material of Comparative Example 14. About this flame retardant sheet material, flame retardancy, hot water wrinkle (treated surface), hot water wrinkle (opposite surface), back-through, friction fastness (dry), bending resistance, haze (glass haze) Table 4 shows the results of evaluation of the anti-seam fatigue resistance.

Comparative Example 15
5 parts by mass of resorcinol bis-dixylenyl phosphate, 1.67 parts by mass of neo-sticker V-500 (0.5 parts by mass as alkali thickening acrylic resin), 18 parts by mass of ammonium polyphosphate, 23 of Sumikaflex 478HQ .3 parts by mass (14 parts by mass as ethylene vinyl acetate resin), 0.1 part by mass of 25% aqueous ammonia and 51.93 parts by mass of water were placed in a mixing vessel to obtain a flame retardant coating agent with uniform mixing and stirring. Using this flame retardant coating agent, the same operation as in Example 1 was performed to obtain a flame retardant sheet material of Comparative Example 15. About this flame retardant sheet material, flame retardancy, hot water wrinkle (treated surface), hot water wrinkle (opposite surface), back-through, friction fastness (dry), bending resistance, haze (glass haze) Table 4 shows the results of evaluation of the anti-seam fatigue resistance.

Comparative Example 16
18 parts by mass of phenoxyphosphazene, 60 parts by mass of aluminum hydroxide, 7.5 parts by mass of tricresyl phosphate, 15 parts by mass of melamine polyphosphate, 100 parts by mass of polyurethane solution of Comparative Synthesis Example 2 (30 parts by mass as polyurethane resin) and dimethyl An appropriate amount of formamide was put in a mixing kettle and mixed and stirred to obtain a flame-retardant coating agent having a viscosity of 8000 mPa · s. Using this flame retardant coating agent, the same operation as in Example 1 was performed to obtain a flame retardant sheet material of Comparative Example 16. About this flame retardant sheet material, flame retardancy, hot water wrinkle (treated surface), hot water wrinkle (opposite surface), back-through, friction fastness (dry), bending resistance, haze (glass haze) Table 4 shows the results of evaluation of the anti-seam fatigue resistance.

Comparative Example 17
5 parts by mass of aluminum hydroxide, 20 parts by mass of aluminum ethylmethylphosphinate, 0.5 parts by mass of TSP20E and 31.8 parts by mass of water were charged into a mixing kettle and dispersed uniformly. Next, 41.7 parts by mass of FX2555A (25 parts by mass as a resin component) and 1 part by mass of hydroxyethylcellulose were charged, mixed and stirred to obtain a flame retardant coating agent. Using this flame retardant coating agent, the same operation as in Example 1 was performed to obtain a flame retardant sheet material of Comparative Example 17. About this flame retardant sheet material, flame retardancy, hot water wrinkle (treated surface), hot water wrinkle (opposite surface), back-through, friction fastness (dry), bending resistance, haze (glass haze) Table 4 shows the results of evaluation of the anti-seam fatigue resistance.

  INDUSTRIAL APPLICABILITY The present invention is industrially useful because it can provide a flame retardant sheet material that is excellent in flame retardancy and texture, and that suppresses the occurrence of cracking through and the occurrence of sticking to hot water.

Claims (5)

It consists of at least one compound (A) selected from the group consisting of phosphazene compounds represented by the following general formulas (1) and (2), and phosphorus compounds represented by the following general formulas (3) to (6). Flame retardant comprising at least one compound (B) selected from the group, an alkali-thickening acrylic resin (C), a self-emulsifiable aqueous polyurethane resin (D) having an anionic group, and water (E) Coating agent.

(In the above formula, X ¹ and X ² each independently have an alkyloxy group having 1 to 18 carbon atoms, an alkenyloxy group having 2 to 18 carbon atoms, or an alkyl group having 1 to 4 carbon atoms. Represents an aryloxy group having 6 to 14 carbon atoms, and m represents an integer of 3 to 25)

(In the above formula, X ¹ and X ² each independently have an alkyloxy group having 1 to 18 carbon atoms, an alkenyloxy group having 2 to 18 carbon atoms, or an alkyl group having 1 to 4 carbon atoms. Represents an aryloxy group having 6 to 14 carbon atoms, Y represents an (X ¹ or X ² ) ₃ P═N— group, or an (X ¹ or X ² ) (O) P═N— group, and Z Represents (X ¹ or X ² ) ₄ P-group or (X ¹ or X ² ) ₂ (O) P- group, and n represents an integer of 3 to 1000)

(In the above formula, R ¹ and R ² may each independently have a phenyl group optionally having an alkyl group having 1 to 4 carbon atoms, or an alkyl group having 1 to 4 carbon atoms. Represents a naphthyl group, E represents a direct bond, —O— or —N (H) —, a represents 1 or 2, and b represents 0 or 1.

(In the above formula, R ³ represents a benzyl group, a methylbenzyl group, a phenethyl group, a naphthylmethyl group, or a group represented by the following formula (7)).

(In the above formula, R ⁴ represents an alkyl group having 1 to 10 carbon atoms, a phenyl group, or a benzyl group)

(In the above formula, R ^{5 to} R ⁸ each independently represent a phenyl group having an alkyl group having 1 to 4 carbon atoms, R ⁹ represents an arylene group which may have a substituent, and c represents Represents an integer of 1 to 5)

(In the above formula, R ¹⁰ and R ¹¹ each independently represents an alkyl group having 1 to 4 carbon atoms,
R ¹² represents a biphenyl group or a naphthyl group)   The alkali-thickened acrylic resin (C) is a polymer of a monomer composition containing at least one monomer selected from the group consisting of a carboxyl group-containing monomer and a (meth) acrylic acid ester monomer. The flame retardant coating agent described.   The self-emulsifiable aqueous polyurethane resin (D) having the anionic group is reacted with (a) a polyisocyanate, (b) a polyol, and (c) a compound having an anionic group and two or more active hydrogens. The resulting neutralized isocyanate group-terminated prepolymer having an anionic group is emulsified and dispersed in water by self-emulsification, and (d) a chain extension reaction is performed using a polyamine compound having two or more amino groups and / or imino groups. The flame-retardant coating agent according to claim 1, which is an aqueous polyurethane resin having an anionic group obtained by the above method.   Compounding ratio (A) :( B) :( C) of the phosphazene compound (A), phosphorus compound (B), alkali-thickened acrylic resin (C) and self-emulsifiable aqueous polyurethane resin (D) having an anionic group ): (D) is a flame retardant coating agent according to any one of claims 1 to 3, wherein the mass ratio is 20 to 200: 10 to 250: 0.5 to 25: 100.   The flame retardant coating agent according to any one of claims 1 to 4 is treated on one side of the sheet material and then dried, and then the treated surface of the sheet material and / or the sheet material contains the phosphazene compound. A flame retardant sheet is formed by forming a flame retardant coating containing (A), a phosphorus compound (B), an alkali thickening acrylic resin (C) and a self-emulsifiable aqueous polyurethane resin (D) having an anionic group. A method for producing a flame-retardant sheet material, characterized in that the material is obtained.