Flame-retardant composition for textile materials, flame-retardant textile material, and method for producing flame-retardant textile material

Abstract

To provide a flame-retardant composition for textile materials that can impart excellent flame retardancy and resistance to surface adhesion to textile materials. [Solution] A flame-retardant composition for fiber materials comprising (A) a water-dispersible polyurethane resin and (B) an aliphatic phosphate amide compound, wherein (A) the water-dispersible polyurethane resin is a water-dispersible polyurethane resin obtained by reacting an isocyanate-terminated prepolymer with a chain extender in water, the isocyanate-terminated prepolymer is a prepolymer obtained by reacting (a) an organic polyisocyanate compound with (b) a high molecular weight polyol having a number average molecular weight of 400 to 5000 and (c) a compound having a carboxyl group or carboxylate group and at least two active hydrogens, and the chain extender comprises at least one selected from the group consisting of water-soluble polyamines, hydrazines and their derivatives, in a flame-retardant composition for fiber materials.

Description

[Technical Field]

[0001] This disclosure relates to a flame-retardant composition for textile materials, a flame-retardant textile material, and a method for producing a flame-retardant textile material. [Background technology]

[0002] Flame retardancy is sometimes required for automotive seat materials, railway car seat materials, and other vehicle seat materials, as well as for textile products such as nonwoven fabrics and felts used in the low-voltage electrical field. In flame retardant processing, which imparts flame retardancy to the fiber material contained in textile products, for example, halogen-based compounds or non-halogen-based compounds are used as flame retardants, along with resins and other binder components to adhere the flame retardants to the fibers.

[0003] For example, Patent Document 1 discloses a flame-retardant resin composition characterized by containing at least one resin emulsion (a) selected from acrylic resin emulsions and urethane resin emulsions, a polyester resin emulsion (b), a liquid phosphorus-based flame retardant (c), and a surfactant having an aromatic group (d). [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2018-058916 [Patent Document 2] International Publication No. 2015 / 064018 [Patent Document 3] International Publication No. 2014 / 002958 [Patent Document 4] International Publication No. 2008 / 085926 [Patent Document 5] U.S. Patent No. 3,887,655 [Overview of the project] [Problems that the invention aims to solve]

[0005] However, the flame-retardant resin composition disclosed in Patent Document 1 has a problem that it is difficult to ensure excellent flame retardancy and resistance to fraying in fiber materials.

[0006] The present disclosure has been made in view of the above circumstances, and provides a flame-retardant composition for fiber materials capable of imparting excellent flame retardancy and resistance to fraying to fiber materials. The present disclosure also provides a flame-retardant fiber material having excellent flame retardancy and resistance to fraying and a method for producing the same.

Means for Solving the Problems

[0007] The inventors of the present invention have intensively studied to solve the above problems. As a result, the inventors have found that a composition containing a specific water-dispersible polyurethane resin and a specific aliphatic phosphoric acid amide compound can impart excellent flame retardancy and resistance to fraying to fiber materials, and have completed the present invention.

[0008] The present disclosure includes the following embodiments [1] to [9]. [1] A flame-retardant composition for fiber materials containing (A) a water-dispersible polyurethane resin and (B) an aliphatic phosphoric acid amide compound, wherein the above (A) water-dispersible polyurethane resin is a water-dispersible polyurethane resin obtained by reacting an isocyanate group-terminated prepolymer and a chain extender in water, the above isocyanate group-terminated prepolymer is a prepolymer obtained by reacting (a) an organic polyisocyanate compound, (b) a high molecular weight polyol having a number average molecular weight of 400 to 5000, and (c) a compound having a carboxyl group or carboxylate group and at least two active hydrogens, the above chain extender contains at least one selected from the group consisting of water-soluble polyamines, hydrazine, and their derivatives, a flame-retardant composition for fiber materials. [2] The flame-retardant composition for fiber materials according to [1], wherein the above (B) aliphatic phosphoric acid amide compound contains a compound represented by the following general formula (I).

Chemical formula

[0009] This disclosure provides a flame-retardant composition for textile materials that can impart excellent flame retardancy and stain resistance to textile materials. Furthermore, this disclosure provides a flame-retardant textile material having excellent flame retardancy and stain resistance, and a method for producing the same. [Modes for carrying out the invention]

[0010] Preferred embodiments of this disclosure are described in detail below. However, this disclosure is not limited to the embodiments described below.

[0011] [Flame-retardant composition for textile materials] The following describes a flame-retardant composition for textile materials according to one embodiment. The flame-retardant composition for textile materials according to this embodiment comprises (A) a water-dispersible polyurethane resin and (B) an aliphatic phosphate amide compound. The water-dispersible polyurethane resin is obtained by reacting an isocyanate-terminated prepolymer with a chain extender in water. The isocyanate-terminated prepolymer is a prepolymer obtained by reacting (a) an organic polyisocyanate compound, (b) a high molecular weight polyol having a number average molecular weight of 400 to 5000, and (c) a compound having a carboxyl group or carboxylate group and at least two active hydrogens. The chain extender comprises at least one selected from the group consisting of water-soluble polyamines, hydrazines, and their derivatives. By using the water-dispersible polyurethane resin obtained in this combination in combination with an aliphatic phosphate amide compound, the flame-retardant composition according to this embodiment can impart excellent flame retardancy and anti-sticking properties to textile materials. The reason for obtaining such effects is not clear, but the inventors speculate as follows. In other words, by combining (A) a water-dispersible polyurethane resin and (B) an aliphatic phosphate amide compound, the (B) aliphatic phosphate amide compound is uniformly and stably dispersed in the (A) water-dispersible polyurethane resin, allowing it to adhere uniformly to the fiber material. As a result, flame retardancy is stabilized. Furthermore, regarding resistance to staining, staining can occur when water comes into contact with the (B) aliphatic phosphate amide compound. By combining (A) a water-dispersible polyurethane resin and (B) an aliphatic phosphate amide compound, the (A) water-dispersible polyurethane resin plays a role in preventing contact between the (B) aliphatic phosphate amide compound and water, and a uniform film of the flame-retardant composition is formed on the fiber material. As a result, resistance to staining is improved.

[0012] (a) The organic polyisocyanate compound (hereinafter also referred to as "component (a)") can be any organic compound having two or more isocyanate groups without particular limitations. However, blocked isocyanate compounds in which the isocyanate groups are protected by a blocking agent can also be used as component (a).

[0013] Examples of organic polyisocyanate compounds include aliphatic diisocyanate compounds, alicyclic diisocyanate compounds, or aromatic diisocyanate compounds. Preferred examples of aliphatic diisocyanates include tetramethylene diisocyanate, hexamethylene diisocyanate, dodecamethylene diisocyanate, trimethylhexamethylene diisocyanate, and lysine diisocyanate. Preferred examples of alicyclic diisocyanate compounds include isophorone diisocyanate, hydrogenated xylylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 3,3'-dimethyl-4,4'-dicyclohexylmethane diisocyanate, and norbornane diisocyanate. Suitable examples of aromatic diisocyanates include m-phenylenediisocyanate, p-phenylenediisocyanate, 2,4-tolinediisocyanate, 2,6-tolinediisocyanate, 4,4'-diphenylmethanediisocyanate, 2,4'-diphenylmethanediisocyanate, 3,3'-dimethyl-4,4'-biphenylenediisocyanate, 3,3'-dichloro-4,4'-biphenylenediisocyanate, 1,5-naphthalenediisocyanate, tolidinediisocyanate, tetramethylenexylylenediisocyanate, and xylylenediisocyanate. Among these, aliphatic diisocyanate compounds and alicyclic diisocyanate compounds can be suitably used from the viewpoint of less discoloration due to ultraviolet light and nitrogen oxide gas, and slow reaction between the isocyanate group and water, which is advantageous for obtaining an aqueous dispersion. Among these, isophorone diisocyanate and dicyclohexylmethane diisocyanate are particularly preferred. These organic polyisocyanate compounds can be used individually or in combination of two or more.

[0014] (b) High molecular weight polyols (hereinafter also referred to as "component (b)") are compounds having two or more hydroxyl groups and a number average molecular weight of 400 to 5000. Examples of high molecular weight polyols having two hydroxyl groups include polyester diols, polyether diols, polycarbonate diols, and dimer ols.

[0015] Suitable examples of polyester diols include aliphatic polyester diols such as polyethylene adipate diol, polyethylene propylene adipate diol, polybutylene adipate diol, polyhexamethylene adipate diol, polydiethylene adipate diol, polyethylene terephthalate diol, polyethylene succinate diol, polybutylene succinate diol, polyethylene sebacate diol, polybutylene sebacate diol, poly-ε-caprolactam diol, polyethylene isophthalate diol, and poly(3-methyl-1,5-pentylene adipate), as well as aromatic polyester diols such as polyhexamethylene isophthalate diol, 3-methyl-1,5-pentane isophthalate diol, and 3-methyl-1,5-pentane terephthalate diol.

[0016] Preferred examples of polyetherdiols include polyoxytetramethylene glycol, polyoxypropylene glycol, polyoxyethylene glycol, and polyoxyethylene-propylene glycol.

[0017] Suitable examples of polycarbonate diols include polytetramethylene carbonate diol, polyhexamethylene carbonate diol, 3-methyl-1,5-pentane carbonate diol, and poly-1,4-cyclohexanedimethylene carbonate diol.

[0018] A suitable example of a dimer ol is one in which the diol obtained by reducing polymerized fatty acids is the main component. These polymerized fatty acids are obtained, for example, by a Diels-Alder type bimolecular polymerization reaction of carbon-18 unsaturated fatty acids such as oleic acid and linoleic acid, drying oil fatty acids, semi-drying oil fatty acids, or lower monoalcohol esters thereof, with or without a catalyst. Various types of polymerized fatty acids are commercially available, but a typical example is one consisting of 0-5% by mass of carbon-18 monocarboxylic acid, 70-98% by mass of carbon-36 dimer acid, and 0-30% by mass of carbon-54 trimer acid.

[0019] The high molecular weight polyols listed above, and others, can be used individually or in combination of two or more. In particular, polycarbonate diols and aromatic polyester diols are preferably used from the viewpoint of hydrolysis resistance, light resistance, and heat resistance.

[0020] (b) The number average molecular weight of component (b) may be 400 or more, 800 or more, or 1000 or more, and may be 5000 or less, 4000 or less, or 3000 or less. (b) From the viewpoint of texture, the number average molecular weight of component (b) is preferably 1000 or more and 3000 or less. (b) The number average molecular weight of component (b) is a value converted using a calibration curve with a standard substance (polyethylene glycol) measured by GPC (Gel Permeation Chromatography) under the following conditions. (conditions) Device: HLC-8220GPC (product name, manufactured by Tosoh Corporation) Mobile phase: Tetrahydrofuran (THF) Columns: Tsk-gel SuperHZ2000 x 25cm x 2 / SuperHZ4000 x 15cm x 1

[0021] (c) Compounds having a carboxyl group or carboxylate group and at least two active hydrogens (hereinafter also referred to as "component (c)") are compounds that have a functional group having active hydrogens in addition to the carboxyl group. If the compound of component (c) has a carboxylate group, the carboxylate group forms a carboxylate salt. Preferred specific examples of component (c) include 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, 2,2-dimethylolheptanoic acid and their ammonium salts, organic amine salts, or alkali metal salts. Organic amines that constitute organic amine salts include trimethylamine, triethylamine, tri-n-propylamine, tributylamine, triethanolamine, N,N-dimethyldiethanolamine, and N,N-diethylethanolamine. Alkali metals that constitute alkali metal salts include sodium and potassium. These compounds can be used individually or in combination of two or more. Alternatively, after generating an isocyanate-terminated prepolymer using a compound having a carboxyl group, the carboxyl group may be converted to a carboxylate salt such as an ammonium salt, organic amine salt, or alkali metal salt by neutralization.

[0022] (c) The content of carboxyl groups or carboxylate groups derived from the compound of component (c) relative to the polyurethane resin is preferably 0.5 to 2% by mass. When this content is 0.5% by mass or more, sufficient emulsification stability tends to be ensured. When this content is 2% by mass or less, the hydrophilicity of the polyurethane resin does not become too high, the friction fastness improves, and the viscosity of the aqueous dispersion does not become too high, ensuring sufficient handling.

[0023] When synthesizing isocyanate-terminated prepolymers, the chain extender (d) may be reacted together with the components (a), (b), and (c) above. As the chain extender, a compound having two functional groups that react with the isocyanate group is used. Specifically, low molecular weight polyols or low molecular weight polyamines are preferably used. Low molecular weight polyols and low molecular weight polyamines are compounds with approximately 10 or fewer carbon atoms. Suitable examples of low molecular weight polyols include ethylene glycol, diethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, trimethylolpropane, pentaerythritol, and sorbitol. Suitable examples of low molecular weight polyamines include ethylenediamine, propylenediamine, hexamethylenediamine, diaminocyclohexylmethane, piperazine, 2-methylpiperazine, isophoronediamine, diethylenetriamine, and triethylenetetramine. These chain extenders can be used individually or in combination of two or more.

[0024] The method for producing an isocyanate-terminated prepolymer using (a) an organic polyisocyanate, (b) a high molecular weight polyol, and (c) a compound having a carboxyl group or carboxylate group and at least two active hydrogens, or (a) an organic polyisocyanate, (b) a high molecular weight polyol, (c) a compound having a carboxyl group or carboxylate group and at least two active hydrogens, and (d) a chain extender is not particularly limited, and as will be understood by those skilled in the art, commonly used methods may be employed as appropriate.

[0025] For example, the reaction can be carried out at a temperature of 40 to 150°C by a one-shot (single-stage) or multi-stage isocyanate polyaddition reaction. In this case, reaction catalysts such as dibutyltin dilaurate, stanus octoate, dibutyltin-2-ethylhexoate, triethylamine, triethylenediamine, and N-methylmorpholine, or reaction inhibitors such as phosphoric acid, sodium hydrogen phosphate, and p-toluenesulfonic acid may be added as needed. Furthermore, an organic solvent that does not react with the isocyanate group may be added during or after the reaction. Examples of such organic solvents include acetone, methyl ethyl ketone, methyl isobutyl ketone, toluene, xylene, tetrahydrofuran, dioxane, dimethylformamide, N-methylpyrrolidone, ethyl acetate, and butyl acetate. Among these organic solvents, methyl ethyl ketone, toluene, and ethyl acetate are particularly preferred. These organic solvents can be easily removed by heating under reduced pressure after emulsification, dispersion, and chain extension of the prepolymer. The carboxyl groups of the resulting prepolymer may be neutralized by a reaction with ammonia, organic amines, etc., to produce a neutralized product, which may then be reacted with a chain extender to produce a polyurethane resin.

[0026] In the reaction to produce isocyanate-terminated prepolymers, the charging ratios of each raw material are adjusted so that the NCO / OH (molar ratio) is preferably in the range of 1.1 / 1.0 to 1.7 / 1.0, and more preferably in the range of 1.2 / 1.0 to 1.5 / 1.0.

[0027] The content of free isocyanate groups in the isocyanate-terminated urethane prepolymer at the end of the reaction is preferably 0.8 to 5.0% by mass relative to the total isocyanate-terminated prepolymer. When the content of free isocyanate groups is 0.8% by mass or more, a significant increase in viscosity during the reaction is suppressed, thus reducing the need for a large amount of organic solvent and lowering manufacturing costs, and also tends to allow for sufficient emulsification and dispersion. On the other hand, when the content of free isocyanate groups is 5.0% by mass or less, the balance after emulsification and dispersion and after the chain extension reaction with the chain extender does not change significantly, so it tends to ensure sufficient storage stability and processing stability of the flame-retardant composition over time.

[0028] Water-dispersible polyurethane resins are obtained by adding at least one chain extender selected from the group consisting of water-soluble polyamines, hydrazines, and their derivatives to a reaction solution in which an isocyanate-terminated urethane prepolymer is emulsified and dispersed in water, and allowing the chain extension reaction to proceed in water, thereby obtaining the resin in the form of an aqueous dispersion.

[0029] More specifically, for example, an isocyanate-terminated urethane prepolymer is mixed with an emulsifier as needed, and the mixture is emulsified and dispersed in water using a homomixer or homogenizer, after which a chain extender is added. The emulsification and dispersion is preferably carried out at a temperature range of room temperature to 40°C in order to minimize the reaction between the isocyanate groups in the isocyanate-terminated urethane prepolymer and water. Reaction inhibitors such as phosphoric acid and sodium hydrogen phosphate may be added to the reaction solution.

[0030] The emulsifiers used may be those that are conventionally known, such as polyoxyethylene alkyl ethers and their fatty acid esters or aromatic carboxylic acid esters; polyoxyalkylene glycols such as polyoxyethylene glycol and polyoxyethylene polyoxypropylene block polymer and their fatty acid esters; nonionic surfactants such as polyoxyethylene alkylphenyl ethers and polyoxyethylene styrene phenyl ether derivatives and their fatty acid esters; and anionic surfactants such as sulfated polyoxyethylene alkyl ethers, polyoxyalkylene glycols or polyoxyalkylene ether derivatives and aromatic sulfonic acids. The amount of these emulsifiers used is preferably 5% by mass or less relative to the urethane prepolymer in order to ensure good friction fastness.

[0031] Examples of water-soluble polyamines used as chain extenders include ethylenediamine, propylenediamine, tetramethylenediamine, hexamethylenediamine, diaminocyclohexylmethane, hydrazine, piperazine, 2-methylpiperazine, tolylenediamine, xylylenediamine, isophoronediamine, norbornanediamine, diethylenetriamine, and triethylenetetramine. Derivatives of water-soluble polyamines include amideamines obtained by reacting a compound having two primary amines with a monocarboxylic acid, and monokethimines of compounds having two primary amines.

[0032] As the hydrazine used as a chain extender, for example, 1,1'-ethylenedihydrazine, 1,1'-trimethylenedihydrazine, and 1,1'-(1,4-butylene)dihydrazine, which are aliphatic water-soluble dihydrazine compounds having 2 or more hydrazino groups and having 2 to 4 carbon atoms, and oxalic acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, glutaric acid dihydrazide, adipic acid dihydrazide, sebacic acid dihydrazide, maleic acid dihydrazide, fumaric acid dihydrazide, and itaconic acid dihydrazide, which are dihydrazide compounds of dicarboxylic acids having 2 to 10 carbon atoms, can be mentioned. These chain extenders are used alone or in combination of two or more. [[ID=~2]]

[0033] The reaction between the isocyanate group-terminated urethane prepolymer and the chain extender is typically completed by mixing the isocyanate group-terminated urethane prepolymer and the chain extender and reacting them at a temperature of 20 to 50°C for 30 to 120 minutes. At this time, it is preferable to use a chain extender containing 0.9 to 1.1 equivalents of an amino group or a hydrazino group with respect to the free isocyanate groups in the isocyanate group-terminated urethane prepolymer.

[0034] Examples of the aliphatic phosphoric acid amide compound include an aliphatic phosphoric acid amide compound represented by the following general formula (I), an aliphatic phosphoric acid amide compound having a functional group described in International Publication No. 2008 / 085926, and a bromine-containing aliphatic phosphoric acid amide compound described in US Patent No. 3887655.

[0035] [Chemical formula] [In the formula, R1 and R2 are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R 11 and R 12 are each independently an alkylene group having 1 to 3 carbon atoms, R 13 is an alkylene group having 1 to 6 carbon atoms, B1 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and A is a hydrogen atom or a general formula (II) [Chemical formula] (In the formula, R3 and R4 are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R 14 and R 15 Each of the following is an organic group represented by an alkylene group having 1 to 3 carbon atoms, B2 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and * is a bond. Here, if A is a hydrogen atom and B1 is an alkyl group having 1 to 6 carbon atoms, then B1 and R 13 -A may bond with the nitrogen atom to which it is bonded, forming a nitrogen-containing heterocycle. If A is an organic group represented by general formula (II), B2 is an alkyl group having 1 to 6 carbon atoms, and B1 is an alkyl group having 1 to 6 carbon atoms, then B1 and B2 are bonded together, and the nitrogen atom to which they are bonded and R 13 They may also form a nitrogen-containing heterocycle together.

[0036] Examples of C1-C3 alkyl groups in general formula (I) include methyl, ethyl, n-propyl, and isopropyl groups. Among these, methyl and ethyl groups are preferred, and methyl is particularly preferred because it tends to further improve flame retardancy. Examples of C1-C3 alkylene groups include methylene, ethylene, 1,3-propylene, and 1,2-propylene groups. Among these, methylene and ethylene groups are preferred, and methylene is particularly preferred because it tends to further improve flame retardancy.

[0037] Examples of alkyl groups having 1 to 6 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, and n-hexyl groups. Among these, methyl and ethyl groups are preferred, and methyl groups are particularly preferred because they tend to further improve flame retardancy. Examples of alkylene groups having 1 to 6 carbon atoms include methylene, ethylene, 1,3-propylene, 1,2-propylene, 1,4-butylene, 1-methyl-1,3-propylene, 2-methyl-1,3-propylene, 1,1-dimethylethylene, 1,2-dimethylethylene, 1,5-pentylene, and 1,6-hexylene groups. Among these, alkylene groups having 4 or fewer carbon atoms are preferred, and methylene and ethylene groups are particularly preferred because they tend to further improve flame retardancy.

[0038] The nitrogen-containing heterocycle formed when A is a hydrogen atom is a heterocycle with 3 to 13 members, preferably 4 to 8 members, containing one nitrogen atom.

[0039] When A is an organic group represented by general formula (II), the nitrogen-containing heterocycle formed is a heterocycle containing two nitrogen atoms, with 5 to 20 members, preferably 5 to 8 members.

[0040] Aliphatic phosphate amide compounds represented by general formula (I) include compounds represented by general formulas (III) to (VI). In general formula (III), A is a hydrogen atom in general formula (I). In general formula (IV), B1 is an alkyl group having 1 to 6 carbon atoms in general formula (I), and A is a hydrogen atom, and B1 and R 13 -A is bonded to it, and together with the nitrogen atom to which they are bonded, they form a nitrogen-containing heterocycle. General formula (V) is in general formula (I), where A is the organic group represented by general formula (II), and B1 and B2 are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. General formula (VI) is in general formula (I), where B1 is an alkyl group having 1 to 6 carbon atoms, and A is the organic group represented by general formula (II), and B2 is an alkyl group having 1 to 6 carbon atoms, and B1 and B2 are bonded to it, and together with the nitrogen atom to which they are bonded and R13 Together with it, it forms a nitrogen-containing heterocycle.

[0041] [ka] [In the formula, R1, R2, R 11 , and R 12 The definition is the same as that of general formula (I), where R5 is an alkyl group having 1 to 6 carbon atoms, and R6 is an alkyl group having 1 to 6 carbon atoms or a hydrogen atom.

[0042] [ka] [In the formula, R1, R2, R 11 , and R 12 This is the same as the definition of general formula (I), and R 16 This is an alkylene group with 2 to 12 carbon atoms.

[0043] [ka]

[0044] [In the formula, R1, R2, R 11 , R 12 , and R 13 This is the same as the definition of general formula (I), and R3, R4, R 14 , and R 15 The definition is the same as that of general formula (II), and R7 and R8 are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

[0045] [ka] [In the formula, R1, R2, R 11 , R 12 , and R 13 This is the same as the definition of general formula (I), and R3, R4, R 14 , and R 15 This is the same as the definition of general formula (II), and R 17This is an alkylene group with 2 to 12 carbon atoms.

[0046] Among aliphatic phosphate amide compounds represented by general formula (I), R1 and R2 are methyl groups, as R tends to exhibit even greater flame retardancy. 11 and R 12 A compound in which the group is a methylene group is preferred.

[0047] In general formula (I), A is preferably an organic group represented by general formula (II), and since this tends to further improve flame retardancy, R3 and R4 are methyl groups, and R 14 and R 15 It is preferable that it is a methylene group.

[0048] R in general formula (I) 13 Since this tends to further improve flame retardancy, the carbon number is preferably 1 to 4, and more preferably 1 to 2.

[0049] In the case of an aliphatic phosphate amide compound represented by general formula (I), when A is an organic group represented by general formula (II), B1 of general formula (I) and B2 of general formula (II) tend to have even greater flame retardancy, so if they are not bonded, they are preferably hydrogen atoms, and if they are bonded, they form an ethylene group, and the nitrogen atom and R to which these are bonded 13 It is preferable that they combine to form a 5-8 member nitrogen-containing heterocycle.

[0050] Aliphatic phosphate amide compounds represented by general formula (I) tend to exhibit further improved flame retardancy and stain resistance, therefore compounds represented by the following formulas (B1) to (B5) are preferred. Aliphatic phosphate amide compounds represented by general formula (I) tend to exhibit even further improved flame retardancy, therefore compounds represented by the following formulas (B1), (B2), (B4), and (B5) are preferred. Aliphatic phosphate amide compounds represented by general formula (I) tend to exhibit even further improved stain resistance, therefore compounds represented by the following formulas (B1) to (B4) are preferred.

[0051] [ka] [ka] [ka] [ka] [ka]

[0052] The method for synthesizing the aliphatic phosphate amide compound represented by general formula (I) is not particularly limited. The aliphatic phosphate amide compound represented by general formula (I) can be synthesized by known methods. For example, it may be synthesized according to the methods described in International Publication No. 2014 / 002958 and International Publication No. 2015 / 064018. Furthermore, it is possible to appropriately modify these known synthesis methods. Therefore, the aliphatic phosphate amide compound represented by general formula (I) can be synthesized by applying various known reactions for the synthesis of aliphatic phosphate amide compounds.

[0053] There are no particular limitations on the method for preparing dispersions and emulsions of aliphatic phosphate amide compounds. For example, an emulsion of a phosphorus-based flame retardant can be prepared by mixing the aliphatic phosphate amide compound with an emulsifier and emulsifying and dispersing it in water using a homomixer, homogenizer, colloid mill, sand grinder, bead mill, ball mill, attritor, etc. There are no particular limitations on suitable emulsifiers, and for example, polyoxyethylene alkyl ethers and their fatty acid esters or aromatic carboxylic acid esters; polyoxyalkylene glycols such as polyoxyethylene glycol and polyoxyethylene polyoxypropylene block polymer and their fatty acid esters; nonionic surfactants such as polyoxyethylene alkylphenyl ethers and polyoxyethylene styrene phenyl ether derivatives and their fatty acid esters; and anionic surfactants such as sulfated esters of the above polyoxyethylene alkyl ethers, polyoxyalkylene glycols or polyoxyalkylene ether derivatives and aromatic sulfonic acids can be used.

[0054] The mass ratio (B / A) of the aliphatic phosphate amide compound (B) to (A) the water-dispersible polyurethane resin may be, for example, greater than 0 and less than or equal to 99.0. In particular, when the mass ratio (B / A) is between 0.1 and 10, even better flame retardancy and edge-staining resistance are more easily obtained.

[0055] The flame-retardant composition according to this embodiment may further contain a crosslinking agent. Examples of crosslinking agents include polyisocyanate compounds, polycarbodiimide compounds, and oxazoline compounds. The crosslinking agent may be used alone or in combination of two or more. It is preferable that all of these are water-dispersible.

[0056] Water-dispersible polyisocyanate compounds are obtained, for example, by adding a hydrophilic chain having active hydrogen and, optionally, a lipophilic chain to a starting isocyanate selected from aromatic polyisocyanates, aliphatic polyisocyanates, alicyclic polyisocyanates, and their derivatives. Examples of hydrophilic chains include alkylene oxide chains. Blocked isocyanate compounds, in which the isocyanate groups are protected with a blocking agent, can also be used as water-dispersible polyisocyanates.

[0057] There are no particular restrictions on the aromatic polyisocyanates used to obtain water-dispersible polyisocyanate compounds; for example, tolylene diisocyanate, xylene diisocyanate, or diphenylmethane diisocyanate can be used. There are also no particular restrictions on aliphatic polyisocyanates; for example, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, or lysine diisocyanate can be used. There are also no particular restrictions on alicyclic polyisocyanates; for example, isophorone diisocyanate or hydrogenated xylylene diisocyanate can be used. Among these isocyanates, aromatic polyisocyanates, aliphatic polyisocyanates, and alicyclic polyisocyanates can be used for fabrics dyed in extremely dark colors such as black. Aliphatic polyisocyanates and alicyclic polyisocyanates are particularly suitable for use on lightly dyed fabrics because the products do not yellow after treatment.

[0058] The polyisocyanate derivatives used to obtain water-dispersible polyisocyanates are not particularly limited as long as they are compounds having two or more isocyanate groups. Examples include polyisocyanates having biuret structures, isocyanurate structures, urethane structures, uretdione structures, allophanate structures, trimer structures, etc., and aliphatic isocyanate adducts of trimethylolpropane.

[0059] In the case of water-dispersible polyisocyanate compounds having alkylene oxide chains, the number of repeating units in the alkylene oxide chain is preferably 5 to 50 on average, and more preferably 10 to 30 on average. If the number of repeating units in the alkylene oxide chain is less than 5, the self-emulsifying properties of the water-dispersible polyisocyanate compound may be insufficient. If the number of repeating units in the alkylene oxide chain exceeds 50, the crystallinity of the water-dispersible polyisocyanate compound increases, making solidification more likely.

[0060] Examples of alkylene oxides constituting an alkylene oxide chain include ethylene oxide, propylene oxide, and butylene oxide. These may be used individually or in combination of two or more. Preferably, 70% by mass or more of the alkylene oxide chain consists of ethylene oxide units. Examples of compounds used to introduce an alkylene oxide chain include polyethylene glycol monoalkyl ethers and monoalkyl ethers of random or block copolymers of ethylene oxide and propylene oxide.

[0061] The proportion of alkylene oxide chains bound to the polyisocyanate is preferably 2 to 50 parts by mass, and more preferably 5 to 30 parts by mass, per 100 parts by mass of the water-dispersible polyisocyanate compound. When the amount of alkylene oxide chains is 2 parts by mass or more per 100 parts by mass of the water-dispersible polyisocyanate compound, the effect of reducing the interfacial tension of the water-dispersible polyisocyanate compound is sufficient, and self-emulsification tends to be sufficient. When the amount of alkylene oxide chains is 50 parts by mass or less per 100 parts by mass of the water-dispersible polyisocyanate compound, stability tends to be ensured without the reactivity between the isocyanate group of the water-dispersible polyisocyanate compound and water becoming too high.

[0062] When the water-dispersible polyisocyanate compound is a blocked isocyanate compound, there are no particular restrictions on the blocking agent. Examples of blocking agents include secondary alcohols, tertiary alcohols, activated methylene compounds, phenol compounds, oxime compounds, lactam compounds, or bisulfites. An example of a secondary alcohol is sec-butyl alcohol. An example of a tertiary alcohol is t-butyl alcohol. An example of an activated methylene compound is ethyl malonate and ethyl acetoacetate. An example of a phenol compound is phenol and m-cresol. An example of an oxime compound is acetooxime, methyl ketoxime, methylamyl ketoxime, and diisobutyl ketoxime. An example of a lactam compound is ε-caprolactam. An example of a bisulfite is sodium bisulfite and potassium bisulfite.

[0063] The water-dispersible polyisocyanate compounds described above can be used stably for extended periods in aqueous solutions while maintaining the high reactivity of the isocyanate group, and also exhibit excellent self-emulsification properties in water. Therefore, they can be suitably used to adhere polyester fiber fabrics in aqueous dispersion form together with polyurethane resins.

[0064] Polycarbodiimide compounds can be used without particular limitations, as long as they have two or more carbodiimide groups. As a water-dispersible carbodiimide compound, for example, a polycarbodiimide resin can be used, which is obtained by reacting a polyisocyanate compound with a compound having one functional group that can react with isocyanate groups, such as a hydroxyl group and an amino group, in the presence of a carbodiimide catalyst. Examples of polyisocyanate compounds used to obtain polycarbodiimide resins include hexamethylene diisocyanate, hydrogenated xylylene diisocyanate, xylylene diisocyanate, norbornane diisocyanate, and isophorone diisocyanate. Examples of compounds having one functional group that can react with isocyanate groups include monoalkyl ethers of polyethylene glycol and monoalkyl ethers of random or block copolymers of polyethylene glycol-polypropylene glycol.

[0065] As water-dispersible oxazoline compounds, compounds having two or more oxazolinyl groups can be used. For example, copolymers of 2-isopropenyl-2-oxazoline, ethyl acrylate and methyl methacrylate, copolymers of 2-isopropenyl-2-oxazoline and styrene, copolymers of 2-isopropenyl-2-oxazoline, styrene and acrylonitrile, and copolymers of 2-isopropenyl-2-oxazoline, styrene, butyl acrylate and divinylbenzene can be used as water-dispersible oxazoline compounds.

[0066] These crosslinking agents may be used individually or in combination. In particular, from the viewpoint of improving wear resistance, a combination of a polycarbodiimide compound and a polyisocyanate compound is especially preferred.

[0067] The flame-retardant composition according to this embodiment may further contain a smoothing agent. As the smoothing agent, those commonly used as smoothing agents for fibrous materials can be used as appropriate. Specifically, a smoothing agent containing wax or silicone (preferably wax) can be used. These are usually used in the form of an emulsion dispersed in water.

[0068] Examples of waxes include animal-derived waxes such as beeswax, whale wax, and shellac wax; plant-derived waxes such as carnauba wax, wood wax, rice bran wax, and candelilla wax; petroleum-derived waxes such as paraffin wax and microcrystalline wax; mineral-derived waxes such as montan wax and ozokerite; synthetic waxes such as Fischer-Tropsch wax, polyethylene wax, polypropylene wax, oil-based synthetic waxes (esters, ketones, amides), and hydrogenated waxes; oxidized waxes; blended waxes (blends of synthetic resins such as ethylene vinyl acetate copolymer, polyethylene, and synthetic rosin); and modified waxes such as modified montan wax.

[0069] Examples of silicones include dimethyl silicone, methylphenyl silicone, and diphenyl silicone.

[0070] Among these smoothing agents, paraffin wax, polyethylene wax, polypropylene wax, oxide wax, carnauba wax, and montan wax, all with melting points of 50°C to 150°C, are preferably used because they minimize the reduction in flame retardancy and friction fastness. Furthermore, among these, paraffin wax or oxide wax is particularly preferred.

[0071] The method for producing an emulsion by emulsifying and dispersing a wax or silicone in water is not particularly limited. For example, the wax or silicone and an emulsifier can be mixed and then emulsified and dispersed in water using a homomixer or homogenizer. The emulsifier is not particularly limited and can be, for example, polyoxyethylene alkyl ethers and their fatty acid esters or aromatic carboxylic acid esters; polyoxyalkylene glycols such as polyoxyethylene glycol and polyoxyethylene polyoxypropylene block polymer and their fatty acid esters; nonionic surfactants such as polyoxyethylene alkylphenyl ethers and polyoxyethylene styrene phenyl ether derivatives and their fatty acid esters; and anionic surfactants such as sulfated polyoxyethylene alkyl ethers, polyoxyalkylene glycols or polyoxyalkylene ether derivatives and aromatic sulfonic acids.

[0072] The flame-retardant composition according to this embodiment may be used, for example, in padding and spraying treatments.

[0073] The fiber material in which the flame-retardant composition according to this embodiment is used may be any of the fiber materials exemplified in the flame-retardant fiber materials described later.

[0074] [Flame-retardant fiber material] The following describes a flame-retardant fiber material according to one embodiment. The flame-retardant fiber material according to this embodiment comprises a fiber material and a flame-retardant composition according to the above embodiment attached to the fiber material. Such a flame-retardant fiber material has excellent flame retardancy and resistance to staining.

[0075] While there are no particular limitations on the fiber material, examples include natural fibers such as cotton, linen, silk, and wool; semi-synthetic fibers such as rayon and acetate; synthetic fibers such as nylon, polyester, polyurethane, and polypropylene; and composite and blended fibers thereof.

[0076] The polyester content in the fiber material may be 50% by mass or more, 60% by mass or more, 70% by mass or more, 80% by mass or more, 90% by mass or more, 95% by mass or more, or 100% by mass.

[0077] Polyester fibers are typically dyed using a predetermined dye. The polyester fibers are not particularly limited. Examples include regular polyester fibers, cationic dyeable polyester fibers, recycled polyester fibers, or combinations thereof.

[0078] The fiber material may be a composite fiber made by blending polyester fibers with other fibers. Other fibers that can be combined in this case include natural fibers such as cotton, linen, silk, and wool; semi-synthetic fibers such as rayon and acetate; synthetic fibers such as nylon, acrylic, and polyamide; inorganic fibers such as carbon fibers, glass fibers, ceramic fibers, and metal fibers; and combinations of two or more of these.

[0079] The fibrous material may be any fabric. The type of fabric is not particularly limited, but polyester fiber fabrics are preferred in terms of durability and versatility. In particular, for vehicle interior materials, polyester woven fabrics, polyester jersey knits, and polyester nonwoven fabrics are preferred.

[0080] The amount of (A) water-dispersible polyurethane resin and (B) aliphatic phosphate amide compound attached to the fiber material is not particularly limited, but is usually preferably about 0.1 to 20 parts by weight per 100 parts by weight of the fiber material. From the viewpoint of suppressing the weight increase of the attached fiber material, it is more preferably about 0.1 to 10 parts by weight.

[0081] One aspect of this disclosure is a flame-retardant vehicle interior material comprising a vehicle interior material containing the above-described fiber material and a flame-retardant composition according to the above embodiment attached to the vehicle interior material. Such a flame-retardant vehicle interior material has excellent flame retardancy and resistance to surface adhesion.

[0082] [Method for manufacturing flame-retardant fiber material] The following describes a method for producing a flame-retardant fiber material according to one embodiment. The method for producing a flame-retardant fiber material according to this embodiment comprises the step of contacting a fiber material with an aqueous dispersion containing the flame-retardant composition according to the above embodiment. The resulting flame-retardant fiber material has excellent flame retardancy and resistance to staining. The method for producing a flame-retardant fiber material according to this embodiment may further include a step of drying the fiber material to remove water after the step of contacting the fiber material with the aqueous dispersion.

[0083] By bringing an aqueous dispersion into contact with a fiber material, the water-dispersible polyurethane resin and the aliphatic phosphate amide compound adhere to the fiber material. There are no particular restrictions on the method of bringing the aqueous dispersion into contact with the fiber material, and it can be done by known methods such as the padding method and the spray method. The components of the flame-retardant composition, such as the water-dispersible polyurethane resin and the aliphatic phosphate amide compound, may be attached to the fiber material simultaneously or separately. When attached separately, the fiber material is preferably treated by a process that includes the steps of attaching a first aqueous dispersion containing the aliphatic phosphate amide compound to the fiber material and drying the first aqueous dispersion attached to the fiber material, and then attaching a second aqueous dispersion containing the water-dispersible polyurethane resin to the fiber material and drying the second aqueous dispersion attached to the fiber material.

[0084] The aqueous dispersion adhering to the fiber material can be dried by conventional methods such as natural drying or heat drying. Drying the aqueous dispersion removes most of the water, and the polyurethane resin is crosslinked by reaction with the crosslinking agent, forming a coating that covers the surface of the fiber material. From the viewpoint of improving processing efficiency and further improving flame retardancy and anti-sticking properties, it is preferable to dry the aqueous dispersion by heating. More specifically, it is preferable to dry the aqueous dispersion by heating at 120 to 180°C for 30 seconds to 3 minutes. In particular, when a blocked isocyanate compound is used as the crosslinking agent, it is even more preferable to dry the aqueous dispersion by heating at 150 to 180°C for 30 seconds to 2 minutes.

[0085] The amount of aqueous dispersion to be attached to the fiber material is not particularly limited, but it is usually preferably about 0.2 to 10 parts by mass per 100 parts by mass of the fiber material.

[0086] The fiber material may be one of those exemplified in the flame-retardant fiber material according to the above embodiment. The amount of water-dispersible polyurethane resin and aliphatic phosphate amide compound to be attached to the fiber material may be the same as the amount of (A) water-dispersible polyurethane resin and (B) aliphatic phosphate amide compound attached to the fiber material in the flame-retardant fiber material according to the above embodiment. [Examples]

[0087] The present disclosure will be described in more detail below with reference to examples. However, the present disclosure is not limited to these examples.

[0088] (1) Synthesis of polyurethane resin Synthesis Example 1 In a four-necked flask equipped with a stirrer, reflux condenser, thermometer, and nitrogen inlet, 129.44 g of polyhexamethylene carbonate diol (number average molecular weight 400), 10.84 g of dimethylolpropionic acid, 0.005 g of dibutyltine dilaurate, and 125.01 g of methyl ethyl ketone were placed and mixed uniformly. Then, 151.4 g of dicyclohexylmethane diisocyanate was added, and the reaction was carried out by heating at 80°C for 220 minutes to obtain a methyl ethyl ketone solution of urethane prepolymer with a free isocyanate group content of 3.7% by mass relative to the nonvolatile content. This solution was neutralized with 8.17 g of triethylamine and transferred to another container. At a temperature below 30°C, 707.22 g of water was gradually added while emulsifying and dispersing using a disperser blade. After adding 49.7 g of a 30% aqueous solution of piperazine, the mixture was stirred for 90 minutes to produce a polyurethane resin. Next, the dispersion containing the polyurethane resin was heated to 50°C under reduced pressure to remove methyl ethyl ketone, thereby obtaining an aqueous dispersion of polyurethane resin (non-volatile content 30.0% by mass).

[0089] Synthesis Example 2 In a four-necked flask equipped with a stirrer, reflux condenser, thermometer, and nitrogen inlet, 216.81 g of polyhexamethylene carbonate diol (number average molecular weight 2000), 10.89 g of dimethylolpropionic acid, 0.005 g of dibutyltin dilaurate, and 128.02 g of methyl ethyl ketone were placed and mixed uniformly. Then, 71.00 g of dicyclohexylmethane diisocyanate was added, and the reaction was carried out by heating at 80°C for 220 minutes to obtain a methyl ethyl ketone solution of urethane prepolymer with a free isocyanate group content of 1.7% by mass relative to the nonvolatile content. This solution was neutralized with 8.21 g of triethylamine and then transferred to another container. At a temperature of 30°C or below, 705.08 g of water was gradually added while emulsifying and dispersing using a disperser blade. 23.31 g of a 30% aqueous solution of piperazine was added to this, and the mixture was stirred for 90 minutes to produce a polyurethane resin. Next, the dispersion of polyurethane resin was heated to 50°C under reduced pressure to remove methyl ethyl ketone and obtain an aqueous dispersion of polyurethane resin (non-volatile content 30.0% by mass).

[0090] Synthesis Example 3 In a four-necked flask equipped with a stirrer, reflux condenser, thermometer, and nitrogen inlet, 229.84 g of polyhexamethylene carbonate diol (number average molecular weight 3000), 10.87 g of dimethylolpropionic acid, 0.005 g of dibutyltin dilaurate, and 128.46 g of methyl ethyl ketone were placed and mixed uniformly. Then, 59.04 g of dicyclohexylmethane diisocyanate was added, and the reaction was carried out by heating at 80°C for 220 minutes to obtain a methyl ethyl ketone solution of urethane prepolymer with a free isocyanate group content of 1.4% by mass relative to the nonvolatile content. This solution was neutralized with 8.19 g of triethylamine and then transferred to another container. At a temperature of 30°C or below, 704.78 g of water was gradually added while emulsifying and dispersing using a disperser blade. 19.38 g of a 30% aqueous solution of piperazine was added to this, and the mixture was stirred for 90 minutes to produce a polyurethane resin. Next, the dispersion of polyurethane resin was heated to 50°C under reduced pressure to remove methyl ethyl ketone and obtain an aqueous dispersion of polyurethane resin (non-volatile content 30.0% by mass).

[0091] Synthesis Example 4 In a four-necked flask equipped with a stirrer, reflux condenser, thermometer, and nitrogen inlet, 241.13 g of polyhexamethylene carbonate diol (number average molecular weight 5000), 10.94 g of dimethylolpropionic acid, 0.005 g of dibutyltine dilaurate, and 128.85 g of methyl ethyl ketone were placed and mixed uniformly. Then, 48.60 g of dicyclohexylmethane diisocyanate was added, and the reaction was carried out by heating at 80°C for 220 minutes to obtain a methyl ethyl ketone solution of urethane prepolymer with a free isocyanate group content of 1.2% by mass relative to the nonvolatile content. This solution was neutralized with 8.24 g of triethylamine and then transferred to another container. At a temperature of 30°C or below, 704.46 g of water was gradually added while emulsifying and dispersing using a disperser blade. After adding 15.95 g of a 30% aqueous solution of piperazine, the mixture was stirred for 90 minutes to produce a polyurethane resin. Next, the dispersion containing the polyurethane resin was heated to 50°C under reduced pressure to remove methyl ethyl ketone and obtain an aqueous dispersion of polyurethane resin (non-volatile content 30.0% by mass).

[0092] Synthesis Example 5 In a four-necked flask equipped with a stirrer, reflux condenser, thermometer, and nitrogen inlet, 216.81 g of 3-methyl-1,5-pentanediol isophthalate (number average molecular weight 2000), 10.89 g of dimethylolpropionic acid, 0.005 g of dibutyltin dilaurate, and 128.02 g of methyl ethyl ketone were placed and mixed uniformly. Then, 71.00 g of dicyclohexylmethane diisocyanate was added, and the reaction was carried out by heating at 80°C for 220 minutes to obtain a methyl ethyl ketone solution of urethane prepolymer with a free isocyanate group content of 1.7% by mass relative to the nonvolatile content. This solution was neutralized with 8.21 g of triethylamine and then transferred to another container. At a temperature of 30°C or below, 705.08 g of water was gradually added while emulsifying and dispersing using a disperser blade. 23.31 g of a 30% aqueous solution of piperazine was added to this, and the mixture was stirred for 90 minutes to produce a polyurethane resin. Next, the dispersion of polyurethane resin was heated to 50°C under reduced pressure to remove methyl ethyl ketone and obtain an aqueous dispersion of polyurethane resin (non-volatile content 30.0% by mass).

[0093] Synthesis Example 6 In a four-necked flask equipped with a stirrer, reflux condenser, thermometer, and nitrogen inlet, 108.41 g of polyhexamethylene carbonate diol (number average molecular weight 2000), 108.41 g of 3-methyl-1,5-pentanediol isophthalate (average molecular weight 2000), 10.89 g of dimethylolpropionic acid, 0.005 g of dibutyltin dilaurate, and 128.02 g of methyl ethyl ketone were placed and mixed uniformly. Then, 71.00 g of dicyclohexylmethane diisocyanate was added, and the reaction was carried out by heating at 80°C for 220 minutes to obtain a methyl ethyl ketone solution of urethane prepolymer with a free isocyanate group content of 1.7% by mass relative to the nonvolatile content. This solution was neutralized with 8.21 g of triethylamine and then transferred to another container. At a temperature of 30°C or below, 705.08 g of water was gradually added while emulsifying and dispersing using a disperser blade. 23.31 g of a 30% aqueous solution of piperazine was added to this, and the mixture was stirred for 90 minutes to produce a polyurethane resin. Next, the dispersion of polyurethane resin was heated to 50°C under reduced pressure to remove methyl ethyl ketone and obtain an aqueous dispersion of polyurethane resin (non-volatile content 30.00% by mass).

[0094] Synthesis Example 7 In a four-necked flask equipped with a stirrer, reflux condenser, thermometer, and nitrogen inlet, 110.16 g of polyhexamethylene carbonate diol (number average molecular weight 300), 11.22 g of dimethylolpropionic acid, 0.005 g of dibutyltine dilaurate, and 124.36 g of methyl ethyl ketone were placed and mixed uniformly. Then, 168.79 g of dicyclohexylmethane diisocyanate was added, and the reaction was carried out by heating at 80°C for 220 minutes to obtain a methyl ethyl ketone solution of urethane prepolymer with a free isocyanate group content of 4.2% by mass relative to the nonvolatile content. This solution was neutralized with 8.46 g of triethylamine and then transferred to another container. At a temperature of 30°C or below, 707.39 g of water was gradually added while emulsifying and dispersing using a disperser blade. 55.40 g of a 30% aqueous solution of piperazine was added to this, and the mixture was stirred for 90 minutes to produce a polyurethane resin. Next, the dispersion of polyurethane resin was heated to 50°C under reduced pressure to remove methyl ethyl ketone and obtain an aqueous dispersion of polyurethane resin (non-volatile content 30.0% by mass).

[0095] Synthesis Example 8 In a four-necked flask equipped with a stirrer, reflux condenser, thermometer, and nitrogen inlet, 243.53 g of polyhexamethylene carbonate diol (number average molecular weight 6000), 11.11 g of dimethylolpropionic acid, 0.005 g of dibutyltin dilaurate, and 128.94 g of methyl ethyl ketone were placed and mixed uniformly. Then, 46.23 g of dicyclohexylmethane diisocyanate was added, and the reaction was carried out by heating at 80°C for 220 minutes to obtain a methyl ethyl ketone solution of urethane prepolymer with a free isocyanate group content of 1.1% by mass relative to the nonvolatile content. This solution was neutralized with 8.38 g of triethylamine and then transferred to another container. At a temperature below 30°C, 704.26 g of water was gradually added while emulsifying and dispersing using a disperser blade. After adding 15.18 g of a 30% aqueous solution of piperazine, the mixture was stirred for 90 minutes to produce a polyurethane resin. Next, the dispersion containing the polyurethane resin was heated to 50°C under reduced pressure to remove methyl ethyl ketone and obtain an aqueous dispersion of polyurethane resin (non-volatile content 30.0% by mass).

[0096] Synthesis Example 9 In a four-necked flask equipped with a stirrer, reflux condenser, thermometer, and nitrogen inlet, 110.16 g of 3-methyl-1,5-pentanediol isophthalate (number average molecular weight 300), 11.22 g of dimethylolpropionic acid, 0.005 g of dibutyltine dilaurate, and 124.36 g of methyl ethyl ketone were placed and mixed uniformly. Then, 168.79 g of dicyclohexylmethane diisocyanate was added, and the reaction was carried out by heating at 80°C for 220 minutes to obtain a methyl ethyl ketone solution of urethane prepolymer with a free isocyanate group content of 4.2% by mass relative to the nonvolatile content. This solution was neutralized with 8.46 g of triethylamine and then transferred to another container. At a temperature of 30°C or below, 707.39 g of water was gradually added while emulsifying and dispersing using a disperser blade. 55.40 g of a 30% aqueous solution of piperazine was added to this, and the mixture was stirred for 90 minutes to produce a polyurethane resin. Next, the dispersion of polyurethane resin was heated to 50°C under reduced pressure to remove methyl ethyl ketone and obtain an aqueous dispersion of polyurethane resin (non-volatile content 30.0% by mass).

[0097] Synthesis Example 10 In a four-necked flask equipped with a stirrer, reflux condenser, thermometer, and nitrogen inlet, 243.52 g of 3-methyl-1,5-pentanediol isophthalate (number average molecular weight 6000), 11.11 g of dimethylolpropionic acid, 0.005 g of dibutyltin dilaurate, and 128.94 g of methyl ethyl ketone were placed and mixed uniformly. Then, 46.23 g of dicyclohexylmethane diisocyanate was added, and the reaction was carried out by heating at 80°C for 220 minutes to obtain a methyl ethyl ketone solution of urethane prepolymer with a free isocyanate group content of 1.1% by mass relative to the nonvolatile content. This solution was neutralized with 8.38 g of triethylamine and then transferred to another container. At a temperature of 30°C or below, 704.26 g of water was gradually added while emulsifying and dispersing using a disperser blade. After adding 15.18 g of a 30% aqueous solution of piperazine, the mixture was stirred for 90 minutes to produce a polyurethane resin. Next, the dispersion containing the polyurethane resin was heated to 50°C under reduced pressure to remove methyl ethyl ketone and obtain an aqueous dispersion of polyurethane resin (non-volatile content 30.0% by mass).

[0098] (2) Synthesis of aliphatic phosphate amide compounds Synthesis Example 11 Synthesis of phosphate amide B1 According to Synthesis Example 2 (paragraphs

[0114] to

[0116] ) in International Publication No. 2014 / 002958, phosphate amide B1 represented by the following formula (B1) was synthesized.

[0099] [ka]

[0100] Synthesis Example 12 Synthesis of phosphate amide B2 The phosphate amide B2 represented by the following formula (B2) was synthesized by performing the same procedure as in Synthesis Example 1 (paragraphs

[0110] to

[0113] ) in International Publication No. 2014 / 002958.

[0101] [ka]

[0102] Synthesis Example 13 Synthesis of phosphate amide B3 Except for using 89.0 g (1.20 mol) of 1,2-propylenediamine instead of ethylenediamine, the same procedure as in Synthesis Example 1 (paragraphs

[0110] to

[0113] ) in International Publication No. 2014 / 002958 was performed to synthesize phosphate amide B3 represented by the following formula (B3).

[0103] [ka]

[0104] Synthesis Example 14 Synthesis of phosphate amide B4 Except for using 89.0 g (1.20 mol) of 1,3-propylenediamine instead of ethylenediamine, the same procedure as in Synthesis Example 1 (paragraphs

[0110] to

[0113] ) in International Publication No. 2014 / 002958 was performed to synthesize phosphate amide B4 represented by the following formula (B4).

[0105] [ka]

[0106] Synthesis Example 15 Synthesis of phosphate amide B5 The phosphate amide B5 represented by the following formula (B5) was synthesized by performing the same procedure as in Synthesis Example 5 (paragraphs

[0196] to

[0198] ) in International Publication No. 2015 / 064018.

[0107] [ka]

[0108] (3) Phosphate ester compounds The following products were used as phosphate esters 1 and 2. Phosphate ester 1: CR-741 (Bisphenol A bis(diphenyl phosphate)) manufactured by Daihachi Chemical Industry Co., Ltd. Phosphate ester 2: PX-200 (1,3-phenylenebis(di-2,6-xylylphosphate)) manufactured by Daihachi Chemical Industry Co., Ltd.

[0109] (4) Preparation of flame retardant dispersion Preparation of flame retardant dispersion 1 In a four-necked flask equipped with a stirrer, reflux condenser, thermometer, and nitrogen inlet tube, 5 parts by mass of sodium lauryl sulfate was dissolved in 695 parts by mass of water, and 300 parts by mass of phosphate amide B1 was gradually introduced and mixed for 30 minutes to obtain flame retardant dispersion 1 (30% by mass of flame retardant dispersion).

[0110] Preparation of flame retardant dispersion 2 Flame retardant dispersion 2 (30% by mass of flame retardant dispersion) was obtained in the same manner as the preparation of flame retardant dispersion 1, except that phosphate amide B2 was used instead of phosphate amide B1.

[0111] Preparation of flame retardant dispersion 3 Flame retardant dispersion 3 (30% by mass of flame retardant dispersion) was obtained in the same manner as the preparation of flame retardant dispersion 1, except that phosphate amide B3 was used instead of phosphate amide B1.

[0112] Preparation of flame retardant dispersion 4 Flame retardant dispersion 4 (30% by mass of flame retardant dispersion) was obtained in the same manner as the preparation of flame retardant dispersion 1, except that phosphate amide B4 was used instead of phosphate amide B1.

[0113] Preparation of flame retardant dispersion 5 Flame retardant dispersion 5 (30% by mass of flame retardant dispersion) was obtained in the same manner as the preparation of flame retardant dispersion 1, except that phosphate amide B5 was used instead of phosphate amide B1.

[0114] Preparation of flame retardant dispersion 6 Flame retardant dispersion 6 (30% by mass of flame retardant dispersion) was obtained in the same manner as the preparation of flame retardant dispersion 1, except that phosphate ester 1 was used instead of phosphate amide B1.

[0115] Preparation of flame retardant dispersion 7 Flame retardant dispersion 7 (30% by mass of flame retardant dispersion) was obtained in the same manner as the preparation of flame retardant dispersion 1, except that phosphate ester 2 was used instead of phosphate amide B1.

[0116] Flame retardant dispersion 8 Avinon 307 (guanidine phosphate-based flame retardant dispersion, manufactured by Sanwa Chemical Co., Ltd., 50% by mass of flame retardant dispersion) was used as the flame retardant dispersion 8.

[0117] (5) Preparation of the test cloth Sample fabric A A dyeing solution was prepared containing 8% owf of disperse dye (Dianix Black HF-B), 0.5 g / L of dispersing and leveling agent (Nikka Sun Salt (product name) RM-340E, manufactured by Nikka Chemical Co., Ltd.), and 0.2 cc / L of acetic acid. This dyeing solution was placed in a mini color dyeing machine (manufactured by Texam Giken Co., Ltd.) and dyed at a bath ratio of 1:15 and 130°C for 60 minutes to achieve a basis weight of 360 g / m². 2 A polyester jersey knit fabric was dyed. The dyed jersey knit fabric was reduced and washed by heating at 80°C for 20 minutes in an aqueous solution containing 1 g / L of soaping agent Sunmall® RC-700E (Nikka Chemical Co., Ltd.), 2 g / L of hydrosulfite, and 1 g / L of caustic soda, followed by hot water washing and cold water washing. After that, it was dried by heating at 140°C for 3 minutes to obtain test fabric A.

[0118] (6) Manufacturing of vehicle interior materials Example 1 A flame-retardant treatment solution (aqueous dispersion) was prepared by mixing 93 parts by mass of water, 2 parts by mass of the aqueous dispersion of polyurethane resin obtained in Synthesis Example 1, and 5 parts by mass of flame retardant dispersion 1. Test fabric A was padded using the treatment solution at a squeezing ratio of 60%. The padded test fabric was dried by heating at 150°C for 5 minutes to obtain a vehicle interior material.

[0119] Example 2 A flame-retardant treatment solution was prepared by mixing 93 parts by mass of water, 2 parts by mass of the aqueous dispersion of polyurethane resin obtained in Synthesis Example 2, and 5 parts by mass of flame retardant dispersion 1. Test fabric A was padded with the treatment solution at a squeezing ratio of 60%. The padded test fabric was dried by heating at 150°C for 5 minutes to obtain a vehicle interior material.

[0120] Example 3 A flame-retardant treatment solution was prepared by mixing 93 parts by mass of water, 2 parts by mass of the aqueous dispersion of polyurethane resin obtained in Synthesis Example 3, and 5 parts by mass of flame retardant dispersion 1. Test fabric A was padded using the treatment solution at a squeezing ratio of 60%. The padded test fabric was dried by heating at 150°C for 5 minutes to obtain a vehicle interior material.

[0121] Example 4 A flame-retardant treatment solution was prepared by mixing 93 parts by mass of water, 2 parts by mass of the aqueous dispersion of polyurethane resin obtained in Synthesis Example 4, and 5 parts by mass of flame retardant dispersion 1. Test fabric A was padded with the treatment solution at a squeezing ratio of 60%. The padded test fabric was dried by heating at 150°C for 5 minutes to obtain a vehicle interior material.

[0122] Example 5 A flame-retardant treatment solution was prepared by mixing 93 parts by mass of water, 2 parts by mass of the aqueous dispersion of polyurethane resin obtained in Synthesis Example 5, and 5 parts by mass of flame retardant dispersion 1. Test fabric A was padded with the treatment solution at a squeezing ratio of 60%. The padded test fabric was dried by heating at 150°C for 5 minutes to obtain a vehicle interior material.

[0123] Example 6 A flame-retardant treatment solution was prepared by mixing 93 parts by mass of water, 2 parts by mass of the aqueous dispersion of polyurethane resin obtained in Synthesis Example 6, and 5 parts by mass of flame retardant dispersion 1. Test fabric A was padded with the treatment solution at a squeezing ratio of 60%. The padded test fabric was dried by heating at 150°C for 5 minutes to obtain a vehicle interior material.

[0124] Example 7 A flame-retardant treatment solution was prepared by mixing 93 parts by mass of water, 2 parts by mass of the aqueous dispersion of polyurethane resin obtained in Synthesis Example 2, and 5 parts by mass of flame retardant dispersion 2. Test fabric A was padded with the treatment solution at a squeezing ratio of 60%. The padded test fabric was dried by heating at 150°C for 5 minutes to obtain a vehicle interior material.

[0125] Example 8 A flame-retardant treatment solution was prepared by mixing 93 parts by mass of water, 2 parts by mass of the aqueous dispersion of polyurethane resin obtained in Synthesis Example 2, and 5 parts by mass of flame retardant dispersion 3. Test fabric A was padded with the treatment solution at a squeezing ratio of 60%. The padded test fabric was dried by heating at 150°C for 5 minutes to obtain a vehicle interior material.

[0126] Example 9 A flame-retardant treatment solution was prepared by mixing 93 parts by mass of water, 2 parts by mass of the aqueous dispersion of polyurethane resin obtained in Synthesis Example 2, and 5 parts by mass of flame retardant dispersion 4. Test fabric A was padded with the treatment solution at a squeezing ratio of 60%. The padded test fabric was dried by heating at 150°C for 5 minutes to obtain a vehicle interior material.

[0127] Example 10 A flame-retardant treatment solution was prepared by mixing 93 parts by mass of water, 2 parts by mass of the aqueous dispersion of polyurethane resin obtained in Synthesis Example 2, and 5 parts by mass of flame retardant dispersion 5. Test fabric A was padded with the treatment solution at a squeezing ratio of 60%. The padded test fabric was dried by heating at 150°C for 5 minutes to obtain a vehicle interior material.

[0128] Example 11 A flame-retardant treatment solution was prepared by mixing 90.85 parts by mass of water, 2 parts by mass of the aqueous dispersion of polyurethane resin obtained in Synthesis Example 2, 5 parts by mass of flame retardant dispersion 1, 0.15 parts by mass of NK Assist CI-02 (manufactured by Nikka Chemical) as a crosslinking agent, and 2 parts by mass of Sanmariner TS-155GT as a thread breakage prevention agent. Test fabric A was padded with the treatment solution at a squeezing ratio of 60%. The padded test fabric was dried by heating at 150°C for 5 minutes to obtain a vehicle interior material.

[0129] Comparative Example 1 A flame-retardant treatment solution was prepared by mixing 98 parts by mass of water with 2 parts by mass of the aqueous dispersion of polyurethane resin obtained in Synthesis Example 2. Test fabric A was padded using the treatment solution at a squeezing ratio of 60%. The padded test fabric was dried by heating at 150°C for 5 minutes to obtain a vehicle interior material.

[0130] Comparative Example 2 A flame-retardant treatment solution was prepared by mixing 95 parts by mass of water with 5 parts by mass of flame retardant dispersion 1. Test fabric A was padded using the treatment solution at a squeezing ratio of 60%. The padded test fabric was dried by heating at 150°C for 5 minutes to obtain a vehicle interior material.

[0131] Comparative Example 3 A flame-retardant treatment solution was prepared by mixing 93 parts by mass of water, 2 parts by mass of the aqueous dispersion of polyurethane resin obtained in Synthesis Example 7, and 5 parts by mass of flame retardant dispersion 1. Test fabric A was padded with the treatment solution at a squeezing ratio of 60%. The padded test fabric was dried by heating at 150°C for 5 minutes to obtain a vehicle interior material.

[0132] Comparative Example 4 A flame-retardant treatment solution was prepared by mixing 93 parts by mass of water, 2 parts by mass of the aqueous dispersion of polyurethane resin obtained in Synthesis Example 8, and 5 parts by mass of flame retardant dispersion 1. Test fabric A was padded with the treatment solution at a squeezing ratio of 60%. The padded test fabric was dried by heating at 150°C for 5 minutes to obtain a vehicle interior material.

[0133] Comparative Example 5 A flame-retardant treatment solution was prepared by mixing 93 parts by mass of water, 2 parts by mass of the aqueous dispersion of polyurethane resin obtained in Synthesis Example 9, and 5 parts by mass of flame retardant dispersion 1. Test fabric A was padded with the treatment solution at a squeezing ratio of 60%. The padded test fabric was dried by heating at 150°C for 5 minutes to obtain a vehicle interior material.

[0134] Comparative Example 6 A flame-retardant treatment solution was prepared by mixing 93 parts by mass of water, 2 parts by mass of the aqueous dispersion of polyurethane resin obtained in Synthesis Example 10, and 5 parts by mass of flame retardant dispersion 1. Test fabric A was padded with the treatment solution at a squeezing ratio of 60%. The padded test fabric was dried by heating at 150°C for 5 minutes to obtain a vehicle interior material.

[0135] Comparative Example 7 A flame-retardant treatment solution was prepared by mixing 93 parts by mass of water, 2 parts by mass of the aqueous dispersion of polyurethane resin obtained in Synthesis Example 1, and 5 parts by mass of flame retardant dispersion 6. Test fabric A was padded with the treatment solution at a squeezing ratio of 60%. The padded test fabric was dried by heating at 150°C for 5 minutes to obtain a vehicle interior material.

[0136] Comparative Example 8 A flame-retardant treatment solution was prepared by mixing 93 parts by mass of water, 2 parts by mass of the aqueous dispersion of polyurethane resin obtained in Synthesis Example 1, and 5 parts by mass of the flame retardant dispersion 7. Test fabric A was padded with the treatment solution at a squeezing ratio of 60%. The padded test fabric was dried by heating at 150°C for 5 minutes to obtain a vehicle interior material.

[0137] Comparative Example 9 A flame-retardant treatment solution was prepared by mixing 94.2 parts by mass of water, 2 parts by mass of the aqueous dispersion of polyurethane resin obtained in Synthesis Example 1, and 3.8 parts by mass of the flame retardant dispersion 8. The test fabric A was padded using the treatment solution at a squeezing ratio of 60%. The padded test fabric was dried by heating at 150°C for 5 minutes to obtain a vehicle interior material.

[0138] Comparative Example 10 A flame-retardant treatment solution was prepared by mixing 93.67 parts by mass of water, 1.33 parts by mass of Nipol 874 (acrylic resin), and 5 parts by mass of flame retardant dispersion 1. Test fabric A was padded using the treatment solution at a squeezing ratio of 60%. The padded test fabric was dried by heating at 150°C for 5 minutes to obtain a vehicle interior material.

[0139] (7) Evaluation method for vehicle interior materials The vehicle interior materials obtained in each example and comparative example were evaluated for their resistance to chipping and flame retardancy as follows. The results are shown in Tables 1 and 2.

[0140] 7.1 Edge-scratch resistance A 10mm thick foamed urethane sheet was placed on a table, and the vehicle seat material was placed on top of it. 2 mL of 90°C pure water was then dropped onto its surface. After air-drying at room temperature, the presence or absence of discoloration (whitening or darkening) on ​​the surface of the vehicle seat material was visually observed, and the discoloration was evaluated using the following five-level scale, with Grade 4 of the JIS L0805 gray scale for contamination being 1 point. 5 points: No discernible flaws whatsoever. (Passing level) 4 points: 5% to less than 15% of the edge marks are observed compared to a 1-point mark. (Passing level) 3 points: 15% to less than 25% of the edge marks are observed compared to a 1-point mark. (Passing level) 2 points: 25% to less than 35% of the edge defects are observed compared to a 1-point mark. (Failure level) 1 point: The flaws are clearly visible. (Failure level)

[0141] 7.2 Flame retardancy The burning distance, burning time, and burning rate of vehicle seat materials were measured according to the FMVSS-302 method (safety standards for automotive interior materials), and flame retardancy was evaluated using the following combustion score criteria. The combustion score was calculated by averaging the scores from 10 measurements and comparing the results to one decimal place. 5 points: No ignition occurred. (Passing level) 4 points: The fire ignites but does not burn beyond the A mark (self-extinguishing before the A mark). (Passing level) 3 points: The flame extends beyond the A mark, but the burning distance is less than 50 mm and the burning speed is less than 80 mm / min. (Passing level) Points 2: The combustion extends beyond the A mark, the combustion distance is 50 mm or more, and the combustion speed is less than 80 mm / min. (Failure level) 1 point: Burning exceeds the A mark, the burning distance is 50 mm or more, and the burning speed is 80 mm / min or more. (Failure level)

[0142] [Table 1]

[0143] [Table 2]

[0144] As shown in Table 1, when the treatment solution contained a combination of a polyurethane resin obtained from a polycarbonate polyol or polyester polyol with a number average molecular weight of 400 to 5000 and a phosphate amide compound (Examples 1-11), the flame retardancy and edge adhesion resistance were at an acceptable level. In contrast, as shown in Table 2, when the treatment solution contained only polyurethane resin (Comparative Example 1), when the treatment solution contained only phosphate amide compounds (Comparative Example 2), and when the treatment solution contained a combination of polyurethane resin obtained from polyols other than polycarbonate polyols or polyester polyols with a number average molecular weight of 300 or 6000, and phosphate amide compounds (Comparative Examples 3-6), flame retardancy and edge-stain resistance were not achieved simultaneously. Furthermore, when the treatment solution contained a combination of polyurethane resin obtained from polycarbonate polyols with a number average molecular weight of 400, and phosphate ester compounds (Comparative Examples 7-8), flame retardancy and edge-stain resistance failed. When a guanidine-based flame retardant was used as the flame retardant (Comparative Example 9), and when the treatment solution contained acrylic resin and phosphate amide compounds (Comparative Example 10), flame retardancy and edge-stain resistance were not achieved simultaneously.

Claims

1. A flame-retardant composition for textile materials comprising (A) a water-dispersible polyurethane resin and (B) an aliphatic phosphate amide compound, The (A) water-dispersible polyurethane resin is a water-dispersible polyurethane resin obtained by reacting an isocyanate group-terminated prepolymer with a chain extender in water. The isocyanate-terminated prepolymer is a prepolymer obtained by reacting (a) an organic polyisocyanate compound, (b) a high molecular weight polyol having a number average molecular weight of 400 to 5000, and (c) a compound having a carboxyl group or carboxylate group and at least two active hydrogens. A flame-retardant composition for fiber materials, wherein the chain extender comprises at least one selected from the group consisting of water-soluble polyamines, hydrazines, and derivatives thereof.

2. The flame retardant composition for fiber materials according to claim 1, wherein the (B) aliphatic phosphate amide compound comprises a compound represented by the following general formula (I). 【Chemistry 1】 [In the formula, R １ and R ２ Each is independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R １１ and R １２ Each of these is an alkylene group having 1 to 3 carbon atoms, and R １３ This is an alkylene group having 1 to 6 carbon atoms, and B １ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and A is a hydrogen atom or general formula (II): 【Chemistry 2】 (In the formula, R ３ and R ４ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R １４ and R １５ are each independently an alkylene group having 1 to 3 carbon atoms, B ２ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and ※ is a bond) and is an organic group represented by. Here, A is a hydrogen atom, and B １ If is an alkyl group having 1 to 6 carbon atoms, then B １ and R １３ -A may bond with the nitrogen atom to which it is bonded, forming a nitrogen-containing heterocycle. A is an organic group represented by general formula (II), and B ２ is an alkyl group having 1 to 6 carbon atoms, and B １ If is an alkyl group having 1 to 6 carbon atoms, then B １ and B ２ and are bonded together, and the nitrogen atom and R to which they are bonded １３ It may also form a nitrogen-containing heterocycle together with it.

3. The flame-retardant composition for fiber materials according to claim 2, wherein in the general formula (I), A is an organic group represented by general formula (II).

4. The flame-retardant composition for fiber materials according to claim 3, wherein the (B) aliphatic phosphate amide compound comprises at least one of the compounds represented by the following formula (B1) and the compounds represented by the following formula (B2). 【Transformation 3】 【Chemistry 4】

5. The flame-retardant composition for fiber materials according to claim 1, wherein the isocyanate-terminated prepolymer is a prepolymer obtained by reacting (a) an organic polyisocyanate compound, (b) a high molecular weight polyol having a number average molecular weight of 400 to 5000, (c) a compound having a carboxyl group or carboxylate group and at least two active hydrogens, and (d) a chain extender.

6. The flame-retardant composition for fiber materials according to claim 1, wherein the high molecular weight polyol comprises at least one of a polycarbonate diol and an aromatic polyester diol.

7. A flame-retardant composition for textile materials according to any one of claims 1 to 6, for use in padding treatment.

8. A flame-retardant fiber material comprising a fiber material and a flame-retardant composition according to any one of claims 1 to 6 attached to the fiber material.

9. A method for producing a flame-retardant fiber material, comprising the step of bringing an aqueous dispersion containing the flame-retardant composition according to any one of claims 1 to 6 into contact with a fiber material.

Images