JP2010189328A - Condensed phosphonic acid derivative, aqueous dispersion thereof and flame-proofing method using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an aqueous dispersion of a halogen-free flame-proofing agent imparting durable, excellent flame-proof performance to a fiber, particularly a CDP fiber, a blended fiber of CDP and polyester or a fiber to which various functions such as antibacterial property, deodorizing property and surface treatment are imparted. <P>SOLUTION: The aqueous dispersion comprises: at least one condensed phosphonic acid derivative chosen from the group consisting of fused phosphonic acid derivatives represented by formulas (1) to (4); and a surfactant. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to an aqueous dispersion for flameproofing, which contains a non-halogen compound, particularly a condensed phosphonic acid derivative, which can impart a flameproof performance with excellent durability to a synthetic fiber structure. The present invention relates to a flame processing method and a fiber subjected to flameproofing.

Conventionally, as a method for imparting flameproofing performance to a fiber by post-processing, a method in which a halogen compound is dispersed in water to form a flameproofing agent and the fiber is flameproofed using this is known. Representative examples of the halogen compounds include brominated cycloalkanes such as 1,2,5,6,9,10-hexabromocyclododecane.
It is known that the flameproofing performance of halogenated compounds is generally high. However, when the flameproofed fiber burns, harmful halogenated gas is generated, which causes harmful effects on the human body and the natural environment. There is. Therefore, in recent years, the use of halogen compounds as flameproofing agents has been regulated.

  Therefore, flame retardants using phosphorus compounds such as organic phosphates as flame retardants in place of halogen compounds, and flameproofing methods for fibers using the same have been proposed (Patent Documents 1 to 4). .

  However, when these phosphorus compounds are used, various functions such as fibers, in particular, CDP (cation dyeable polyester) fibers and blended fibers thereof with polyester fibers, antibacterial processing, deodorization processing, surface processing, etc. A sufficient flameproofing performance cannot be imparted to the fibers imparted with the.

JP 2001-254268 A JP 2000-328445 A JP 2004-225176 A JP 2006-70417 A

  An object of the present invention is to provide a flameproofing agent and a flameproofing agent capable of imparting excellent and excellent flameproofing performance to fibers, particularly CDP fibers, blended fibers of polyester fibers with them, and functionalized fibers. It is to provide a processing method.

  As a result of diligent research to solve the above-mentioned problems, the present inventors have used a specific condensed phosphonic acid derivative and a surfactant to provide a flameproof performance excellent in durability between CDP fiber and polyester fiber. The present invention has been completed by finding that it can be applied to a blended fiber of the above, and a fiber imparted with functionality.

（式中、ｎ_１は１〜３の整数を示し、Ｒ_１１、Ｒ_１２、Ｒ_１３、Ｒ_１４は、それぞれ独立に水酸基、アミノ基、シアノ基、ホルミル基、カルボキシ基、ウレイド基、（Ｃ１−Ｃ１０）アルキル基、（Ｃ１−Ｃ１０）アルキルアミノ基、ジ（Ｃ１−Ｃ１０）アルキルアミノ基、フェニル基、フェノキシ基若しくは（Ｃ１−Ｃ１０）アルコキシ基によって置換されていてもよいアリール基、又は、（Ｃ１−Ｃ１０）アルキル基を示し、Ｒ_１５は水酸基、アミノ基、シアノ基、ホルミル基、カルボキシ基、ウレイド基、（Ｃ１−Ｃ１０）アルキル基、（Ｃ１−Ｃ１０）アルキルアミノ基、ジ（Ｃ１−Ｃ１０）アルキルアミノ基、フェニル基、フェノキシ基若しくは（Ｃ１−Ｃ１０）アルコキシ基によって置換されていてもよいアリール基、直鎖若しくは分岐鎖の（Ｃ１−Ｃ６）アルキル基、（Ｃ５−Ｃ８）シクロアルキル基、（C２〜C６）アルケニル基、フェネチル基、カルボニル基、又は、下記式（５）

で表わされる縮合型ホスホン酸誘導体あるいはその塩、又は、下記式（２） That is, the present invention relates to the following 1) to 10).
1) The following formula (1)

(In the formula, n ₁ represents an integer of ₁ to 3, and R ₁₁ , R ₁₂ , R ₁₃ , and R ₁₄ are each independently a hydroxyl group, an amino group, a cyano group, a formyl group, a carboxy group, a ureido group, (C1 -C10) an aryl group optionally substituted by an alkyl group, a (C1-C10) alkylamino group, a di (C1-C10) alkylamino group, a phenyl group, a phenoxy group or a (C1-C10) alkoxy group, or It shows the (C1-C10) alkyl _{group, R 15} represents a hydroxyl group, an amino group, a cyano group, a formyl group, a carboxy group, a ureido group, (C1-C10) alkyl group, (C1-C10) alkylamino group, di (C1 -C10) aryl group optionally substituted by alkylamino group, phenyl group, phenoxy group or (C1-C10) alkoxy group, Or branched (C1-C6) alkyl, (C5-C8) cycloalkyl group, (C2 -C6) alkenyl group, a phenethyl group, a carbonyl group, or the following formula (5)

A condensed phosphonic acid derivative represented by the following formula (2):

（式中、ｎ_２は０〜３の整数を示し、Ｒ_２１、Ｒ_２２、Ｒ_２３、Ｒ_２４はそれぞれ独立に水酸基、アミノ基、シアノ基、ホルミル基、カルボキシ基、ウレイド基、（Ｃ１−Ｃ１０）アルキル基、（Ｃ１−Ｃ１０）アルキルアミノ基、ジ（Ｃ１−Ｃ１０）アルキルアミノ基、フェニル基、フェノキシ基若しくは（Ｃ１−Ｃ１０）アルコキシ基によって置換されていてもよいアリール基、又は、（Ｃ１−Ｃ１０）アルキル基を示し、Ｒ_２５、Ｒ_２６はそれぞれ独立に水素原子、（Ｃ１−Ｃ３）アルキル基、フェネチル基、又は、水酸基、アミノ基、シアノ基、ホルミル基、カルボキシ基、ウレイド基、（Ｃ１−Ｃ１０）アルキル基、（Ｃ１−Ｃ１０）アルキルアミノ基、ジ（Ｃ１−Ｃ１０）アルキルアミノ基、フェニル基、フェノキシ基若しくは（Ｃ１−Ｃ１０）アルコキシ基によって置換されていてもよいアリール基を示し、Ｒ_２７は水酸基、アミノ基、シアノ基、ホルミル基、カルボキシ基、ウレイド基、（Ｃ１−Ｃ１０）アルキル基、（Ｃ１−Ｃ１０）アルキルアミノ基、ジ（Ｃ１−Ｃ１０）アルキルアミノ基、フェニル基、フェノキシ基若しくは（Ｃ１−Ｃ１０）アルコキシ基によって置換されていてもよいアリール基、（Ｃ１〜Ｃ６）アルキル基、（Ｃ２〜Ｃ６）アルケニル基、フェネチル基、カルボニル基、又は上記式（５）で表わされる縮合型ホスホン酸誘導体あるいはその塩、又は、下記式（３）

(In the formula, n ₂ represents an integer of 0 to 3, and R ₂₁ , R ₂₂ , R ₂₃ and R ₂₄ are each independently a hydroxyl group, amino group, cyano group, formyl group, carboxy group, ureido group, (C1- C10) an aryl group optionally substituted by an alkyl group, a (C1-C10) alkylamino group, a di (C1-C10) alkylamino group, a phenyl group, a phenoxy group or a (C1-C10) alkoxy group, or ( C1-C10) represents an alkyl group, and R ₂₅ and R ₂₆ are each independently a hydrogen atom, (C1-C3) alkyl group, phenethyl group, or hydroxyl group, amino group, cyano group, formyl group, carboxy group, ureido group. , (C1-C10) alkyl group, (C1-C10) alkylamino group, di (C1-C10) alkylamino group, phenyl group, phenoxy group Properly represents a (C1-C10) aryl group optionally substituted by alkoxy _{group, R 27} represents a hydroxyl group, an amino group, a cyano group, a formyl group, a carboxy group, a ureido group, (C1-C10) alkyl group, ( C1-C10) an alkylamino group, a di (C1-C10) alkylamino group, a phenyl group, a phenoxy group, or an aryl group optionally substituted by a (C1-C10) alkoxy group, (C1-C6) alkyl group, ( C2-C6) Alkenyl group, phenethyl group, carbonyl group, condensed phosphonic acid derivative represented by the above formula (5) or a salt thereof, or the following formula (3)

（式中、ｎ_３は１〜３の整数を示し、Ｒ_３１、Ｒ_３２、Ｒ_３３、Ｒ_３４は、それぞれ独立に水酸基、アミノ基、シアノ基、ホルミル基、カルボキシ基、ウレイド基、（Ｃ１−Ｃ１０）アルキル基、（Ｃ１−Ｃ１０）アルキルアミノ基、ジ（Ｃ１−Ｃ１０）アルキルアミノ基、フェニル基、フェノキシ基若しくは（Ｃ１−Ｃ１０）アルコキシ基によって置換されていてもよいアリール基、又は、（Ｃ１−Ｃ１０）アルキル基を示し、Ｒ_３５は水素原子、（Ｃ１−Ｃ３）アルキル基、フェネチル基、又は、水酸基、アミノ基、シアノ基、ホルミル基、カルボキシ基、ウレイド基、（Ｃ１−Ｃ１０）アルキル基、（Ｃ１−Ｃ１０）アルキルアミノ基、ジ（Ｃ１−Ｃ１０）アルキルアミノ基、フェニル基、フェノキシ基若しくは（Ｃ１−Ｃ１０）アルコキシ基によって置換されていてもよいアリール基を示し、Ｒ_３６は水酸基、アミノ基、シアノ基、ホルミル基、カルボキシ基、ウレイド基、（Ｃ１−Ｃ１０）アルキル基、（Ｃ１−Ｃ１０）アルキルアミノ基、ジ（Ｃ１−Ｃ１０）アルキルアミノ基、フェニル基、フェノキシ基若しくは（Ｃ１−Ｃ１０）アルコキシ基によって置換されていてもよいアリール基、（Ｃ１〜Ｃ６）アルキル基、（Ｃ２〜Ｃ６）アルケニル基、フェネチル基、カルボニル基、又は、上記式（５）で表わされる縮合型ホスホン酸誘導体あるいはその塩、又は、下記式（４）

(In the formula, n ₃ represents an integer of 1 to 3, and R ₃₁ , R ₃₂ , R ₃₃ and R ₃₄ are each independently a hydroxyl group, an amino group, a cyano group, a formyl group, a carboxy group, a ureido group, (C1 -C10) an aryl group optionally substituted by an alkyl group, a (C1-C10) alkylamino group, a di (C1-C10) alkylamino group, a phenyl group, a phenoxy group or a (C1-C10) alkoxy group, or (C1-C10) represents an alkyl group, R ₃₅ represents a hydrogen atom, (C1-C3) alkyl group, phenethyl group, or a hydroxyl group, amino group, cyano group, formyl group, carboxy group, ureido group, (C1-C10 ) Alkyl group, (C1-C10) alkylamino group, di (C1-C10) alkylamino group, phenyl group, phenoxy group or (C1-C10) Represents an aryl group which may be substituted by an alkoxy _{group, R 36} represents a hydroxyl group, an amino group, a cyano group, a formyl group, a carboxy group, a ureido group, (C1-C10) alkyl group, (C1-C10) alkylamino group An aryl group optionally substituted by a di (C1-C10) alkylamino group, a phenyl group, a phenoxy group or a (C1-C10) alkoxy group, a (C1-C6) alkyl group, a (C2-C6) alkenyl group, Phenethyl group, carbonyl group, condensed phosphonic acid derivative represented by the above formula (5) or a salt thereof, or the following formula (4)

（式中、ｎ_４は１〜３の整数を示し、Ｒ_４１、Ｒ_４２、Ｒ_４３、Ｒ_４４は、それぞれ独立に水酸基、アミノ基、シアノ基、ホルミル基、カルボキシ基、ウレイド基、（Ｃ１−Ｃ１０）アルキル基、（Ｃ１−Ｃ１０）アルキルアミノ基、ジ（Ｃ１−Ｃ１０）アルキルアミノ基、フェニル基、フェノキシ基若しくは（Ｃ１−Ｃ１０）アルコキシ基によって置換されていてもよいアリール基、又は、（Ｃ１−Ｃ１０）アルキル基を示し、Ｒ_４５、Ｒ_４６はそれぞれ独立に水素原子、（Ｃ１〜Ｃ３）アルキル基、フェネチル基、又は、水酸基、アミノ基、シアノ基、ホルミル基、カルボキシ基、ウレイド基、（Ｃ１−Ｃ１０）アルキル基、（Ｃ１−Ｃ１０）アルキルアミノ基、ジ（Ｃ１−Ｃ１０）アルキルアミノ基、フェニル基、フェノキシ基若しくは（Ｃ１−Ｃ１０）アルコキシ基によって置換されていてもよいアリール基を示し、Ｒ_４７は、水酸基、アミノ基、シアノ基、ホルミル基、カルボキシ基、ウレイド基、（Ｃ１−Ｃ１０）アルキル基、（Ｃ１−Ｃ１０）アルキルアミノ基、ジ（Ｃ１−Ｃ１０）アルキルアミノ基、フェニル基、フェノキシ基若しくは（Ｃ１−Ｃ１０）アルコキシ基によって置換されていてもよいアリール基、（Ｃ１〜Ｃ６）アルキル基、（Ｃ２〜Ｃ６）アルケニル基、フェネチル基、カルボニル基、又は上記式（５）で表わされる縮合型ホスホン酸誘導体あるいはその塩。

(In the formula, n ₄ represents an integer of 1 to 3, and R ₄₁ , R ₄₂ , R ₄₃ and R ₄₄ each independently represent a hydroxyl group, an amino group, a cyano group, a formyl group, a carboxy group, a ureido group, (C1 -C10) an aryl group optionally substituted by an alkyl group, a (C1-C10) alkylamino group, a di (C1-C10) alkylamino group, a phenyl group, a phenoxy group or a (C1-C10) alkoxy group, or (C1-C10) represents an alkyl group, and R ₄₅ and R ₄₆ are each independently a hydrogen atom, (C1-C3) alkyl group, phenethyl group, or hydroxyl group, amino group, cyano group, formyl group, carboxy group, ureido. Group, (C1-C10) alkyl group, (C1-C10) alkylamino group, di (C1-C10) alkylamino group, phenyl group, phenoxy Or it indicates (C1-C10) aryl group optionally substituted by alkoxy _{group, R 47} represents a hydroxyl group, an amino group, a cyano group, a formyl group, a carboxy group, a ureido group, (C1-C10) alkyl group, ( C1-C10) an alkylamino group, a di (C1-C10) alkylamino group, a phenyl group, a phenoxy group, or an aryl group optionally substituted by a (C1-C10) alkoxy group, (C1-C6) alkyl group, ( C2-C6) An alkenyl group, a phenethyl group, a carbonyl group, or a condensed phosphonic acid derivative represented by the above formula (5) or a salt thereof.

2) An aqueous dispersion containing at least one condensed phosphonic acid derivative selected from the group consisting of condensed phosphonic acid derivatives represented by formulas (1) to (4) and a surfactant.
3) 1 to 90% by weight of the total amount of one or more condensed phosphonic acid derivatives selected from the group consisting of the condensed phosphonic acid derivatives represented by formulas (1) to (4) in the aqueous dispersion The aqueous dispersion as described in 2) above.
4) The aqueous dispersion according to any one of 2) or 3) above, wherein the surfactant is a nonionic surfactant, an anionic surfactant, or both.
5) Furthermore, the aqueous dispersion as described in any one of said 2) -4) containing a ultraviolet absorber.

6) The aqueous dispersion according to any one of 2) to 5) above, which is used as a flameproofing agent for fibers.
7) The aqueous dispersion according to 6) above, wherein the fibers are polyester fibers.
8) The aqueous dispersion according to 7) above, wherein the polyester fiber is a cationic dyeable polyester fiber or a blended fiber containing a cationic dyeable polyester fiber.

9) A method for flameproofing a fiber, comprising using the aqueous dispersion according to any one of 2) to 8) above.
10) A fiber that has been flameproofed by the method described in 9) above.

  The aqueous dispersion of the present invention contains a condensed phosphonic acid derivative and a surfactant and is suitable as a flameproofing agent, and has light resistance and durability by applying a flameproofing treatment to the fiber using this. Excellent flameproofing performance can be imparted to fibers, particularly CDP fibers, blended fibers of polyester fibers and polyester fibers, and fibers with added functionality.

Hereinafter, the present invention will be described in detail.
The aqueous dispersion for flameproofing of the present invention comprises one or more condensed phosphonic acid derivatives selected from the group of compounds represented by the above formula (1), formula (2), formula (3), and formula (4). And a surfactant. Moreover, you may contain a ultraviolet absorber in order to improve light fastness more.

R _{11 to} R ₁₅ in Formula (1), R _{21 to} R ₂₇ in Formula (2), R _{31 to} R ₃₆ in Formula (3), and R _{41 to} R ₄₇ in Formula (4) are each independent. Is a substituent.

R _{11 to} R ₁₄ , R _{21 to} R ₂₄ , R _{31 to} R ₃₄ , R _{41 to} R ₄₄ , a hydroxyl group, an amino group, a cyano group, a formyl group, a carboxy group, a ureido group, a (C1-C10) alkyl group, ( Examples of the aryl group optionally substituted by a C1-C10) alkylamino group, a di (C1-C10) alkylamino group, a phenyl group, a phenoxy group, or a (C1-C10) alkoxy group include, for example, a phenyl group, methylphenyl Group, ethylphenyl group, propylphenyl group, dimethylphenyl group, hydroxyphenyl group, methoxyphenyl group, ethoxyphenyl group, aminophenyl group, N, N-dimethylaminophenyl group, N, N-diethylaminophenyl group, N, N -Diphenylaminophenyl group, cyanophenyl group, biphenyl , Naphthyl group and the like. When it has a substituent, the substitution position of the substituent is not particularly limited, and any substitution position is included in the present invention.
Examples of the (C1-C10) alkyl group in R _{11 to} R ₁₄ , R _{21 to} R ₂₄ , R _{31 to} R ₃₄ , and R _{41 to} R ₄₄ include a methyl group, an ethyl group, an n-propyl group, and a cyclohexyl group. Group, n-octyl group and the like.

R ₂₅ , R ₂₆ , R ₃₅ , R ₄₅ , R ₄₆ hydroxyl group, amino group, cyano group, formyl group, carboxy group, ureido group, (C1-C10) alkyl group, (C1-C10) alkylamino group, di Examples of the aryl group optionally substituted by (C1-C10) alkylamino group, phenyl group, phenoxy group or (C1-C10) alkoxy group include phenyl group, methylphenyl group, ethylphenyl group, propylphenyl group. , Dimethylphenyl group, hydroxyphenyl group, methoxyphenyl group, ethoxyphenyl group, aminophenyl group, N, N-dimethylaminophenyl group, N, N-diethylaminophenyl group, N, N-diphenylaminophenyl group, cyanophenyl group , Biphenyl group, naphthyl group and the like. When it has a substituent, the substitution position of the substituent is not particularly limited, and any substitution position is included in the present invention.
Examples of the (C1-C3) alkyl group in R ₂₅ , R ₂₆ , R ₃₅ , R ₄₅ , and R ₄₆ include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group.

R ₁₅ , R ₂₇ , R ₃₆ , R ₄₇ hydroxyl group, amino group, cyano group, formyl group, carboxy group, ureido group, (C1-C10) alkyl group, (C1-C10) alkylamino group, di (C1- Examples of the aryl group optionally substituted by C10) alkylamino group, phenyl group, phenoxy group or (C1-C10) alkoxy group include phenyl group, methylphenyl group, ethylphenyl group, propylphenyl group, and dimethylphenyl. Group, hydroxyphenyl group, methoxyphenyl group, ethoxyphenyl group, aminophenyl group, N, N-dimethylaminophenyl group, N, N-diethylaminophenyl group, N, N-diphenylaminophenyl group, cyanophenyl group, biphenyl group And a naphthyl group. When it has a substituent, the substitution position of the substituent is not particularly limited, and any substitution position is included in the present invention.
Examples of the (C1-C6) alkyl group in R ₁₅ , R ₂₇ , R ₃₆ and R ₄₇ include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group, and (C5-C8) cyclo Examples of the alkyl group include a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group. Examples of the (C2-C6) alkenyl group include a vinyl group, a propenyl group, and a cyclohexenyl group.

Preferred groups as R _{11 to} R ₁₄ , R _{21 to} R ₂₄ , R _{31 to} R ₃₄ , R _{41 to} R ₄₄ include a phenyl group, a methylphenyl group, a biphenyl group, a methoxyphenyl group, and the like. A methylphenyl group and a methoxyphenyl group are particularly preferred.
R ₁₅ , R ₂₅ , R ₂₆ , R ₃₅ , R ₄₅ and R ₄₆ are preferably hydrogen atoms.
Preferred groups as R ₁₅ , R ₂₇ , R ₃₆ , and R ₄₇ are phenyl group, methylphenyl group, biphenyl group, methoxyphenyl group, m-xylenyl group, p-xylenyl group, carbonyl group or the above formula (5). The substituent represented is mentioned, Among them, a phenyl group, a methylphenyl group, a biphenyl group, an m-xylenyl group, a p-xylenyl group, and a substituent represented by the above formula (5) are particularly preferable.

n _{1, n} 3, _{n 4} is an integer from 1 to 3, _{n 2} is an integer of 0 to 3, preferably 1 or 2.
Examples of the salt of the condensed phosphonic acid derivative in the present invention include a salt with a base in the case of an acidic substance, and a salt with an acid in the case of a basic substance, so long as it can be obtained by a normal salt formation reaction. There is no particular limitation.

  Among the condensed phosphonic acid derivatives of the above formulas (1) to (4) contained in the aqueous dispersion of the present invention, preferred compounds include those used in the following examples.

  As the ultraviolet absorber that may be contained in the aqueous dispersion of the present invention, any compound that absorbs ultraviolet rays can be used without particular limitation. Moreover, this ultraviolet absorber is used in order to improve light fastness more.

  Examples of the ultraviolet absorber include salicylic acid compounds, benzophenone compounds, benzotriazole compounds, hindered amine compounds, triazine compounds, cinnamic acid compounds, stilbene compounds; or ultraviolet rays represented by benzoxazole compounds. It is also possible to use a compound that absorbs light and emits fluorescence (so-called fluorescent whitening agent).

Among the ultraviolet absorbers that may be contained in the aqueous dispersion of the present invention, the structural formulas of preferred compounds are shown below.

In the above formula (106), which is a benzotriazole-based ultraviolet absorber, R ₅ includes (C1-C12) linear or branched alkyl group or cumyl group, more preferably (C3-C6) linear or A branched alkyl group is mentioned, More preferably, a (C3-C5) branched alkyl group is mentioned, for example, isopropyl group, isobutyl group, s-butyl group, t-butyl group, 1-methylbutyl group, 2-methylbutyl. Group, 3-methylbutyl group, 1-ethylpropyl group and the like.

In the above formula (106), examples of R ₆ include a hydroxyl group, a (C1-C12) linear or branched alkyl group, a (C1-C12) linear or branched alkoxy group, or a benzyloxy group. ) A linear or branched alkyl group is preferred. More preferred is a (C1-C6) linear or branched alkyl group, and further preferred is a (C1-C3) linear or branched alkyl group, such as a methyl group, an ethyl group, or an n-propyl group. And isopropyl group.

In the above formula (106), examples of R ₇ include a hydrogen atom, a hydroxyl group, a (C1-C12) linear or branched alkyl group, or a (C1-C12) linear or branched alkoxy group. A hydrogen atom, a methyl group , An ethyl group, an n-propyl group or an isopropyl group is preferable, and a hydrogen atom is more preferable. R ₈ may be a hydrogen atom or a hydroxyl group, preferably a hydroxyl group, and X may be a hydrogen atom or a chlorine atom, preferably a chlorine atom.

As a particularly preferred combination of R _{5 to} R ₈ and X, R ₅ is a t-butyl group, R ₆ is a methyl group, R ₇ is a hydrogen atom, R ₈ is a hydroxyl group, and X is a chlorine atom.

Moreover, as a compound preferable as an ultraviolet absorber other than the benzotriazole compound represented by the above formula (106), a benzophenone compound represented by the above formula (101), the formula (102), and the formula (103), a formula ( 104) (wherein R ₉ and R ₁₀ each independently represents a hydrogen atom, a hydroxyl group or a (C1-C5) alkyl group), a benzotriazole represented by the formula (105) complex compound systems and benzophenone (wherein, _{R 1} is a (C1-C2) alkyl group or cumyl group, _{R 2} is a hydroxyl group, a (C1-C2) alkoxy or benzyloxy group, _{R 3} is a hydrogen atom , A hydroxyl group or a (C1-C2) alkoxy group, R ₄ represents a hydrogen atom or a hydroxyl group, and X represents a hydrogen atom or a chlorine atom.

  A particularly preferred compound as an ultraviolet absorber that may be contained in the aqueous dispersion of the present invention is a benzotriazole-based compound represented by the formula (106).

  As the surfactant, a cation type, a nonionic type or an anion type is known, and any type of the surfactant contained in the aqueous dispersion of the present invention can be used. When preparing the aqueous dispersion of the present invention, it is preferable to use a nonionic type or an anionic type, or a mixture of a nonionic type and an anionic type.

  Examples of the anionic surfactants include alkyl sulfate salts such as higher alcohol sulfates, higher alkyl ether sulfates, sulfated fatty acid esters, alkylbenzene sulfonates, and alkyl sulfonate salts such as alkyl naphthalene sulfonates. Furthermore, alkyl phosphate salts such as a higher alcohol phosphate ester salt and a phosphate ester salt of an alkylene oxide adduct of a higher alcohol may be mentioned. In addition, alkyl aryl sulfonate salt, polyoxyalkylene alkyl ether sulfate salt, polyoxyalkylene alkyl ester phosphate salt, polyoxyalkylene alkyl ether carboxylate salt, polycarboxylate, funnel oil, petroleum sulfonate, alkyl diphenyl ether sulfonate salt, etc. Among them, polyoxyethylene distyrenated phenyl ether sulfate salt or polyoxyethylene tristyrenated phenyl ether sulfate salt is exemplified.

（式中Ｒは水素原子、（Ｃ１−Ｃ１８）アルキル基、スチリル基又はベンジル基を示し、ｎは１〜１５の整数を示す。）で表わされるポリオキシエチレンフェニルエーテルの硫酸エステルあるいは下記一般式（３１）

（式中Ｒ’は（Ｃ８−Ｃ３０）アルキル基又は（Ｃ８−Ｃ３０）アルキルアリール基を、ｙは１〜３０の整数を、Ｒ’’は水素原子又はＲ’Ｏ（ＣＨ２ＣＨ２Ｏ）ｙ基を示す。）で表されるポリオキシエチレンアルキルアリルエーテルのリン酸エステルが特に好ましい。 As an anionic surfactant which may be contained in the aqueous dispersion of the present invention, the following formula (107)

(Wherein R represents a hydrogen atom, a (C1-C18) alkyl group, a styryl group or a benzyl group, and n represents an integer of 1 to 15) or a sulfate of polyoxyethylene phenyl ether represented by the following general formula: (31)

Wherein R ′ is a (C8-C30) alkyl group or (C8-C30) alkylaryl group, y is an integer of 1 to 30, and R ″ is a hydrogen atom or R′O (CH 2 CH 2 O) y group. The phosphoric acid ester of polyoxyethylene alkyl allyl ether represented by.

  Examples of the compound represented by the general formula (31) include Prisurf AL (trade name, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.).

  In general formula (107) and general formula (31), although described as a free acid for convenience, it may be used as a salt having an alkali metal, ammonium or the like as a counter cation. Examples of the counter cation include lithium. Sodium, potassium, ammonium and the like, among which sodium salt or ammonium salt is preferable.

  Preferred examples of the compound represented by the formula (107) include compounds in which R is a (C1-C12) straight chain alkyl group and n is 4 to 12, particularly a compound in which R is an n-nonyl group and n is 7. preferable.

  As the nonionic surfactant, for example, polyoxyethylene styrenated phenyl ether, polyoxyethylene distyrenated phenyl ether, polyoxyethylene tristyrenated phenyl ether, or the like can be preferably used.

  Examples of the polyoxyethylene styrenated phenyl ether include a compound represented by the following formula (108) or a mixture of compounds represented by the formula (108). In the formula (108), m ′ is preferably 1 to 3 and n ′ is preferably 8 to 30.

Examples of the mixture of compounds represented by the above formula (108) include Neugen EA-87 (trade name, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.).

  The above surfactants may be used alone or in combination. That is, one to plural types of anionic or nonionic types may be used, or one to plural types of anionic and nonionic types may be mixed and used.

  The above surfactants may be used alone or in combination. That is, a plurality of anionic types or nonionic types may be mixed and used, or one to a plurality of types of anionic types and nonionic types may be mixed and used.

The following is mentioned as a preferable aspect in the aqueous dispersion of the flameproofing agent of this invention. That is, a phosphorus compound selected from the compound group consisting of the condensed phosphoric ester amide compound (A) represented by the above formula (1) and the condensed phosphoric amide compound (B) represented by the above formula (2). The total amount of the aqueous dispersion is 1 to 90% by weight, preferably 5 to 70% by weight, particularly preferably 5 to 50% by weight.
When the condensed phosphoramide compound (C) represented by the above formula (3) is contained in the aqueous dispersion of the flameproofing agent of the present invention, the content is preferably about 1 to 90% by weight in the aqueous dispersion, preferably Is about 5 to 70% by weight.

  When the ultraviolet absorber is contained, its content is in the range of 0.1 to 10% by weight, preferably 0.5 to 10% by weight, particularly preferably 1 to 5% by weight in the aqueous dispersion.

  The surfactant contained in the aqueous dispersion of the flameproofing agent of the present invention is 5 to 80% by weight, preferably 10 to 50% by weight, based on the total amount of the organic phosphorus compound and the optional ultraviolet absorber. Particularly preferably, it is contained in the range of 15 to 35% by weight.

The aqueous dispersion of the present invention may contain additives other than the above, such as surfactants and dispersants, as necessary, within a range not impairing the effects of the present invention. If necessary, protective colloids or thickeners such as polyvinyl alcohol, methylcellulose, carboxymethylcellulose, starch paste and the like to enhance storage stability; anti-flammability to enhance flameproofing effects such as phosphate esters and phosphate amides It may contain a flame aid, an antioxidant and the like.
Alkali agents, acids, fats and oils, higher alcohols, higher fatty acids, lower alcohols, organic solvents, penetration enhancers, polyhydric alcohols, antifoaming agents, antiseptics, fungicides, chelating agents, pH adjusters, dyes Alternatively, a pigment or the like may be added.

  The aqueous dispersion of the present invention is prepared by adding each of the above components to water.

  The fiber that can be flameproofed by the dispersion of the present invention is not particularly limited, and examples thereof include polyester fibers, particularly CDP (cation dyeable polyester) fibers, and blended fibers of CDP fibers and polyester fibers. Moreover, the fiber which provided various functionality, such as antibacterial processing, deodorizing processing, and surface processing, is also mentioned.

  Examples of the CDP fiber and the polyester fiber include polyethylene terephthalate, polybutylene terephthalate, polyoxyethoxybenzoate, polyethylene naphthalate, cyclohexanedimethylene terephthalate, and other polyester fibers. Examples include, but are not limited to, fibers of materials obtained by copolymerization of dicarboxylic acid components such as adipic acid and sulfoisophthalic acid, and diol components such as propylene glycol, butylene glycol, cyclohexane dimethanol, and diethylene glycol. It is not something.

  The fiber structure may be in any form such as yarn, woven fabric, knitted fabric, and non-woven fabric.

  In order to flameproof the fibers with the aqueous dispersion of the present invention, a known method such as a dip dyeing bath method or a padding method can be used.

  When using the dip dyeing bath method, the above-mentioned aqueous dispersion is used in combination with a disperse dye or disperse cationic dye for fibers and the like, and a temperature in the range of 110 to 150 ° C, preferably 120 to 140 ° C. Processing is performed for about 60 minutes. If necessary, a dye such as a fluorescent dye can be further added.

  In the case of using the padding method, the fiber structure is heat-treated after padding by dry heat treatment, or steam heat treatment such as saturated atmospheric steam treatment, superheated steam treatment, or high-pressure steam treatment. In both dry heat treatment and steam heat treatment, the heat treatment temperature is usually in the range of 110 to 210 ° C, preferably in the range of 170 to 210 ° C. If the heat treatment temperature exceeds 210 ° C, the polyester synthetic fibers may be yellowed or embrittled.

  If necessary, the dip dyeing bath method and the padding method may be used in combination. In this case, it is preferable that the fiber is subjected to flameproofing by the dip dyeing bath method and then reprocessed by the padding method. By this method, higher flameproof performance can be imparted.

  The present invention also includes the condensed phosphoric ester amide compound (A) represented by the above formula (1) or a salt thereof. As a method for producing the compound, for example, as shown in the following examples, a phosphoric acid halide may be reacted with a compound having a phenolic hydroxyl group or an alcoholic hydroxyl group or a compound having an amino group.

  EXAMPLES The present invention will be further described below with reference to examples, but the present invention is not limited only to these examples. In the examples, “parts” and “%” indicate “parts by weight” and “% by weight”, respectively, unless otherwise specified.

The structural formulas of the compounds used in the following examples and comparative examples are described below. Each compound can be produced by a known production method in the literature or by applying the production method.
[Synthesis example]

Formula (201) is a compound of the above formula (1) in which R _{11 to} R ₁₄ are a phenyl group, R ₁₅ is an ethyl group, and n ₁ is 1. This compound was prepared by reacting 50 parts of phenyl dichlorophosphate (C ₆ H ₅ POCl ₂ ), 24 parts of phenol and 31 parts of triethylamine in 300 parts of tetrahydrofuran at 1 ° C. or less for 1 hour, and then 8 parts of ethylene glycol and 26 parts of triethylamine. The mixture is reacted at 10 ° C. or lower for 1 hour and at room temperature for 10 hours, 100 parts of water is added, and the solvent and the like are distilled off from the separated upper layer. The obtained compound was a pale yellow liquid, and the compound was identified from the measurement of LC-MS.
MS: 494.10 (found), 494.11 (theory)

Formula (202) is a compound of the above formula (1) in which R ₁₁ and R ₁₂ are phenyl groups, R ₁₃ and R ₁₄ are 4-methylphenyl groups, R ₁₅ is an ethyl group and n ₁ is 1. This compound was prepared by reacting 50 parts of phenyl dichlorophosphate, 28 parts of 4-methylphenol and 31 parts of triethylamine in 300 parts of tetrahydrofuran at 10 ° C. or less for 1 hour, and then 8 parts of ethylene glycol and 26 parts of triethylamine at 10 ° C. or less. It is obtained by reacting for 1 hour at room temperature for 10 hours, adding 100 parts of water, and distilling off the solvent and the like from the separated upper layer. The obtained compound was a pale yellow liquid, and the compound was identified from the measurement of LC-MS.
MS: 522.14 (found), 522.14 (theory)

Formula (203) is a compound of the above formula (2) in which R _{21 to} R ₂₄ are phenyl groups, R ₂₅ and R ₂₆ are hydrogen atoms, R ₂₇ is an ethyl group, and n ₂ is 1. This compound was prepared by reacting 50 parts of phenyl dichlorophosphate, 24 parts of phenol and 31 parts of triethylamine in 10 parts of tetrahydrofuran at 300 ° C. for 1 hour, and then 8 parts of 1,2-ethylenediamine and 26 parts of triethylamine at 10 ° C. or less. It is obtained by reacting for 1 hour at room temperature for 10 hours, adding 100 parts of water, and distilling off the solvent and the like from the separated upper layer. The obtained compound was a white solid, and the compound was identified from the measurement of LC-MS.
MS: 492.14 (found), 492.15 (theory)

Formula (204) is the above formula wherein R ₂₁ and R ₂₂ are phenyl groups, R ₂₃ and R ₂₄ are 4-methylphenyl groups, R ₂₅ and R ₂₆ are hydrogen atoms, R ₂₇ is an ethyl group and n ₂ is 1. It is a compound of (2). This compound was prepared by reacting 50 parts of phenyl dichlorophosphate, 28 parts of 4-methylphenol and 31 parts of triethylamine in 10 parts of tetrahydrofuran at 10 ° C. or less for 1 hour, and then adding 8 parts of 1,2-ethylenediamine and 26 parts of triethylamine to 10 parts. The reaction is carried out at 1 ° C. or lower for 1 hour and at room temperature for 10 hours, 100 parts of water is added, and the solvent is distilled off from the separated upper layer. The obtained compound was a pale yellow solid and was identified by LC-MS measurement.
MS: 520.17 (found), 520.17 (theory)

Formula (205) is a compound of the above formula (3) in which R _{31 to} R ₃₄ are a phenyl group, R ₃₅ is a hydrogen atom, R ₃₆ is an ethyl group, and n ₃ is 1. This compound was prepared by reacting 50 parts of phenyl dichlorophosphate, 24 parts of phenol and 31 parts of triethylamine in 10 parts or less of tetrahydrofuran at 300 ° C for 1 hour, and then adding 8 parts of 2-aminoethanol and 26 parts of triethylamine at 10 ° C or less. It is obtained by reacting for 10 hours at room temperature, adding 100 parts of water, and distilling off the solvent and the like from the separated upper layer. The obtained compound was a pale yellow solid and was identified by LC-MS measurement.
MS: 493.12 (found), 493.13 (theory)

In formula (206), R ₃₁ and R ₃₂ are phenyl groups, R ₃₃ and R ₃₄ are 4-methylphenyl groups, R ₃₅ is a hydrogen atom, R ₃₆ is an ethyl group, and n ₃ is 1. It is a compound. This compound was prepared by reacting 50 parts of phenyl dichlorophosphate, 28 parts of 4-methylphenol and 31 parts of triethylamine in 10 parts of tetrahydrofuran at 10 ° C. or less for 1 hour, and then adding 8 parts of 2-aminoethanol and 26 parts of triethylamine to 10 ° C. The reaction is carried out for 1 hour at room temperature for 10 hours below, 100 parts of water is added, and the solvent and the like are distilled off from the separated upper layer. The obtained compound was a pale yellow solid and was identified by LC-MS measurement.
MS: 521.15 (found), 521.14 (theory)

Formula (207) is a compound of the above formula (4) in which R _{41 to} R ₄₄ are phenyl groups, R ₄₅ and R ₄₆ are hydrogen atoms, R ₄₇ is an ethyl group, and n ₄ is 1. This compound was prepared by reacting 50 parts of phenyl dichlorophosphate, 8 parts of ethylene glycol and 39 parts of triethylamine in 10 parts of tetrahydrofuran at 300 ° C. for 1 hour, and then 24 parts of aniline and 31 parts of triethylamine at 10 ° C. or less for 1 hour. The reaction is carried out at room temperature for 10 hours, 100 parts of water is added, and the solvent and the like are distilled off from the separated upper layer. The obtained compound was a pale yellow solid and was identified by LC-MS measurement.
MS: 492.14 (found), 492.15 (theory)

In formula (208), R ₄₁ and R ₄₂ are phenyl groups, R ₄₃ and R ₄₄ are 4-methylphenyl groups, R ₄₅ and R ₄₆ are hydrogen atoms, R ₄₇ is an ethyl group, and n ₄ is 1. It is a compound of (4). This compound was prepared by reacting 50 parts of phenyl dichlorophosphate, 8 parts of ethylene glycol and 39 parts of triethylamine in 10 parts of tetrahydrofuran at 300 ° C for 1 hour, and then 28 parts of 4-methylaniline and 31 parts of triethylamine at 10 ° C or less. It is obtained by reacting for 1 hour at room temperature for 10 hours, adding 100 parts of water, and distilling off the solvent and the like from the separated upper layer. The obtained compound was a pale yellow solid and was identified by LC-MS measurement.
MS: 520.17 (found), 520.18 (theory)

Formula (209) is a compound of the above formula (3) in which R _{31 to} R ₃₄ are a phenyl group, R ₃₅ is a hydrogen atom, R ₃₆ is an o-substituted phenyl group, and n ₃ is 1. This compound was prepared by reacting 50 parts of phenyl dichlorophosphate, 24 parts of phenol and 31 parts of triethylamine in 10 parts or less of tetrahydrofuran at 300 ° C for 1 hour, then 14 parts of 2-aminophenol and 39 parts of triethylamine at 10 ° C or less. It is obtained by reacting for 10 hours at room temperature, adding 100 parts of water, and distilling off the solvent and the like from the separated upper layer. The obtained compound was a pale yellow solid and was identified by LC-MS measurement.
MS: 541.12 (found), 573.11 (theory)

Formula (210) is a compound of the above formula (3) in which R _{31 to} R ₃₄ are phenyl groups, R ₃₅ is a hydrogen atom, R ₃₆ is an m-substituted phenyl group, and n ₃ is 1. This compound was prepared by reacting 50 parts of phenyl dichlorophosphate, 24 parts of phenol and 31 parts of triethylamine in 10 parts or less of tetrahydrofuran at 300 ° C for 1 hour, then 14 parts of 3-aminophenol and 39 parts of triethylamine at 10 ° C or less. It is obtained by reacting for 10 hours at room temperature, adding 100 parts of water, and distilling off the solvent and the like from the separated upper layer. The obtained compound was a pale yellow solid and was identified by LC-MS measurement.
MS: 541.12 (found), 541.12 (theory)

Formula (211) is a compound of the above formula (3) in which R _{31 to} R ₃₄ are a phenyl group, R ₃₅ is a hydrogen atom, and R ₃₆ is a p-substituted phenyl group. This compound was prepared by reacting 50 parts of phenyl dichlorophosphate, 24 parts of phenol and 31 parts of triethylamine in 10 parts of tetrahydrofuran at 300 ° C. for 1 hour, and then adding 14 parts of 4-aminophenol and 39 parts of triethylamine at 10 ° C. or less. It is obtained by reacting for 10 hours at room temperature, adding 100 parts of water, and distilling off the solvent and the like from the separated upper layer. The obtained compound was a pale yellow solid and was identified by LC-MS measurement.
MS: 541.12 (found), 541.13 (theory)

Formula (212) is a compound of the above formula (4) in which R _{41 to} R ₄₄ are phenyl groups, R ₄₅ and R ₄₆ are hydrogen atoms, R ₄₇ is diphenyl sulfone and n ₄ is 1. This compound was prepared by reacting 50 parts of phenyl dichlorophosphate, 32 parts of bis (4-hydroxyphenyl) sulfone and 39 parts of triethylamine in 300 parts of tetrahydrofuran at 10 ° C. or less for 1 hour, and then adding 24 parts of aniline and 31 parts of triethylamine to 10 parts. The reaction is carried out at 1 ° C. or lower for 1 hour and at room temperature for 10 hours, 100 parts of water is added, and the solvent is distilled off from the separated upper layer. The obtained compound was a pale yellow solid and was identified by LC-MS measurement.
MS: 680.13 (found), 680.14 (theory)

Formula (213) is a compound of the above formula (2) in which R _{21 to} R ₂₄ are phenyl groups, R ₂₅ and R ₂₆ are hydrogen atoms, R ₂₇ is diphenyl sulfone and n ₂ is 1. This compound was prepared by reacting 50 parts of phenyl dichlorophosphate, 24 parts of phenol and 31 parts of triethylamine in 300 parts of tetrahydrofuran at 10 ° C. or less for 1 hour, and then adding 32 parts of bis (4-aminophenyl) sulfone and 39 parts of triethylamine to 10 parts. The reaction is carried out at 1 ° C. or lower for 1 hour and at room temperature for 10 hours, 100 parts of water is added, and the solvent is distilled off from the separated upper layer. The obtained compound was a pale yellow solid and was identified by LC-MS measurement.
MS: 680.13 (found), 680.13 (theory)

Formula (217) is a compound of the above formula (3) in which R _{31 to} R ₃₄ are a phenyl group, R ₃₅ is a hydrogen atom, R ₃₆ is an ethyl group, and n ₃ is 2. This compound was prepared by reacting 50 parts of phenyl dichlorophosphate, 24 parts of phenol and 31 parts of triethylamine in 300 parts of tetrahydrofuran at 10 ° C. or less for 1 hour, and then adding 14 parts of 2- (2-aminoethoxy) ethanol and 39 parts of triethylamine. It is obtained by reacting at 10 ° C. or lower for 1 hour and at room temperature for 10 hours, adding 100 parts of water, and distilling off the solvent and the like from the separated upper layer. The obtained compound was a pale yellow solid and was identified by LC-MS measurement.
MS: 537.15 (found), 537.14 (theory)

Formula (218) is a compound of the above formula (2) in which R _{21 to} R ₂₄ are phenyl groups, R ₂₅ and R ₂₆ are hydrogen atoms, R ₂₇ is an o-substituted phenyl group, and n ₂ is 1. This compound is obtained by reacting 50 parts of phenyl dichlorophosphate, 24 parts of phenol and 31 parts of triethylamine in 10 parts of tetrahydrofuran at 300 ° C. for 1 hour, then 14 parts of 1,2-phenylenediamine and 39 parts of triethylamine at 10 ° C. or less. For 1 hour at room temperature for 10 hours, 100 parts of water is added, and the solvent is distilled off from the separated upper layer. The obtained compound was a white solid, and the compound was identified from the measurement of LC-MS.
MS: 540.14 (found), 540.13 (theory)

Formula (219) is a compound of the above formula (2) in which R _{21 to} R ₂₄ are phenyl groups, R ₂₅ and R ₂₆ are hydrogen atoms, R ₂₇ is an m-substituted phenyl group, and n ₂ is 1. This compound was prepared by reacting 50 parts of phenyl dichlorophosphate, 24 parts of phenol and 31 parts of triethylamine in 10 parts of tetrahydrofuran at 300 ° C. for 1 hour, and then 14 parts of 1,3-phenylenediamine and 39 parts of triethylamine at 10 ° C. or less. For 1 hour at room temperature for 10 hours, 100 parts of water is added, and the solvent is distilled off from the separated upper layer. The obtained compound was a white solid, and the compound was identified from the measurement of LC-MS.
MS: 540.14 (found), 540.14 (theory)

Formula (220) is a compound of the above formula (2) in which R _{21 to} R ₂₄ are phenyl groups, R ₂₅ and R ₂₆ are hydrogen atoms, R ₂₇ is a p-substituted phenyl group, and n ₂ is 1. This compound was prepared by reacting 50 parts of phenyl dichlorophosphate, 24 parts of phenol and 31 parts of triethylamine in 10 parts or less of tetrahydrofuran at 300 ° C for 1 hour, then 14 parts of 1,4-phenylenediamine and 39 parts of triethylamine at 10 ° C or less. For 1 hour at room temperature for 10 hours, 100 parts of water is added, and the solvent is distilled off from the separated upper layer. The obtained compound was a white solid, and the compound was identified from the measurement of LC-MS.
MS: 540.14 (found), 540.14 (theory)

Formula (221) is a compound of the above formula (2) in which R _{21 to} R ₂₄ are phenyl groups, R ₂₅ and R ₂₆ are hydrogen atoms, R ₂₇ is diphenylmethane and n ₂ is 1. This compound was prepared by reacting 50 parts of phenyl dichlorophosphate, 24 parts of phenol and 31 parts of triethylamine in 10 parts of tetrahydrofuran at 300 ° C. for 1 hour, then 25 parts of 4,4′-diaminodiphenylmethane and 39 parts of triethylamine at 10 ° C. The reaction is carried out for 1 hour at room temperature for 10 hours below, 100 parts of water is added, and the solvent and the like are distilled off from the separated upper layer. The obtained compound was a white solid, and the compound was identified from the measurement of LC-MS.
MS: 630.18 (found), 630.19 (theory)

Formula (223) is a compound of the above formula (2) in which R _{21 to} R ₂₄ are phenyl groups, R ₂₅ and R ₂₆ are hydrogen atoms, R ₂₇ is diphenyl ether and n ₂ is 1. This compound was prepared by reacting 50 parts of phenyl dichlorophosphate, 24 parts of phenol and 31 parts of triethylamine at 10 ° C. or less for 1 hour in 300 parts of tetrahydrofuran, and then 26 parts of 4,4′-diaminodiphenyl ether and 39 parts of triethylamine at 10 ° C. The reaction is carried out for 1 hour at room temperature for 10 hours below, 100 parts of water is added, and the solvent and the like are distilled off from the separated upper layer. The obtained compound was a white solid, and the compound was identified from the measurement of LC-MS.
MS: 632.16 (found), 632.17 (theory)

Formula (224) is a compound of the above formula (4) in which R _{41 to} R ₄₄ are phenyl groups, R ₄₅ and R ₄₆ are hydrogen atoms, R ₄₇ is diphenylpropane and n ₄ is 1. This compound was prepared by reacting 50 parts of phenyl dichlorophosphate, 29 parts of 2,2-bis (4-hydroxyphenyl) propane and 39 parts of triethylamine in 300 parts of tetrahydrofuran for 1 hour at 10 ° C. or less, and then 24 parts of aniline and triethylamine. It is obtained by reacting 31 parts at 10 ° C. or less for 1 hour and at room temperature for 10 hours, adding 100 parts of water, and distilling off the solvent and the like from the separated upper layer. The obtained compound was a pale yellow solid and was identified by LC-MS measurement.
MS: 658.22 (found), 658.21 (theory)

Formula (225) is a compound of the above formula (2) in which R _{21 to} R ₂₄ are phenyl groups, R ₂₅ and R ₂₆ are hydrogen atoms, R ₂₇ is m-substituted dibenzyl and n ₂ is 1. This compound was prepared by reacting 50 parts of phenyl dichlorophosphate, 24 parts of phenol and 31 parts of triethylamine in 10 parts of tetrahydrofuran at 10 ° C. or less for 1 hour, and then 18 parts of m-xylylenediamine and 39 parts of triethylamine at 10 ° C. or less. It is obtained by reacting for 1 hour at room temperature for 10 hours, adding 100 parts of water, and distilling off the solvent and the like from the separated upper layer. The obtained compound was a white solid, and the compound was identified from the measurement of LC-MS.
MS: 568.16 (found), 568.17 (theory)

A compound of the following formula (301) is commercially available from Daihachi Chemical Co., Ltd. under the trade name NDPP.
The compound of the following formula (302) is commercially available from Hokuko Chemical Co., Ltd. under the trade name TPPO.
The compound of the following formula (303) is commercially available from Daihachi Chemical Co., Ltd. under the trade name TPP.

  Each organic phosphonic acid derivative shown in the following table was pulverized with a sand grinder as necessary, and each component was added to water to obtain an aqueous dispersion.

[Example 1]
Table 1
Water 63.0%
Formula (201) (Compound of general formula (1)) 30.0%
Prisurf ALNa salt 6.3%
Thickener 0.5%
Antifoam 0.1%
Antifungal agent 0.1%
100.0%

[Example 2]
Table 2
Water 63.0%
Formula (202) (Compound of general formula (1)) 30.0%
Prisurf ALNa salt 6.3%
Thickener 0.5%
Antifoam 0.1%
Antifungal agent 0.1%
100.0%

[Example 3]
Table 3
Water 63.0%
Formula (203) (Compound of general formula (2)) 30.0%
Prisurf ALNa salt 6.3%
Thickener 0.5%
Antifoam 0.1%
Antifungal agent 0.1%
100.0%

[Example 4]
Table 4
Water 63.0%
Formula (204) (Compound of General Formula (2)) 30.0%
Prisurf ALNa salt 6.3%
Thickener 0.5%
Antifoam 0.1%
Antifungal agent 0.1%
100.0%

[Example 5]
Table 5
Water 63.0%
Formula (205) (Compound of general formula (3)) 30.0%
Prisurf ALNa salt 6.3%
Thickener 0.5%
Antifoam 0.1%
Antifungal agent 0.1%
100.0%

[Example 6]
Table 6
Water 63.0%
Formula (206) (Compound of general formula (3)) 30.0%
Prisurf ALNa salt 6.3%
Thickener 0.5%
Antifoam 0.1%
Antifungal agent 0.1%
100.0%

[Example 7]
Table 7
Water 63.0%
Formula (207) (Compound of general formula (4)) 30.0%
Prisurf ALNa salt 6.3%
Thickener 0.5%
Antifoam 0.1%
Antifungal agent 0.1%
100.0%

[Example 8]
Table 8
Water 63.0%
Formula (208) (Compound of general formula (4)) 30.0%
Prisurf ALNa salt 6.3%
Thickener 0.5%
Antifoam 0.1%
Antifungal agent 0.1%
100.0%

[Example 9]
Table 9
Water 63.0%
Formula (209) (Compound of general formula (3)) 30.0%
Prisurf ALNa salt 6.3%
Thickener 0.5%
Antifoam 0.1%
Antifungal agent 0.1%
100.0%

[Example 10]
Table 10
Water 63.0%
Formula (210) (Compound of general formula (3)) 30.0%
Prisurf ALNa salt 6.3%
Thickener 0.5%
Antifoam 0.1%
Antifungal agent 0.1%
100.0%

[Example 11]
Table 11
Water 63.0%
Formula (211) (Compound of general formula (3)) 30.0%
Prisurf ALNa salt 6.3%
Thickener 0.5%
Antifoam 0.1%
Antifungal agent 0.1%
100.0%

[Example 12]
Table 12
Water 63.0%
Formula (212) (Compound of general formula (4)) 30.0%
Prisurf ALNa salt 6.3%
Thickener 0.5%
Antifoam 0.1%
Antifungal agent 0.1%
100.0%

[Example 13]
Table 13
Water 63.0%
Formula (213) (Compound of general formula (2)) 30.0%
Prisurf ALNa salt 6.3%
Thickener 0.5%
Antifoam 0.1%
Antifungal agent 0.1%
100.0%

[Example 14]
Table 14
Water 63.0%
Formula (217) (Compound of general formula (3)) 30.0%
Prisurf ALNa salt 6.3%
Thickener 0.5%
Antifoam 0.1%
Antifungal agent 0.1%
100.0%

[Example 15]
Table 15
Water 63.0%
Formula (218) (Compound of general formula (2)) 30.0%
Prisurf ALNa salt 6.3%
Thickener 0.5%
Antifoam 0.1%
Antifungal agent 0.1%
100.0%

[Example 16]
Table 16
Water 63.0%
Formula (219) (Compound of general formula (2)) 30.0%
Prisurf ALNa salt 6.3%
Thickener 0.5%
Antifoam 0.1%
Antifungal agent 0.1%
100.0%

[Example 17]
Table 17
Water 63.0%
Formula (220) (Compound of general formula (2)) 30.0%
Prisurf ALNa salt 6.3%
Thickener 0.5%
Antifoam 0.1%
Antifungal agent 0.1%
100.0%

[Example 18]
Table 18
Water 63.0%
Formula (221) (Compound of general formula (2)) 30.0%
Prisurf ALNa salt 6.3%
Thickener 0.5%
Antifoam 0.1%
Antifungal agent 0.1%
100.0%

[Example 19]
Table 19
Water 63.0%
Formula (223) (Compound of general formula (2)) 30.0%
Prisurf ALNa salt 6.3%
Thickener 0.5%
Antifoam 0.1%
Antifungal agent 0.1%
100.0%

[Example 20]
Table 20
Water 63.0%
Formula (224) (Compound of general formula (4)) 30.0%
Prisurf ALNa salt 6.3%
Thickener 0.5%
Antifoam 0.1%
Antifungal agent 0.1%
100.0%

[Example 21]
Table 21
Water 63.0%
Formula (225) (Compound of general formula (2)) 30.0%
Prisurf ALNa salt 6.3%
Thickener 0.5%
Antifoam 0.1%
Antifungal agent 0.1%
100.0%

[Comparative Example 1]
Table 22
Water 63.0%
Formula (301) 30.0%
Prisurf ALNa salt 6.3%
Thickener 0.5%
Antifoam 0.1%
Antifungal agent 0.1%
100.0%

[Comparative Example 2]
Table 23
Water 63.0%
Formula (302) 30.0%
Prisurf ALNa salt 6.3%
Thickener 0.5%
Antifoam 0.1%
Antifungal agent 0.1%
100.0%

[Comparative Example 3]
Table 24
Water 63.0%
Formula (303) 30.0%
Prisurf ALNa salt 6.3%
Thickener 0.5%
Antifoam 0.1%
Antifungal agent 0.1%
100.0%

Using the aqueous flame retardant dispersion prepared in Examples 1 to 21 or Comparative Examples 1 to 3 above, 40 cm squares of a mixed fiber fabric containing 70% polyester and 30% CDP by the same dyeing bath method. Flameproofing at the same time as dyeing.
That is, 0.72% o. w. f. (On weight of fiber) and cationic dye 0.92% o. w. f. The flameproofing agents prepared in Examples 1 to 12 or Comparative Examples 1 to 3 were treated with a bath ratio of 1:20 and 130 ° C. for 60 minutes, respectively.

  The dyes used were 0.24% Kayalon Microester Yellow AQ-LE, 0.24% Kayalon Microester Red AQ-LE, 0.24% Kayalon Microester Blue AQ-LE as a disperse dye, As cationic dyes, 0.46% Kayacrill Yellow 3RL-ED, 0.24% Kayacrill Red GL-ED, 0.22% Kayacrill Blue GSL-ED (all manufactured by Nippon Kayaku Co., Ltd.) is there.

  Thereafter, each fabric was subjected to reduction cleaning, and then heat-treated at 170 ° C. for 60 seconds. Furthermore, according to JIS K3371, a weak alkaline first-class detergent was used at a rate of 1 g / L, a bath ratio of 1:40, and each fabric was washed with water at 60 ° C. ± 2 ° C. for 15 minutes, and then at 40 ° C. ± 2 ° C. Rinsing for 5 minutes was performed 3 times, centrifugal dehydration was performed for 2 minutes, and then the process of hot air drying at 60 ° C. ± 5 ° C. was performed as 5 cycles.

  Twenty-four kinds of blended fiber fabrics obtained by the above operation and untreated blended fiber fabrics were used as test pieces, and a flammability test was performed on them.

  In addition, said reduction | restoration washing | cleaning means the following operation. That is, an aqueous solution of hydrosulfite 2 g / L, caustic soda 2 g / L, and nonionic surfactant 1 g / L was prepared, heated to 80 ° C., and then the above flameproofed fabric was added for 10 minutes. The operation to process.

Test method of flammability test A fire test method JIS L1091A-1 method (45 degree micro burner method) was used for the following evaluation. The results are shown in the table below.
Evaluation A: Pass rate

  A case where the after flame time was 3 seconds or less was regarded as acceptable, and a numerical value obtained by dividing the number of times of acceptance during the measurement by the number of times of measurement was described as the acceptance rate. The fractional part is rounded off and the unit is%. The higher the acceptance rate, the higher the flameproof performance.

  The parentheses after the pass rate are the number of passes and the number of measurements used to calculate the pass rate, and are indicated by “(pass times / measurement times)”.

Evaluation B: Average after flame time The average after flame time was calculated by dividing the total sum of after flame times measured in Test A by the number of measurements. The unit is seconds. The shorter the average afterflame time, the higher the flameproof performance.

[Table 25]

  From the results of Table 25, the pass rate of evaluation A is 86 to 100% in Examples 1 to 21 of the present invention, while 64 to 65% in each comparative example, and the pass of the examples of the present invention. The rate was high. Moreover, about the average afterflame time of evaluation B, Examples 1-21 is 0.5-3.5, while each comparative example is 3.9-6.2, The latter is an average afterflame. The time was long.

  As described above, it has been found that the test piece using the aqueous dispersion of the present invention exhibits excellent flameproof performance. In addition, the test piece using the aqueous dispersion of the present invention retains the above performance despite repeated water washing and the like for 5 cycles, so it is extremely excellent in durability. It is clear that there is.

  It is possible to provide an aqueous dispersion of a non-halogen flameproofing agent capable of imparting durable and excellent flameproofing performance to a fiber, particularly a blended fiber of CDP and polyester.

Claims (10)

Following formula (1)

(In the formula, n ₁ represents an integer of ₁ to 3, and R ₁₁ , R ₁₂ , R ₁₃ , and R ₁₄ are each independently a hydroxyl group, an amino group, a cyano group, a formyl group, a carboxy group, a ureido group, (C1 -C10) an aryl group optionally substituted by an alkyl group, a (C1-C10) alkylamino group, a di (C1-C10) alkylamino group, a phenyl group, a phenoxy group or a (C1-C10) alkoxy group, or It shows the (C1-C10) alkyl _{group, R 15} represents a hydroxyl group, an amino group, a cyano group, a formyl group, a carboxy group, a ureido group, (C1-C10) alkyl group, (C1-C10) alkylamino group, di (C1 -C10) aryl group optionally substituted by alkylamino group, phenyl group, phenoxy group or (C1-C10) alkoxy group, Or branched (C1-C6) alkyl, (C5-C8) cycloalkyl group, (C2 -C6) alkenyl group, a phenethyl group, a carbonyl group, or the following formula (5)

A condensed phosphonic acid derivative represented by the following formula (2):

(In the formula, n ₂ represents an integer of 0 to 3, and R ₂₁ , R ₂₂ , R ₂₃ and R ₂₄ are each independently a hydroxyl group, amino group, cyano group, formyl group, carboxy group, ureido group, (C1- C10) an aryl group optionally substituted by an alkyl group, a (C1-C10) alkylamino group, a di (C1-C10) alkylamino group, a phenyl group, a phenoxy group or a (C1-C10) alkoxy group, or ( C1-C10) represents an alkyl group, and R ₂₅ and R ₂₆ are each independently a hydrogen atom, (C1-C3) alkyl group, phenethyl group, or hydroxyl group, amino group, cyano group, formyl group, carboxy group, ureido group. , (C1-C10) alkyl group, (C1-C10) alkylamino group, di (C1-C10) alkylamino group, phenyl group, phenoxy group Properly represents a (C1-C10) aryl group optionally substituted by alkoxy _{group, R 27} represents a hydroxyl group, an amino group, a cyano group, a formyl group, a carboxy group, a ureido group, (C1-C10) alkyl group, ( C1-C10) an alkylamino group, a di (C1-C10) alkylamino group, a phenyl group, a phenoxy group, or an aryl group optionally substituted by a (C1-C10) alkoxy group, (C1-C6) alkyl group, ( C2-C6) Alkenyl group, phenethyl group, carbonyl group, condensed phosphonic acid derivative represented by the above formula (5) or a salt thereof, or the following formula (3)

(In the formula, n ₃ represents an integer of 1 to 3, and R ₃₁ , R ₃₂ , R ₃₃ and R ₃₄ are each independently a hydroxyl group, an amino group, a cyano group, a formyl group, a carboxy group, a ureido group, (C1 -C10) an aryl group optionally substituted by an alkyl group, a (C1-C10) alkylamino group, a di (C1-C10) alkylamino group, a phenyl group, a phenoxy group or a (C1-C10) alkoxy group, or (C1-C10) represents an alkyl group, R ₃₅ represents a hydrogen atom, (C1-C3) alkyl group, phenethyl group, or a hydroxyl group, amino group, cyano group, formyl group, carboxy group, ureido group, (C1-C10 ) Alkyl group, (C1-C10) alkylamino group, di (C1-C10) alkylamino group, phenyl group, phenoxy group or (C1-C10) Represents an aryl group which may be substituted by an alkoxy _{group, R 36} represents a hydroxyl group, an amino group, a cyano group, a formyl group, a carboxy group, a ureido group, (C1-C10) alkyl group, (C1-C10) alkylamino group An aryl group optionally substituted by a di (C1-C10) alkylamino group, a phenyl group, a phenoxy group or a (C1-C10) alkoxy group, a (C1-C6) alkyl group, a (C2-C6) alkenyl group, Phenethyl group, carbonyl group, condensed phosphonic acid derivative represented by the above formula (5) or a salt thereof, or the following formula (4)

(In the formula, n ₄ represents an integer of 1 to 3, and R ₄₁ , R ₄₂ , R ₄₃ and R ₄₄ each independently represent a hydroxyl group, an amino group, a cyano group, a formyl group, a carboxy group, a ureido group, (C1 -C10) an aryl group optionally substituted by an alkyl group, a (C1-C10) alkylamino group, a di (C1-C10) alkylamino group, a phenyl group, a phenoxy group or a (C1-C10) alkoxy group, or (C1-C10) represents an alkyl group, and R ₄₅ and R ₄₆ are each independently a hydrogen atom, (C1-C3) alkyl group, phenethyl group, or hydroxyl group, amino group, cyano group, formyl group, carboxy group, ureido. Group, (C1-C10) alkyl group, (C1-C10) alkylamino group, di (C1-C10) alkylamino group, phenyl group, phenoxy Or it indicates (C1-C10) aryl group optionally substituted by alkoxy _{group, R 47} represents a hydroxyl group, an amino group, a cyano group, a formyl group, a carboxy group, a ureido group, (C1-C10) alkyl group, ( C1-C10) an alkylamino group, a di (C1-C10) alkylamino group, a phenyl group, a phenoxy group, or an aryl group optionally substituted by a (C1-C10) alkoxy group, (C1-C6) alkyl group, ( C2-C6) An alkenyl group, a phenethyl group, a carbonyl group, or a condensed phosphonic acid derivative represented by the above formula (5) or a salt thereof. An aqueous dispersion containing at least one condensed phosphonic acid derivative selected from the group consisting of condensed phosphonic acid derivatives represented by formulas (1) to (4) and a surfactant. Claims containing 1 to 90% by weight of the total amount of one or more condensed phosphonic acid derivatives selected from the group consisting of the condensed phosphonic acid derivatives represented by formulas (1) to (4) in the aqueous dispersion. Item 3. The aqueous dispersion according to Item 2. The aqueous dispersion according to any one of claims 2 and 3, wherein the surfactant is a nonionic surfactant, an anionic surfactant, or both. Furthermore, the aqueous dispersion liquid as described in any one of Claims 2-4 containing a ultraviolet absorber. The aqueous dispersion according to any one of claims 2 to 5, which is used as a flameproofing agent for fibers. The aqueous dispersion according to claim 6, wherein the fibers are polyester fibers. The aqueous dispersion according to claim 7, wherein the polyester fiber is a cationic dyeable polyester fiber or a blended fiber containing a cationic dyeable polyester fiber. A method for flameproofing a fiber, comprising using the aqueous dispersion according to any one of claims 2 to 8. A fiber which has been flameproofed by the method according to claim 9.