JP2010184887A - Condensed phosphorus-based compound, dispersion thereof and flameproofing processing method using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an aqueous dispersion of a non-halogen flameproofing agent that can impart excellent durable flameproofing performances to a fiber, particularly a CDP fiber, a mixed spun fiber thereof with a polyester fiber and a fiber endowed with various functionalities by antibacterial processing, deodorizing processing, surface processing or the like. <P>SOLUTION: The aqueous dispersion comprises the condensed phosphoric ester amide represented by formula (1), a condensed phosphoric amide and a surfactant. In the formula, R<SB>11</SB>, R<SB>12</SB>, R<SB>13</SB>and R<SB>14</SB>are each independently a phenyl group or the like; R<SB>15</SB>is a hydrogen atom, a 1-3C alkyl group or the like; and R<SB>16</SB>is a hydroxy group or an amino group. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a non-halogen compound capable of imparting a flame resistance performance having excellent durability to a synthetic fiber structure, in particular, a condensed phosphoric ester amide compound and a flameproof process containing a condensed phosphorus compound. The present invention relates to an aqueous dispersion for use, a flameproofing process using the same, and fibers flameproofed thereby.

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 instead of halogen compounds, and fiber flameproofing methods 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 durable 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 phosphorus compound and a surfactant to provide a flameproof performance excellent in durability between CDP fibers and polyester fibers. The present invention was completed by finding that it can be applied to a blended fiber and a fiber to which functionality is imparted.

（式中、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、または、（Ｃ１−Ｃ１０）アルキル基を示し、Ｒ_１５は水素原子、（Ｃ１〜Ｃ３）アルキル基、フェネチル基、または、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_１６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、または、下記式（４）

で表わされるいずれかの基である縮合型リン酸エステルアミド化合物（Ａ）あるいはその塩。 That is, the present invention relates to the following 1) to 10).
1) The following formula (1)

(Wherein R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ are each independently a hydroxyl group, amino group, cyano group, formyl group, carboxy group, 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, or a (C1-C10) alkyl group; ₁₅ is 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. By a group, di (C1-C10) alkylamino group, phenyl group, phenoxy group or (C1-C10) alkoxy group Conversion is shown an aryl group which may _{have, R 16} is 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 ( An aryl group optionally substituted by a 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, a phenethyl group, Carbonyl group or the following formula (4)

A condensed phosphate ester amide compound (A) or a salt thereof, which is any group represented by the formula:

（式中、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、または、（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、または、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、または、下記式（４）

で表わされるいずれかの基である縮合型リン酸アミド化合物（Ｂ）あるいはその塩、または、下記式（３）

（式中、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、または、（Ｃ１−Ｃ１０）アルキル基を示し、Ｒ_３５、Ｒ_３６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、または、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_３７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、または、上記式（４）で表わされるいずれかの基である縮合型リン酸アミド化合物（Ｃ）あるいはその塩と、界面活性剤とを含有する水性分散液。 2) The condensed phosphoric ester amide compound (A) represented by the formula (1) or the following formula (2)

(Wherein 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) 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, or a (C1-C10) alkyl group; ₂₅ and R ₂₆ are each independently a hydrogen atom, a (C1-C3) alkyl group, a 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 optionally substituted by an alkoxy group, and R ₂₇ represents a hydroxyl group, an amino group, a cyano group, a formyl group, a carboxy group, a ureido group, a (C1-C10) alkyl group, a (C1-C10) alkylamino group. Group, aryl group optionally substituted by di (C1-C10) alkylamino group, phenyl group, phenoxy group or (C1-C10) alkoxy group, (C1-C6) alkyl group, (C2-C6) alkenyl group , A phenethyl group, a carbonyl group, or the following formula (4)

A condensed phosphoramide compound (B) or a salt thereof, or a group represented by the following formula (3):

(Wherein R ₃₁ , R ₃₂ , R ₃₃ and R ₃₄ are each independently a hydroxyl group, amino group, cyano group, formyl group, carboxy group, 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, or a (C1-C10) alkyl group; _{35, R 36} are each independently hydrogen, (C1 to C3) alkyl group, a phenethyl group or 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) alkylamino group, phenyl group, phenoxy group or (C1-C10) ) Represents an aryl group optionally substituted by an alkoxy group, and R ₃₇ represents a hydroxyl group, an amino group, a cyano group, a formyl group, a carboxy group, a ureido group, a (C1-C10) alkyl group, a (C1-C10) alkylamino group. Group, aryl group optionally substituted by di (C1-C10) alkylamino group, phenyl group, phenoxy group or (C1-C10) alkoxy group, (C1-C6) alkyl group, (C2-C6) alkenyl group , A phenethyl group, a carbonyl group, or a condensed phosphoramide compound (C) which is any group represented by the above formula (4) or a salt thereof, and a surfactant.

3) An aqueous dispersion of a phosphorus compound selected from the group consisting of a condensed phosphoric ester amide compound (A) represented by formula (1) and a condensed phosphoric amide compound (B) represented by formula (2) The aqueous dispersion according to 2) above, which is contained in the liquid in a total amount of 1 to 90% by weight.
4) The aqueous dispersion according to 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 phosphorus compound 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 with them, and functional fibers.

Hereinafter, the present invention will be described in detail.
The aqueous dispersion for flameproofing of the present invention is characterized by containing a condensed phosphorus compound represented by the above formula (1), formula (2), and formula (3) and a surfactant. Moreover, you may contain a ultraviolet absorber in order to improve light fastness more.

R _{11 to} R ₁₆ in the formula (1), R _{21 to} R ₂₇ in the formula (2), and R _{31 to} R ₃₇ in the formula (3) are independent substituents.
Hydroxyl group, amino group, cyano group, formyl group, carboxy group, ureido group, (C1-C10) alkyl group, (C1-C10) alkylamino group for R _{11 to} R ₁₄ , R _{21 to} R ₂₄ and R _{31 to} R ₃₄ Examples of the aryl group optionally substituted by a group, di (C1-C10) alkylamino group, phenyl group, phenoxy group or (C1-C10) alkoxy group include a phenyl group, a methylphenyl group, an 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, etc. Can be mentioned. 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 and R _{31 to} R ₃₄ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a cyclohexyl group, n -An octyl group etc. are mentioned.

Hydroxyl group, amino group, cyano group, formyl group, carboxy group, ureido group, (C1-C10) alkyl group, (C1-C10) alkylamino group, di group in R ₁₅ , R ₂₅ , R ₂₆ , R ₃₅ and R ₃₆ 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.
Moreover, as a (C1-C3) alkyl group in R _{< 15>} , R <_25> , R <_26> , R _<35> and R _<36 >, a methyl group, an ethyl group, n-propyl group, an isopropyl group etc. are mentioned, for example.

Hydroxyl group, amino group, cyano group, formyl group, carboxy group, ureido group, (C1-C10) alkyl group, (C1-C10) alkylamino group, di (C1-C10) alkyl in R ₁₆ , R ₂₇ and R ₃₇ Examples of the aryl group which may be substituted with an amino group, a phenyl group, a phenoxy group or a (C1-C10) alkoxy group include, for example, a phenyl group, a methylphenyl group, an ethylphenyl group, a propylphenyl group, a dimethylphenyl group, a hydroxy group Phenyl 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 Etc. 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 ₁₆ , R ₂₇ and R ₃₇ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a cyclohexyl group, and the like (C2-C6) alkenyl. Examples of the 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 or R _{31 to} R ₃₄ include phenyl group, methylphenyl group, biphenyl group, methoxyphenyl group, etc. Among them, phenyl group, methylphenyl group, methoxy A phenyl group is particularly preferred.
R ₁₅ , R ₂₅ , R _26, R ₃₅ and R ₃₆ are preferably hydrogen atoms.
Preferred groups as R ₁₆ , R ₂₇ , and R ₃₇ are phenyl group, methylphenyl group, biphenyl group, methoxyphenyl group, m-xylenyl group, p-xylenyl group, carbonyl group, or a substituent represented by the above formula (4). 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 (4) are particularly preferable.

  Among the condensed phosphorus compounds of the above formulas (1) to (3) 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 typified by benzoxazole compounds. It is also possible to use a compound (so-called fluorescent whitening agent) that absorbs and emits fluorescence.

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), formula (102), and 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. In 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 salt, 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、スチリル基また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）アルキル基または（Ｃ８−Ｃ３０）アルキルアリール基を、ｙは１〜３０の整数を、Ｒ’’は水素原子またはＲ’Ｏ（ＣＨ_２ＣＨ_２Ｏ）_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 1-30, R ″ is a hydrogen atom or R′O (CH ₂ CH ₂ O). The phosphoric ester of polyoxyethylene alkyl allyl ether represented by _y ) is particularly preferred.

  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 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 a compound group consisting of a condensed phosphoric ester amide compound (A) represented by the above formula (1) and a 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 polyester fiber include polyethylene terephthalate, polybutylene terephthalate, polyoxyethoxybenzoate, polyethylene naphthalate, cyclohexanedimethylene terephthalate, and other polyester fibers, and isophthalic acid as an additional component to the above polyester. 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.

  Further, 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 subjected to heat treatment by dry heat treatment or steam heat treatment such as saturated atmospheric pressure steam treatment, superheated steam treatment or high pressure steam treatment after padding. 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 collectively described below. Each compound can be produced by a production method known in the literature or by applying the production method.

Equation (201) _is a _{R 11} to _{R 14} is a phenyl _group, a compound of the formula _{R 15} is a hydrogen _{atom, R 16} is an ethyl group (1).
This compound was prepared by reacting 50 parts of diphenylphosphonic acid chloride (manufactured by Wako Pure Chemical Industries, Ltd.), 38 parts of triethylamine and 5.7 parts of 2-aminoethanol in 300 parts of tetrahydrofuran for 1 hour at 10 ° C. or less and 10 hours at room temperature. Add 100 parts, leave to pH 7 or less with dilute hydrochloric acid, separate upper layer part, add saturated brine, leave to stand, discard lower layer, and evaporate tetrahydrofuran, etc. from upper part with evaporator Is obtained. The obtained compound was a pale yellow liquid, and the compound was identified from the measurement of LC-MS.
MS: 525.12 (found), 525.11 (theory)

Formula (202) is a compound of the above formula (1) in which R _{11 to} R ₁₄ are 4-methylphenyl groups, R ₁₅ is a hydrogen atom, and R ₁₆ is an ethyl group.
This compound was prepared by reacting 50 parts of phosphorus oxychloride, 44 parts of triethylamine and 70.5 parts of 4-methylphenol in 300 parts of tetrahydrofuran at 10 ° C. or less for 1 hour, and then adding 22 parts of triethylamine and 10 parts of 2-aminoethanol. The reaction is carried out at 10 ° C. or lower for 1 hour and at room temperature for 10 hours, 100 parts of water is added and the pH is adjusted to 7 or less with dilute hydrochloric acid to separate the upper layer, and saturated saline is added and left to stand. Is obtained by distilling off tetrahydrofuran and the like from the upper layer with an evaporator. The obtained compound was a pale yellow liquid, and the compound was identified from the measurement of LC-MS.
MS: 581.17 (found), 581.17 (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, and R ₂₇ is an ethyl group.
This compound was prepared by reacting 50 parts of diphenylphosphonic chloride, 38 parts of triethylamine and 5.6 parts of 1,2-ethylenediamine in 300 parts of tetrahydrofuran at 1 ° C. or less for 1 hour and at room temperature for 10 hours, and adding 100 parts of water. The mixture is allowed to stand at a pH of 7 or less with dilute hydrochloric acid, and the upper layer is separated, and a saturated saline solution is added and the mixture is allowed to stand. The lower layer is discarded and tetrahydrofuran or the like is distilled off from the upper layer with an evaporator. The obtained compound was a pale yellow liquid, and the compound was identified from the measurement of LC-MS.
MS: 524.12 (found), 524.13 (theory)

Formula (204) is a compound of the above formula (3) in which R _{31 to} R ₃₄ are phenyl groups, R ₃₅ and R ₃₆ are hydrogen atoms, and R ₃₇ is an ethyl group.
This compound is obtained by reacting 50 parts of dichlorophosphoric acid phenyl ester (manufactured by Wako Pure Chemical Industries, Ltd.), 26 parts of triethylamine and 7.4 parts of ethylene glycol in 300 parts of tetrahydrofuran for 1 hour at 10 ° C. or less and 10 hours at room temperature. Then, 46 parts of triethylamine and 22 parts of aniline were reacted at 10 ° C. or less for 1 hour and at room temperature for 10 hours, 100 parts of water was added and the mixture was allowed to stand at pH 7 or less with dilute hydrochloric acid, and the upper layer part was separated and saturated. It is obtained by adding saline and allowing to stand, discarding the lower layer and distilling off tetrahydrofuran or the like from the upper layer portion with an evaporator. The obtained compound was a pale yellow liquid, and the compound was identified from the measurement of LC-MS.
MS: 524.13 (found), 524.13 (theory)

Formula (205) 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, and R ₂₇ is a phenyl group.
This compound was prepared by reacting 50 parts of diphenylphosphonic chloride, 38 parts of triethylamine and 10 parts of orthophenylenediamine in 300 parts of tetrahydrofuran at 1 ° C. or less for 1 hour and at room temperature for 10 hours, adding 100 parts of water and dilute hydrochloric acid. The mixture is allowed to stand at pH 7 or lower, and the upper layer portion is separated, saturated brine is added and left to stand, the lower layer is discarded, and tetrahydrofuran or the like is distilled off from the upper layer portion with an evaporator. The obtained compound was a pale yellow liquid, and the compound was identified from the measurement of LC-MS.
MS: 572.14 (found), 572.13 (theory)

Formula (206) 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, and R ₂₇ is a phenyl group.
This compound was prepared by reacting 50 parts of diphenylphosphonic chloride, 38 parts of triethylamine and 10 parts of metaphenylenediamine in 300 parts of tetrahydrofuran at 1 ° C. or less for 1 hour and at room temperature for 10 hours, adding 100 parts of water and dilute hydrochloric acid. The mixture is allowed to stand at pH 7 or lower, and the upper layer portion is separated, saturated brine is added and left to stand, the lower layer is discarded, and tetrahydrofuran or the like is distilled off from the upper layer portion with an evaporator. The obtained compound was a pale yellow liquid, and the compound was identified from the measurement of LC-MS.
MS: 572.13 (found), 572.13 (theory)

Formula (207) 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, and R ₂₇ is a phenyl group.
This compound was prepared by reacting 50 parts of diphenylphosphonic chloride, 38 parts of triethylamine and 10 parts of paraphenylenediamine in 300 parts of tetrahydrofuran at 1 ° C. or less for 1 hour and at room temperature for 10 hours, adding 100 parts of water and dilute hydrochloric acid. The mixture is allowed to stand at pH 7 or lower, and the upper layer portion is separated, saturated brine is added and left to stand, the lower layer is discarded, and tetrahydrofuran or the like is distilled off from the upper layer portion with an evaporator. The obtained compound was a pale yellow liquid, and the compound was identified from the measurement of LC-MS.
MS: 572.13 (found), 572.13 (theory)

Formula (208) is a compound of the above formula (1) in which R _{11 to} R ₁₄ are phenyl groups, R ₁₅ is a hydrogen atom, and R ₁₆ is a phenyl group.
This compound was prepared by reacting 50 parts of diphenylphosphonic chloride, 38 parts of triethylamine and 10 parts of 2-aminophenol in 300 parts of tetrahydrofuran at 1 ° C. or less for 1 hour and at room temperature for 10 hours, and adding 100 parts of water to dilute hydrochloric acid. The mixture is allowed to stand at pH 7 or lower, and the upper layer portion is separated, saturated brine is added and left to stand, the lower layer is discarded, and tetrahydrofuran or the like is distilled off from the upper layer portion with an evaporator. The obtained compound was a pale yellow solid, and the compound was identified by LC-MS measurement.
MS: 573.11 (found), 573.11 (theory)

Formula (209) is a compound of the above formula (1) in which R _{11 to} R ₁₄ are phenyl groups, R ₁₅ is a hydrogen atom, and R ₁₆ is a phenyl group.
This compound was prepared by reacting 50 parts of diphenylphosphonic chloride, 38 parts of triethylamine and 10 parts of 3-aminophenol in 300 parts of tetrahydrofuran at 1 ° C. or less for 1 hour and at room temperature for 10 hours, and adding 100 parts of water to dilute hydrochloric acid. The mixture is allowed to stand at pH 7 or lower, and the upper layer portion is separated, saturated brine is added and left to stand, the lower layer is discarded, and tetrahydrofuran or the like is distilled off from the upper layer portion with an evaporator. The obtained compound was a pale yellow solid, and the compound was identified by LC-MS measurement.
MS: 573.12 (found), 573.11 (theory)

Formula (210) is a compound of the above formula (1) in which R _{11 to} R ₁₄ are phenyl groups, R ₁₅ is a hydrogen atom, and R ₁₆ is a phenyl group.
This compound was prepared by reacting 50 parts of diphenylphosphonic chloride, 25 parts of triethylamine and 5.7 parts of 4-aminophenol in 300 parts of tetrahydrofuran for 1 hour at 10 ° C. or less and 10 hours at room temperature, and adding 100 parts of water. The mixture is allowed to stand at a pH of 7 or less with dilute hydrochloric acid, and the upper layer is separated, and a saturated saline solution is added and the mixture is allowed to stand. The lower layer is discarded, and tetrahydrofuran and the like are distilled off from the upper layer with an evaporator. The obtained compound was a pale yellow solid, and the compound was identified by LC-MS measurement.
MS: 573.11 (found), 573.11 (theory)

Formula (211) is a compound of the above formula (3) in which R _{31 to} R ₃₄ are phenyl groups, R ₃₅ and R ₃₆ are hydrogen atoms, and R ₃₇ is diphenyl sulfone.
This compound was prepared by reacting 50 parts of phenyl dichlorophosphate, 25 parts of triethylamine and 32 parts of bisphenol S in 300 parts of tetrahydrofuran for 1 hour at 10 ° C. or less and 10 hours at room temperature, and then adding 31 parts of triethylamine and 24 parts of aniline to 10 parts. 1 hour at room temperature or less, 10 hours at room temperature, 100 parts of water is added and the pH is 7 or less with dilute hydrochloric acid, the upper layer is separated, and saturated saline is added and left to stand. It is discarded and obtained by distilling off tetrahydrofuran and the like from the upper layer with an evaporator. The obtained compound was a pale yellow solid, and the compound was identified by LC-MS measurement.
MS: 712.12 (found), 712.12 (theory)

Equation (212) _is a _{R 21} or _{R 24} is _phenyl, R _{25, R 26} is a hydrogen _atom, a compound of the formula _{R 27} is diphenyl sulfone (2).
This compound was prepared by reacting 50 parts of diphenylphosphonic chloride, 25 parts of triethylamine and 5.7 parts of bis (4-aminophenyl) sulfone in 300 parts of tetrahydrofuran for 1 hour at 10 ° C. or less and 10 hours at room temperature, and 100 parts of water. And the mixture is allowed to stand at pH 7 or less with dilute hydrochloric acid, and the upper layer is separated, saturated brine is added and left to stand, the lower layer is discarded, and tetrahydrofuran and the like are distilled off from the upper layer with an evaporator. can get. The obtained compound was a pale yellow solid, and the compound was identified by LC-MS measurement.
MS: 712.13 (found), 712.12 (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, and R ₂₇ is diphenylmethane.
This compound was prepared by reacting 50 parts of diphenylphosphonic chloride, 25 parts of triethylamine and 5.7 parts of bis (4-aminophenyl) methane in 300 parts of tetrahydrofuran for 1 hour at 10 ° C. or less and 10 hours at room temperature, and 100 parts of water. And the mixture is allowed to stand at pH 7 or less with dilute hydrochloric acid, and the upper layer is separated, saturated brine is added and left to stand, the lower layer is discarded, and tetrahydrofuran and the like are distilled off from the upper layer with an evaporator. can get. The obtained compound was a pale yellow solid, and the compound was identified by LC-MS measurement.
MS: 661.17 (found), 661.17 (theory)

Formula (214) 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, and R ₂₇ is diphenyl ether.
This compound was prepared by reacting 50 parts of diphenylphosphonic chloride, 25 parts of triethylamine and 5.7 parts of bis (4-aminophenyl) ether in 300 parts of tetrahydrofuran for 1 hour at 10 ° C. or less and 10 hours at room temperature, and 100 parts of water. And the mixture is allowed to stand at pH 7 or less with dilute hydrochloric acid, and the upper layer is separated, saturated brine is added and left to stand, the lower layer is discarded, and tetrahydrofuran and the like are distilled off from the upper layer with an evaporator. can get. The obtained compound was a pale yellow solid, and the compound was identified by LC-MS measurement.
MS: 664.15 (found), 664.15 (theory)

Equation (215) _is a _{R 31} or _{R 34} is a phenyl _group, a compound of the formula R _{35, R 36} is a hydrogen _{atom, R 37} is dimethyl diphenylmethane (3).
This compound was prepared by reacting 50 parts of dichlorophosphoric acid phenyl ester, 29 parts of triethylamine and 27 parts of bisphenol A in 300 parts of tetrahydrofuran for 1 hour at 10 ° C. or less and 10 hours at room temperature, and then 32 parts of triethylamine and 29 parts of aniline. The reaction is carried out at 10 ° C. or lower for 1 hour and at room temperature for 10 hours, 100 parts of water is added and the pH is adjusted to 7 or less with dilute hydrochloric acid to separate the upper layer, and saturated saline is added and left to stand. Is obtained by distilling off tetrahydrofuran and the like from the upper layer with an evaporator. The obtained compound was a pale yellow solid, and the compound was identified by LC-MS measurement.
MS: 690.20 (found), 690.20 (theory)

Formula (216) 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, and R ₂₇ is a metaxylenyl group.
This compound was prepared by reacting 50 parts of diphenylphosphonic chloride, 37 parts of triethylamine and 13 parts of metaxylidinyldiamine in 300 parts of tetrahydrofuran at 1 ° C. or less for 1 hour and at room temperature for 10 hours, and adding 100 parts of water to dilute hydrochloric acid. The mixture is allowed to stand at pH 7 or lower, and the upper layer portion is separated, saturated brine is added and left to stand, the lower layer is discarded, and tetrahydrofuran or the like is distilled off from the upper layer portion with an evaporator. The obtained compound was a pale yellow solid, and the compound was identified by LC-MS measurement.
MS: 600.17 (found), 600.16 (theory)

Formula (217) is a compound of the above formula (1) in which R _{11 to} R ₁₄ are phenyl groups, R ₁₅ is a hydrogen atom, and R ₁₆ is an ethoxyethyl group.
This compound is obtained by reacting 50 parts of diphenylphosphonic chloride, 37 parts of triethylamine and 10 parts of diglycolamine in 300 parts of tetrahydrofuran at 10 ° C. or less for 1 hour and at room temperature for 10 hours, adding 100 parts of water and dilute hydrochloric acid. The mixture is allowed to stand at pH 7 or lower, and the upper layer portion is separated, saturated brine is added and left to stand, the lower layer is discarded, and tetrahydrofuran or the like is distilled off from the upper layer portion with an evaporator. The obtained compound was a pale yellow solid, and the compound was identified by LC-MS measurement. The
MS: 569.15 (found), 568.14 (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 phosphorus compound shown in the following table was pulverized with a sand grinder as needed, and added to water together with other components 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 (3)) 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 (2)) 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 (2)) 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 (2)) 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 (1)) 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 (1)) 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 (1)) 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 (2)) 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 (214) (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 15
Table 15
Water 63.0%
Formula (215) (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 16
Table 16
Water 63.0%
Formula (216) (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 (217) (Compound of general formula (1)) 30.0%
Prisurf ALNa salt 6.3%
Thickener 0.5%
Antifoam 0.1%
Antifungal agent 0.1%
100.0%

Comparative Example 1
Table 18
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 19
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 20
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 an aqueous dispersion of the flameproofing agent prepared in Examples 1 to 17 or Comparative Examples 1 to 3 above, 40 cm squares of a blended fiber fabric containing 70% polyester and 30% CDP, respectively, 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 17 or Comparative Examples 1 to 3 were each treated at a bath ratio of 1:20 and 130 ° C. for 60 minutes.

  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 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: Acceptance rate The case where the after flame time was 3 seconds or less was regarded as acceptable, and the numerical value obtained by dividing the number of acceptable times during the measurement by the number of measurements was described as the acceptance rate. Rounded to the nearest whole number, 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 21]

  From the results of Table 21, the pass rate of evaluation A is 86 to 100% for Examples 1 to 17 of the present invention, while 64 to 65% for 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 1-17 of this invention are 0.5-3.5, whereas each comparative example is 3.9-6.2. The average afterflame 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)

(Wherein R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ are each independently a hydroxyl group, amino group, cyano group, formyl group, carboxy group, 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, or a (C1-C10) alkyl group; ₁₅ is 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. By a group, di (C1-C10) alkylamino group, phenyl group, phenoxy group or (C1-C10) alkoxy group Conversion is shown an aryl group which may _{have, R 16} is 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 ( An aryl group optionally substituted by a 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, a phenethyl group, Carbonyl group or the following formula (4)

A condensed phosphate ester amide compound (A) or a salt thereof, which is any group represented by the formula: The condensed phosphoric ester amide compound (A) represented by the formula (1) or the following formula (2)

(Wherein 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) 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, or a (C1-C10) alkyl group; ₂₅ and R ₂₆ are each independently a hydrogen atom, a (C1-C3) alkyl group, a 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 optionally substituted by an alkoxy group, and R ₂₇ represents a hydroxyl group, an amino group, a cyano group, a formyl group, a carboxy group, a ureido group, a (C1-C10) alkyl group, a (C1-C10) alkylamino group. Group, aryl group optionally substituted by di (C1-C10) alkylamino group, phenyl group, phenoxy group or (C1-C10) alkoxy group, (C1-C6) alkyl group, (C2-C6) alkenyl group , A phenethyl group, a carbonyl group, or the following formula (4)

A condensed phosphoramide compound (B) or a salt thereof, or a group represented by the following formula (3):

(Wherein R ₃₁ , R ₃₂ , R ₃₃ and R ₃₄ are each independently a hydroxyl group, amino group, cyano group, formyl group, carboxy group, 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, or a (C1-C10) alkyl group; ₃₅ and R ₃₆ are each independently a hydrogen atom, a (C1-C3) alkyl group, a phenethyl group, a hydroxyl group, an amino group, a cyano group, a formyl group, a carboxy group, a ureido group, a (C1-C10) alkyl group, ( C1-C10) alkylamino group, di (C1-C10) alkylamino group, phenyl group, phenoxy group or (C1-C10) ) Represents an aryl group optionally substituted by an alkoxy group, and R ₃₇ represents a hydroxyl group, an amino group, a cyano group, a formyl group, a carboxy group, a ureido group, a (C1-C10) alkyl group, a (C1-C10) alkylamino group. Group, aryl group optionally substituted by di (C1-C10) alkylamino group, phenyl group, phenoxy group or (C1-C10) alkoxy group, (C1-C6) alkyl group, (C2-C6) alkenyl group , A phenethyl group, a carbonyl group, or a condensed phosphoramide compound (C) which is any group represented by the above formula (4) or a salt thereof, and a surfactant. A phosphorus compound selected from the group consisting of a condensed phosphoric ester amide compound (A) represented by the formula (1) and a condensed phosphoric amide compound (B) represented by the formula (2) in an aqueous dispersion The aqueous dispersion according to claim 2, wherein the total amount is 1 to 90% by weight. The aqueous dispersion according to claim 2 or 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.