JP2005330607A - Flame-retardant finishing agent for polyester fiber and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a flame-retardant finishing agent that is effective for a polyester fiber and woven or knitted fabric and has high stability with time. <P>SOLUTION: The flame-retardant finishing agent for a polyester fiber is obtained by dispersing fine particles of a cyclic phosphazene compound represented by general formula (2) [n is an integer of 3-25; X and Y are each the same or different and O, S or NR<SP>3</SP>(R<SP>3</SP>is a hydrogen atom or a 1-4C alkyl group which may contain a substituent group); R<SP>1</SP>and R<SP>2</SP>are each the same or different and a hydrogen atom, a 1-20C alkyl group which may contain a substituent group, a 3-8C cycloalkyl group which may contain a substituent group or a 5-22C aryl group which may contain a substituent group] crosslinked with a crosslinking group into a dispersion medium. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a flame retardant processing agent for polyester fibers and a method for producing the same.

  Since polyester fiber has a property of being poorly self-extinguishing and burns, researches for making flame-retardant polyester fiber have been extensively conducted. As flame retardant processing agents for polyester fibers, for example, compounds containing elements such as phosphorus, halogen, antimony, aluminum hydroxide, and magnesium hydroxide are widely known.

  As a method for flame retardant treatment of polyester fiber using a phosphorus compound as a flame retardant treatment, for example, a method of copolymerizing a phosphorous compound having flame retardancy with polyester at the production stage of the raw yarn has been proposed. However, this method has a limitation that a dedicated spinning facility is required. On the other hand, various studies have been made on the use of phosphorus compounds that can impart good flame retardancy and do not generate harmful gases. However, the present situation is that they are not practically used for post-processing. The reason for this is, for example, that phosphorus compounds as flame retardants are generally water-soluble, have poor affinity with polyester fibers, and the phosphorus compounds also exhibit plasticizer properties in the fibers. And the like. In addition, the flame retardant treatment agent made of an existing phosphorus compound has a problem that it needs to be applied in a large amount because the phosphorus content in the compound is small.

  In the case of imparting flame retardancy by post-processing in the form of polyester fiber woven or knitted fabric, there is an advantage that flame retardancy can be freely processed as needed, and in particular, there is a method of imparting flame retardancy by post-processing using a halogen compound The current mainstream. However, halogen compounds are liable to generate harmful gases when combusted, and it is desired to refrain from using them in consideration of recent global environmental problems.

  In view of such a current situation, the use of phosphazene compounds containing a large amount of phosphorus has been proposed as a flame retardant processing agent that can be applied to both the production stage of raw yarns and post-processing in the form of fiber knitted fabrics (patents). References 1 and 2). These documents specifically disclose the use of linear or cyclic phosphazene compounds.

  However, since linear or cyclic phosphazene compounds are oily or viscous solids, a large disperser is required for fine particle dispersion. Moreover, the obtained fine particle dispersion has insufficient stability over time, and it is difficult to ensure a stable usable state (dispersed state) for a long period of time.

On the other hand, research is also being conducted on the use of phosphazene compounds as flame retardants for synthetic resins other than polyester fibers. For example, Patent Document 3 discloses that a crosslinked product of a linear or cyclic phosphazene compound is used as a flame retardant for a polycarbonate resin. However, Patent Document 3 describes that a crosslinked product of a phosphazene compound is kneaded into a polycarbonate resin and imparts flame retardancy to the resin molded body, and as a flame retardant processing agent for synthetic fibers. There is no mention about the application of. In order to give flame retardant processing to fibers, it is very important to make fine particles of the processing agent. However, since the phosphazene compound has physical properties that make it difficult to disperse the particles as described above, flame retardant to synthetic fibers. There is room for further improvement in application as a processing agent.
JP-A-8-291467 Japanese Patent Laid-Open No. 10-298188 JP 2002-302597 A

  INDUSTRIAL APPLICABILITY The present invention provides a flame retardant processing agent for polyester fibers containing a phosphazene compound, which can be suitably applied to both the production stage of a polyester fiber yarn and the post-processing in the form of a textile knitted fabric, and has high stability over time. The main purpose is to provide.

  As a result of intensive studies to achieve the above object, the present inventors have found that fine particles of a crosslinked cyclic phosphazene compound produced by a specific production method contribute to the achievement of the above object. It came to be completed.

  That is, this invention relates to the following flame retardant processing agent for polyester fibers, and its manufacturing method.

1.1) which may have a substituent C ₁ ~ ₆ alkylene group, 2) o-phenylene group, 3) m-phenylene group, 4) p-phenylene group, and 5) the following general formula (1 )

〔式中、Ａは−Ｃ（ＣＨ₃）₂−、−ＳＯ₂−、−Ｓ−又は−Ｏ−を示す。ａは０又は１を示す。〕
で表されるビスフェニレン基、からなる群から選択された少なくとも１種の架橋基により架橋された、下記一般式（２）

[In the formula, A represents —C (CH ₃ ) ₂ —, —SO ₂ —, —S— or —O—. a represents 0 or 1; ]
The following general formula (2), which is cross-linked by at least one cross-linking group selected from the group consisting of:

〔式中、ｎは３〜２５の整数を示す。Ｘ及びＹは、同一又は相異なって、−Ｏ−、−Ｓ−又は−ＮＲ³−（Ｒ³は水素原子又は置換基を有していてもよいＣ₁〜₄のアルキル基を示す）を示す。Ｒ¹及びＲ²は、同一又は相異なって、水素原子、置換基を有していてもよいＣ₁〜₂₀のアルキル基、置換基を有していてもよいＣ₃〜₈のシクロアルキル基又は置換基を有していてもよいＣ₅〜₂₂のアリール基を示す。〕
で表される環状ホスファゼン化合物の微粒子が分散媒中に分散してなるポリエステル繊維用難燃加工剤。

[In formula, n shows the integer of 3-25. X and Y are the same or different, -O -, - S- or -NR ³ - and (R ³ represents an alkyl group optionally C ₁ ~ ₄ have a hydrogen atom or a substituent) Show. R ¹ and R ² are the same or different, a hydrogen atom, which may have a substituent C ₁ ~ ₂₀ alkyl group, a cycloalkyl group optionally C ₃ ~ ₈ may have a substituent or an aryl group which may C ₅ ~ ₂₂ have a substituent. ]
A flame retardant processing agent for polyester fibers, in which fine particles of a cyclic phosphazene compound represented by the formula (1) are dispersed in a dispersion medium.

  2. Item 2. The flame retardant processing agent for polyester fibers according to Item 1, wherein the fine particles have an average particle diameter of 0.2 to 2 µm.

  3. Item 3. The flame retardant agent for polyester fiber according to Item 1 or 2, which contains at least one selected from the group consisting of a nonionic surfactant and an anionic surfactant.

  4). Item 3. The flame retardant processing agent for polyester fiber according to Item 1 or 2, which contains an emulsification aid.

  5). Item 3. The flame retardant agent for polyester fiber according to Item 1 or 2, which contains at least one selected from the group consisting of a nonionic surfactant, an anionic surfactant, and an emulsifying aid.

6.1) which may have a substituent C ₁ ~ ₆ alkylene group, 2) o-phenylene group, 3) m-phenylene group, 4) p-phenylene group, and 5) the following general formula (1 )

〔式中、Ａは−Ｃ（ＣＨ₃）₂−、−ＳＯ₂−、−Ｓ−又は−Ｏ−を示す。ａは０又は１を示す。〕
で表されるビスフェニレン基、からなる群から選択された少なくとも１種の架橋基により架橋された、下記一般式（２）

[In the formula, A represents —C (CH ₃ ) ₂ —, —SO ₂ —, —S— or —O—. a represents 0 or 1; ]
The following general formula (2), which is cross-linked by at least one cross-linking group selected from the group consisting of:

〔式中、ｎは３〜２５の整数を示す。Ｘ及びＹは、同一又は相異なって、−Ｏ−、−Ｓ−又は−ＮＲ³−（Ｒ³は水素原子又は置換基を有していてもよいＣ₁〜₄のアルキル基を示す）を示す。Ｒ¹及びＲ²は、同一又は相異なって、水素原子、置換基を有していてもよいＣ₁〜₂₀のアルキル基、置換基を有していてもよいＣ₃〜₈のシクロアルキル基又は置換基を有していてもよいＣ₅〜₂₂のアリール基を示す。〕
で表される環状ホスファゼン化合物を、ノニオン界面活性剤、アニオン界面活性剤及び乳化補助剤からなる群から選択された少なくとも１種の存在下において加熱により溶融させた後、該溶融物を、撹拌下において７０〜１００℃の温湯に滴下することを特徴とするポリエステル繊維用難燃加工剤の製造方法。

[In formula, n shows the integer of 3-25. X and Y are the same or different, -O -, - S- or -NR ³ - and (R ³ represents an alkyl group optionally C ₁ ~ ₄ have a hydrogen atom or a substituent) Show. R ¹ and R ² are the same or different, a hydrogen atom, which may have a substituent C ₁ ~ ₂₀ alkyl group, a cycloalkyl group optionally C ₃ ~ ₈ may have a substituent or an aryl group which may C ₅ ~ ₂₂ have a substituent. ]
Is melted by heating in the presence of at least one selected from the group consisting of a nonionic surfactant, an anionic surfactant and an emulsifying aid, and then the melt is stirred. A method for producing a flame retardant processing agent for polyester fibers, wherein the method is dripped in hot water at 70 to 100 ° C.

  7). The flame retardant processing agent for polyester fibers manufactured by the manufacturing method of said claim | item 6.

  8). After making the flame retardant processing agent for polyester fibers in any one of said item | item 1-5 and 7 contact with polyester fiber, this polyester fiber is dried, and then this polyester fiber is heat-processed at 150-200 degreeC. A method for producing a flame retardant polyester fiber, wherein fine particles in the processing agent are exhausted.

  9. The flame retardant processing agent for polyester fiber according to any one of Items 1 to 5 and 7, wherein the polyester fiber is brought into contact with the polyester fiber heated at 100 to 150 ° C. A method for producing a flame-retardant polyester fiber, wherein the fiber is exhausted.

10.1) may have a substituent group C ₁ ~ ₆ alkylene group, 2) o-phenylene group, 3) m-phenylene group, 4) p-phenylene group, and 5) the following general formula (1 )

〔式中、Ａは−Ｃ（ＣＨ₃）₂−、−ＳＯ₂−、−Ｓ−又は−Ｏ−を示す。ａは０又は１を示す。〕
で表されるビスフェニレン基、からなる群から選択された少なくとも１種の架橋基により架橋された、下記一般式（２）

[In the formula, A represents —C (CH ₃ ) ₂ —, —SO ₂ —, —S— or —O—. a represents 0 or 1; ]
The following general formula (2), which is cross-linked by at least one cross-linking group selected from the group consisting of:

〔式中、ｎは３〜２５の整数を示す。Ｘ及びＹは、同一又は相異なって、−Ｏ−、−Ｓ−又は−ＮＲ³−（Ｒ³は水素原子又は置換基を有していてもよいＣ₁〜₄のアルキル基を示す）を示す。Ｒ¹及びＲ²は、同一又は相異なって、水素原子、置換基を有していてもよいＣ₁〜₂₀のアルキル基、置換基を有していてもよいＣ₃〜₈のシクロアルキル基又は置換基を有していてもよいＣ₅〜₂₂のアリール基を示す。〕
で表される環状ホスファゼン化合物の微粒子を吸尽してなることを特徴とする難燃性ポリエステル繊維。

[In formula, n shows the integer of 3-25. X and Y are the same or different, -O -, - S- or -NR ³ - and (R ³ represents an alkyl group optionally C ₁ ~ ₄ have a hydrogen atom or a substituent) Show. R ¹ and R ² are the same or different, a hydrogen atom, which may have a substituent C ₁ ~ ₂₀ alkyl group, a cycloalkyl group optionally C ₃ ~ ₈ may have a substituent or an aryl group which may C ₅ ~ ₂₂ have a substituent. ]
A flame retardant polyester fiber obtained by exhausting fine particles of a cyclic phosphazene compound represented by the formula:

11. The flame-retardant polyester fiber manufactured by the manufacturing method of said claim | item 8 or 9.

Hereinafter, the flame retardant processing agent for polyester fiber of the present invention and the production method thereof will be described in detail, and the method for producing the flame retardant polyester fiber using the flame retardant processing agent and the flame retardant polyester fiber will also be described. To do.

Polyester fibers for flame retarding agent for polyester flame retarding agent present invention, 1) an alkylene group optionally C ₁ ~ ₆ have a substituent, 2) o-phenylene group, 3) m-phenylene Group, 4) p-phenylene group, and 5) the following general formula (1)

〔式中、Ａは−Ｃ（ＣＨ₃）₂−、−ＳＯ₂−、−Ｓ−又は−Ｏ−を示す。ａは０又は１を示す。〕
で表されるビスフェニレン基、からなる群から選択された少なくとも１種の架橋基により架橋された、下記一般式（２）

[In the formula, A represents —C (CH ₃ ) ₂ —, —SO ₂ —, —S— or —O—. a represents 0 or 1; ]
The following general formula (2), which is cross-linked by at least one cross-linking group selected from the group consisting of:

〔式中、ｎは３〜２５の整数を示す。Ｘ及びＹは、同一又は相異なって、−Ｏ−、−Ｓ−又は−ＮＲ³−（Ｒ³は水素原子又は置換基を有していてもよいＣ₁〜₄のアルキル基を示す）を示す。Ｒ¹及びＲ²は、同一又は相異なって、水素原子、置換基を有していてもよいＣ₁〜₂₀のアルキル基、置換基を有していてもよいＣ₃〜₈のシクロアルキル基又は置換基を有していてもよいＣ₅〜₂₂のアリール基を示す。〕
で表される環状ホスファゼン化合物の微粒子が分散媒中に分散してなるものである。

[In formula, n shows the integer of 3-25. X and Y are the same or different, -O -, - S- or -NR ³ - and (R ³ represents an alkyl group optionally C ₁ ~ ₄ have a hydrogen atom or a substituent) Show. R ¹ and R ² are the same or different, a hydrogen atom, which may have a substituent C ₁ ~ ₂₀ alkyl group, a cycloalkyl group optionally C ₃ ~ ₈ may have a substituent or an aryl group which may C ₅ ~ ₂₂ have a substituent. ]
The fine particles of the cyclic phosphazene compound represented by the formula are dispersed in a dispersion medium.

Fine particles are crosslinked, cyclic phosphazene compound represented by the general formula (2) is 1) may have a substituent group C ₁ ~ ₆ alkylene group, 2) o-phenylene group, 3 It is crosslinked by at least one of m) phenylene group, 4) p-phenylene group, and 5) bisphenylene group represented by general formula (1). The average particle diameter of the fine particles is about 0.2 to 2 μm. In addition, the value of an average particle diameter is the value measured using the laser diffraction / scattering type particle size distribution measuring apparatus.

The alkylene group optionally C ₁ ~ ₆ have a substituent is a bridging group may be either linear or branched. For example, methylene group, ethylmethylene group, diethylmethylene group, methylmethylene group, ethylmethylmethylene group, ethylene group, trimethylene group, 2-methyltrimethylene group, 2,2-dimethyltrimethylene group, 1-methyltrimethylene group , Tetramethylene group, pentamethylene group and the like.

In the bisphenylene group represented by the general formula (1) which is a bridging group, A is —C (CH ₃ ) ₂ —, —SO ₂ —, —S— or —O—, and among them, —C (CH ₃ ) _2- is preferred. In the general formula (1), a is 0 or 1.

  In the cyclic phosphazene compound represented by the general formula (2), n represents an integer of 3 to 25, preferably 3 to 20.

X and Y are the same or different, -O -, - S- or -NR ³ - and (R ³ represents an alkyl group optionally C ₁ ~ ₄ have a hydrogen atom or a substituent) Show. As X and Y, —O— is particularly preferable. The alkyl group of C ₁ ~ _4, for example, a methyl group, an ethyl group, n- propyl group, an isopropyl group, n- butyl group, sec- butyl group, etc. tert- butyl group.

R ¹ and R ² are the same or different, a hydrogen atom, which may have a substituent C ₁ ~ ₂₀ alkyl group, a cycloalkyl group optionally C ₃ ~ ₈ may have a substituent or an aryl group which may C ₅ ~ ₂₂ have a substituent.

The alkyl group of C ₁ ~ _20, for example, a methyl group, an ethyl group, n- propyl group, an isopropyl group, n- butyl group, sec- butyl group, tert- butyl group, n- pentyl group, n- hexyl group N-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, hexadecyl group, heptadecyl group Group, octadecyl group, nonadecyl group, icosyl group and the like.

Examples of the cycloalkyl group C ₃ ~ _8, for example, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, methylcyclopentyl group, cycloheptyl group, cyclooctyl group and the like.

The aryl group of C ₅ ~ _22, for example, a phenyl group, a naphthyl group, an anthryl group and a phenanthryl group.

R ¹ and R ² are preferably a phenyl group (hereinafter also abbreviated as “Ph”) which is one of C ₆ aryl groups. That is, the cyclic phosphazene compound represented by the general formula (2) is preferably X = Y = O (oxygen) and R ¹ = R ² = Ph.

In the cross-linked product (fine particles), the location of each cross-linking group is not particularly limited as long as the cyclic phosphazene compounds can be bonded together by cross-linking. For example, when the cyclic phosphazene compound is a preferred embodiment (X = Y = O (oxygen) and R ¹ = R ² = Ph), the bridging group is generally the phenyl group (Ph) of the cyclic phosphazene compound. It exists between the two oxygen atoms remaining after desorption. In this manner, when crosslinked by crosslinking groups other than alkylene group C ₁ ~ _6, the content of the phenyl groups in the crosslinked product of the general formula (2) in the phenyl group of the cyclic phosphazene compound represented Based on the total number, a range of 50 to 99.9% is preferable, and a range of 70 to 90% is more preferable. Moreover, in this aspect, it is preferable that the hydroxyl group of a free state is not contained in the molecule | numerator of a crosslinked body.

  The flame retardant processing agent for polyester fiber is not particularly limited as long as it has properties suitable for the flame retardant processing of polyester fiber, and the fine particles of the predetermined crosslinked cyclic phosphazene compound are dispersed in a dispersion medium. . Although it does not specifically limit as a dispersion medium, Usually, water can be used. That is, the flame retardant finish can usually be composed of an aqueous dispersion (emulsion) of the fine particles.

  The flame retardant for polyester fiber may contain an additive as appropriate in order to enhance the dispersion stability of the fine particles. The additive is not particularly limited as long as it can increase the dispersion stability of the granular material, and various dispersion stabilizers can be used. As the dispersion stabilizer, for example, at least one of a nonionic surfactant, an anionic surfactant and an emulsification aid is suitable.

  Examples of nonionic surfactants include polyoxyalkylene natural oil alkyl ethers, polyoxyalkylene higher alcohol alkyl ethers, polyoxyalkylene alkylphenyl ethers, polyhydric alcohol fatty acid esters, and the like. Examples of the anionic surfactant include higher alcohol sulfates, polyoxyethylene alkylphenyl sulfates, sulfated fatty acid esters, alkylbenzene sulfonates, alkyl naphthalene sulfonates, higher alcohol phosphates, etc. Is mentioned.

  The addition amount of these surfactants is not particularly limited, and can be appropriately set in consideration of the type of surfactant, the degree of dispersion stability of the fine particles, and the like. For example, when the flame retardant processing agent is an emulsion of the fine particles, the content of the surfactant is usually about 3 to 15% by weight, preferably about 4 to 10% by weight, based on the weight of the emulsion.

  Although it does not specifically limit as an emulsification adjuvant, For example, Triglycerides, such as a castor oil and rapeseed oil; Esters, such as a phosphate ester and a phthalate ester; Higher alcohol etc. are mentioned.

  The addition amount of the emulsification aid is not particularly limited, and can be appropriately set in consideration of the type of the emulsification aid, the degree of dispersion stability of the granular material, and the like. For example, when the flame retardant processing agent is an emulsion of the fine particles, the content of the emulsification aid is usually 1 to 7% by weight, preferably about 2 to 4% by weight, based on the weight of the emulsion.

  In a preferred embodiment, the flame retardant processing agent for polyester fibers includes both the above-described surfactant (at least one of a nonionic surfactant and an anionic surfactant) and an emulsification aid. For example, as a preferred composition of the flame retardant, in the case of an emulsion, the fine particles are 20 to 40% by weight, preferably about 30 to 35% by weight, and the surfactant is 3 to 15% by weight, based on the weight of the emulsion. , Preferably 4 to 10% by weight, emulsification aid 1 to 4% by weight, preferably about 2 to 3% by weight.

  When the polyester fiber is actually flame retardant processed using the flame retardant processing agent of the present invention, the flame retardant processing agent is appropriately diluted (emulsion) in consideration of ease of processing, the degree of flame retardant processing, and the like. (If diluted, it can be diluted with water).

  The flame retardant processing agent for polyester fiber may further contain a stabilizer for the fine particles as long as the flame retardant performance is not lowered. Examples of the stabilizer include polyvinyl alcohol, carboxymethyl cellulose, polyvinyl pyrrolidone, starch and the like that form a protective colloid of the fine particles. In addition, the flame retardant processing agent may contain fiber processing agents such as various softening agents, deodorizing agents, and antistatic agents. These can use a well-known thing. The kind and addition amount of the stabilizer can be appropriately set according to desired characteristics.

  The flame retardant processing agent for polyester fibers of the present invention has a very small average particle diameter (about 0.2 to 2 μm) of crosslinked fine particles of cyclic phosphazene compound, so that the fine particles are easily exhausted by the polyester fibers. Can be easily flame-retardant processed. In addition, since the phosphazene compound containing a large amount of phosphorus is contained, the polyester fiber can be flame-retardant processed even if the amount used is small compared to the conventional flame retardant processing agent containing a phosphorus compound.

Method for Producing Flame Retardant for Polyester Fiber The method for producing the flame retardant for polyester fiber of the present invention is not particularly limited as long as the flame retardant for polyester fiber is obtained. For example, the method for producing shown below Are mentioned as preferred.

That is, 1) may have a substituent group C ₁ ~ ₆ alkylene group, 2) o-phenylene group, 3) m-phenylene group, 4) p-phenylene group, and 5) the following general formula (1 )

〔式中、Ａは−Ｃ（ＣＨ₃）₂−、−ＳＯ₂−、−Ｓ−又は−Ｏ−を示す。ａは０又は１を示す。〕
で表されるビスフェニレン基、からなる群から選択された少なくとも１種の架橋基により架橋された、下記一般式（２）

[In the formula, A represents —C (CH ₃ ) ₂ —, —SO ₂ —, —S— or —O—. a represents 0 or 1; ]
The following general formula (2), which is cross-linked by at least one cross-linking group selected from the group consisting of:

〔式中、ｎは３〜２５の整数を示す。Ｘ及びＹは、同一又は相異なって、−Ｏ−、−Ｓ−又は−ＮＲ³−（Ｒ³は水素原子又は置換基を有していてもよいＣ₁〜₄のアルキル基を示す）を示す。Ｒ¹及びＲ²は、同一又は相異なって、水素原子、置換基を有していてもよいＣ₁〜₂₀のアルキル基、置換基を有していてもよいＣ₃〜₈のシクロアルキル基又は置換基を有していてもよいＣ₅〜₂₂のアリール基を示す。〕
で表される環状ホスファゼン化合物を、ノニオン界面活性剤、アニオン界面活性剤及び乳化補助剤からなる群から選択された少なくとも１種の存在下において加熱により溶融させた後、該溶融物を、撹拌下において７０〜１００℃の温湯に滴下することを特徴とする製造方法が好ましい（以下、「本発明の製造方法」と称する）。

[In formula, n shows the integer of 3-25. X and Y are the same or different, -O -, - S- or -NR ³ - and (R ³ represents an alkyl group optionally C ₁ ~ ₄ have a hydrogen atom or a substituent) Show. R ¹ and R ² are the same or different, a hydrogen atom, which may have a substituent C ₁ ~ ₂₀ alkyl group, a cycloalkyl group optionally C ₃ ~ ₈ may have a substituent or an aryl group which may C ₅ ~ ₂₂ have a substituent. ]
Is melted by heating in the presence of at least one selected from the group consisting of a nonionic surfactant, an anionic surfactant and an emulsifying aid, and then the melt is stirred. Is preferably dripped in hot water at 70 to 100 ° C. (hereinafter referred to as “the production method of the present invention”).

  In the production method of the present invention, the crosslinking group, the cyclic phosphazene compound, and the crosslinked body are as described in the item of flame retardant processing agent for polyester fibers. As a crosslinked product of the cyclic phosphazene compound, a known product or a commercially available product can be used.

A synthetic product may be used as the crosslinked product of the cyclic phosphazene compound. For example, in the general formula (2), a cyclic phosphazene compound in which X = Y = O (oxygen atom) and R ¹ = R ² = Ph (phenyl group) is an o-phenylene group, m-phenylene group, A crosslinked product (crosslinked phenoxyphosphazene compound) crosslinked with at least one crosslinking group of a p-phenylene group and a bisphenylene group represented by the general formula (1) can be synthesized through the following steps.

That is, an alkali metal represented by C ₆ H ₅ —OM (M is an alkali metal) is substituted with cyclic dichlorophosphazene in which XR ¹ and YR ² moieties are substituted with Cl (chlorine atom) in the general formula (2). Phenolate, alkali metal diphenolate represented by M—O—C ₆ H ₄ —OM (where M is an alkali metal), and both ends in the general formula (1) are replaced with —OM (M is an alkali metal). By reacting a mixture of at least one alkali metal diphenolate formed (first step) and then further reacting the reaction product with the alkali metal phenolate (C ₆ H ₅ -OM) (second step) Can be manufactured. According to this method, M of both OM groups of the alkali metal diphenolate is eliminated without leaving a free hydroxyl group in the molecule, and two oxygen atoms are bonded to the phosphorus atom in the cyclic dichlorophosphazene compound. Thus, a crosslinked phenoxyphosphazene compound (that is, having an increased molecular weight) is obtained.

  The reaction in the first step and the second step can be carried out at room temperature (20 ° C.) to about 150 ° C., preferably about 80 to 140 ° C., and is usually completed for about 1 to 12 hours, preferably about 3 to 7 hours. To do. The reaction in the first step and the second step can be carried out in an organic solvent such as aromatic hydrocarbons such as benzene, toluene and xylene; halogenated aromatic hydrocarbons such as monochlorobenzene and dichlorobenzene. The crosslinked phenoxyphosphazene compound produced by the reaction can be easily isolated and purified from the reaction mixture according to a usual isolation method such as washing, filtration, and drying. Moreover, the content rate of the phenyl group in bridge | crosslinking phenoxyphosphazene compound is 50-99.9% normally based on the total number of all the phenyl groups in cyclic phenoxyphosphazene, Preferably it is 70-90%.

  The method for producing a flame retardant for a polyester fiber according to the present invention is characterized in that the predetermined crosslinked cyclic phosphazene compound is at least one selected from the group consisting of a nonionic surfactant, an anionic surfactant and an emulsifying aid. After melting by heating in the presence, the melt is added dropwise to hot water at 70 to 100 ° C. with stirring.

  About the kind, compounding quantity, etc. of a nonionic surfactant, an anionic surfactant, and an emulsification adjuvant, it is as having demonstrated in the item of the flame retardant processing agent for polyester fibers of this invention.

  When melting the cross-linked cyclic phosphazene compound, a reaction vessel containing the compound and at least one selected from the group consisting of a nonionic surfactant, an anionic surfactant and an emulsifying aid is heated. Since the melting point of the compound is generally in the range of 60 to 120 ° C, it can be melted by heating to 90 to 120 ° C.

  After melting, the melt is added dropwise to hot water at 70 to 100 ° C., preferably 80 to 90 ° C. with stirring. The stirring conditions and dropping conditions are not particularly limited as long as a uniform fine particle dispersion can be obtained. Usually, each condition may be set so that the average particle size of the obtained fine particles is 0.2 to 2 μm.

  According to such a production method of the present invention, a flame retardant processing agent in which fine particles of a crosslinked cyclic phosphazene compound are dispersed in a dispersion medium, and the average particle size of the fine particles is preferably 0.2 to 2 μm. Something is obtained. On the other hand, since the average particle diameter of the granular material of the cyclic phosphazene compound pulverized and dispersed by a conventionally known glass bead pulverizer is about 5 to 10 μm at most, smaller particles than the mechanical pulverization / dispersion method are used. Can be easily obtained. The obtained fine particles are easily exhausted by the polyester fiber and easily diffused into the fiber, and can be suitably applied to the flame-retardant processing of the polyester fiber.

  In addition, the flame retardant processing agent obtained by the production method of the present invention has very high dispersion stability even though the average particle size of the crosslinked cyclic phosphazene compound fine particles is preferably as small as 0.2 to 2 μm. Very expensive. And after a flame-retardant processing agent is cooled, the stable usable state can be ensured over a long period of time. On the other hand, if the conventional pulverization / dispersion method using a pulverization medium is used, the obtained flame retardant processing agent has high tenacity and insufficient dispersion stability.

Method for Producing Flame Retardant Polyester Fiber The flame retardant finish for polyester fiber of the present invention can be used to suitably produce flame retardant polyester fiber.

  As a method for producing a flame-retardant polyester fiber, any method may be used in which flame retardancy is imparted by exhausting the active component of the flame-retardant processing agent of the present invention (fine particles of a crosslinked cyclic phosphazene compound) into the polyester fiber. There is no particular limitation.

As a method for producing a flame retardant polyester fiber, for example,
(1) After bringing the flame retardant processing agent for polyester fiber into contact with the polyester fiber, the polyester fiber is dried, and then the polyester fiber is heat-treated at 150 to 200 ° C. to exhaust the fine particles in the processing agent. Production method of flame retardant polyester fiber,
(2) A flame retardant polyester fiber for a polyester fiber, which is heated to 100 to 150 ° C. and brought into contact with the polyester fiber to exhaust the fine particles in the processing agent into the polyester fiber. Manufacturing method,
And the like are preferable. In any of the production methods, as described above, in the case of an emulsion, the flame retardant can be diluted with water or hot water and used.

  In the production method of (1), after the flame retardant processing agent and the polyester fiber are contacted, the polyester fiber is dried, and then the polyester fiber is heat-treated at 150 to 200 ° C. to exhaust the fine particles in the processing agent. Let

  A method of bringing the flame retardant processing agent into contact with the polyester fiber is not particularly limited, and examples thereof include a method of immersing the polyester fiber in the flame retardant processing agent and a method of spraying and applying the flame retardant processing agent to the polyester fiber.

  The drying method is not particularly limited, and at least one of natural drying and heat drying can be applied. In the case of heat drying, the drying temperature is usually about 60 to 100 ° C., and the drying time is usually about 5 to 30 minutes. Prior to drying, reduction cleaning or the like may be performed as appropriate.

  After drying, the polyester fiber is heat-treated at 150 to 200 ° C., preferably 170 to 180 ° C., to exhaust fine particles in the processing agent. The heat treatment time can be appropriately set according to the heat treatment temperature, the exhaustion degree of the processing agent, etc., but is usually 30 seconds to 5 minutes, preferably about 1 to 2 minutes.

  In the production method (2), the flame retardant processing agent heated to 100 to 150 ° C. and the polyester fiber are brought into contact with each other, and the fine particles in the processing agent are exhausted to the polyester fiber.

  The temperature of the flame retardant is 100 to 150 ° C, preferably about 120 to 130 ° C. A contact method is not specifically limited, The above-mentioned immersion, spraying, application | coating, etc. can be utilized. For example, in the case of dipping, the fine particles in the processing agent can be exhausted to the polyester fiber by dipping for about 2 to 60 minutes. After the treatment, reduction cleaning or the like may be performed as appropriate.

  In any of the production methods described above, the flame retardant processing agent of the present invention preferably has a fine particle average particle diameter of preferably about 0.2 to 2 μm and high dispersion stability, so that the fine particles are exhausted by the polyester fiber. The flame retardant polyester fiber can be easily produced because it is easily diffused inside the fiber.

  In the flame retardant processing agent for polyester of the present invention, the average particle diameter of the crosslinked cyclic phosphazene compound fine particles is as small as about 0.2 to 2 μm. Can be fire-processed. In addition, since the phosphazene compound containing a large amount of phosphorus is included, the polyester fiber can be flame-retardant processed even if the amount used is less than that of the conventional flame retardant processing agent containing a phosphorus compound. Furthermore, the flame retardant processing agent of the present invention has high dispersion stability and can ensure a usable state (dispersed state) over a long period of time.

  According to the method for producing a flame retardant processing agent of the present invention, the flame retardant processing agent of the present invention having the above characteristics can be easily manufactured without using a large-scale apparatus (such as a disperser).

  Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples. However, the present invention is not limited to the examples.

Examples 1-3
[Flame Retardant a]
In a container A, 300 parts by weight of a crosslinked cyclic phosphazene compound powder product (manufactured by Otsuka Chemical Co., Ltd .: SPS-100) and at least one of a nonionic surfactant, an anionic surfactant and an emulsifying aid are used. 20 parts by weight of oxyethylene adduct (nonionic surfactant), 9 parts by weight of sorbitan monooleate (nonionic surfactant and emulsifying aid), 38 parts by weight of polyoxyethylene distyrenated phenol ether sulfate (anionic surfactant) And 3 parts by weight of castor oil (emulsification aid) was added and melt-mixed at 100 to 120 ° C.

  Into container B, 630 parts by weight of water was added, and while heating to 80 to 90 ° C. and stirring, the molten mixture in container A was dropped little by little to obtain flame retardant processing agent a. Stirring conditions and dropping conditions were adjusted so that the average particle diameter of the obtained crosslinked fine particles was in the range of about 0.2 to 2 μm.

  As a result of measuring the average particle diameter of the obtained flame retardant finishing agent a with a particle size distribution analyzer (Laser diffraction / scattering particle size distribution analyzer LA-910, manufactured by Horiba, Ltd.), the median diameter was 0.294 μm.

Using the obtained flame retardant finishing agent a, the following treatment liquid capable of imparting flame retardancy simultaneously with dyeing was prepared. The amount of the flame retardant processing agent in the treatment liquid was 5% owf (Example 1), 10% owf (Example 2), and 15% owf (Example 3). The above owf means the weight of the flame retardant processing agent per fiber weight (on weight fiber). Next, after processing for 5 minutes at a bath ratio of 1:10 and a temperature of 45 ° C., the temperature is increased to 120 ° C. at 2 ° C./minute and dyeing is performed at 120 ° C. for 60 minutes. Went. The bath ratio indicates the weight ratio of the fiber to be treated (the former) and the treatment liquid (the latter). Next, after cooling to 80 ° C., reduction cleaning was performed according to a conventional method and drying was performed, and then finishing setting was performed at 130 ° C.
[Treatment solution]
Kiwalon P Blue E-SP (disperse dye) * 1 0.1% owf
Kiwalon P Red E-SP (disperse dye) * 1 0.1% owf
Kiwalon P Yellow E-SP (Disperse Dye) * 1 0.1% owf
Nikka Sun Salt RN340 (Dispersant) * 2 0.5g / L
Citric acid (Ph adjuster) Ph3.0-3.5
Flame retardant finishing agent a 5-15% owf
* 1 Kiwa Chemical Industry Co., Ltd. * 2 Nikka Chemical Co., Ltd. [Performance Test]
About the flame-retardant polyester fabric obtained by the process, the flame-retardant evaluation test by JIS L-1091 A-1 (micro burner method) and JIS L-1091 D (coil method) was done. The evaluation results (performance immediately after processing) are shown in Table 1 below. In addition, the flame retardancy evaluation test was also performed on water-washing and dry-cleaning treatments performed five times in accordance with the Fire and Disaster Management Agency Notification No. 1 on February 21, 1986. The evaluation results (performance after water washing) are shown in Table 2 below. Further, the evaluation results (performance after dry cleaning treatment) are shown in Table 3 below.

Examples 4-6
[Flame Retardant b]
In a container C, 280 parts by weight of a crosslinked cyclic phosphazene compound powder product (manufactured by Otsuka Chemical Co., Ltd .: SPS-100) and at least one of a nonionic surfactant, an anionic surfactant and an emulsifying aid are used. 20 parts by weight of oxyethylene adduct (nonionic surfactant), 20 parts by weight of sorbitan monooleate (nonionic surfactant and emulsifying aid), 40 parts by weight of polyoxyethylene distyrenated phenol ether sulfate (anionic surfactant) And 40 parts by weight of tricresyl phosphate (emulsification aid) were added and melt mixed at 100 to 120 ° C.

  600 parts by weight of water was put into the container D, and the molten mixture in the container A was dropped little by little while heating to 80 to 90 ° C. and stirring to obtain a flame retardant processing agent b. Stirring conditions and dropping conditions were adjusted so that the average particle diameter of the obtained crosslinked fine particles was in the range of 0.2 to 2 μm.

  The average particle size of the obtained flame retardant finishing agent b was measured by a particle size distribution measuring device (Laser diffraction / scattering type particle size distribution analyzer LA-910, manufactured by Horiba, Ltd.). As a result, the median size was 0.314 μm.

Using the obtained flame retardant finishing agent b, the following treatment liquid capable of imparting flame retardancy simultaneously with dyeing was prepared. The amount of the flame retardant processing agent in the treatment liquid was 5% owf (Example 4), 10% owf (Example 5), and 15% owf (Example 6). The above owf means the weight of the flame retardant processing agent per fiber weight (on weight fiber). Next, after processing for 5 minutes at a bath ratio of 1:10 and a temperature of 45 ° C., the temperature is increased to 120 ° C. at 2 ° C./minute and dyeing is performed at 120 ° C. for 60 minutes. Went. The bath ratio indicates the weight ratio of the fiber to be treated (the former) and the treatment liquid (the latter). Next, after cooling to 80 ° C., reduction cleaning was performed according to a conventional method and drying was performed, and then finishing setting was performed at 130 ° C.
[Treatment solution]
Kiwalon P Blue E-SP (disperse dye) * 1 0.1% owf
Kiwalon P Red E-SP (disperse dye) * 1 0.1% owf
Kiwalon P Yellow E-SP (Disperse Dye) * 1 0.1% owf
Nikka Sun Salt RN340 (Dispersant) * 2 0.5g / L
Citric acid (Ph adjuster) Ph3.0-3.5
Flame retardant finishing agent b 5-15% owf
* 1 Kiwa Chemical Industry Co., Ltd. * 2 Nikka Chemical Co., Ltd. [Performance Test]
About the flame-retardant polyester fabric obtained by the process, the flame-retardant evaluation test by JIS L-1091 A-1 (micro burner method) and JIS L-1091 D (coil method) was done. The evaluation results (performance immediately after processing) are shown in Table 1 below. In addition, the flame retardancy evaluation test was also performed on water-washing and dry-cleaning treatments performed five times in accordance with the Fire Department Notification No. 1 of February 21, 1986. The evaluation results (performance after water washing) are shown in Table 2 below. Further, the evaluation results (performance after dry cleaning treatment) are shown in Table 3 below.

Comparative Example 1
An evaluation test was performed in the same manner as in Example 1 except that the processing liquid used in Example 1 did not contain the flame retardant finishing agent a. The evaluation results (performance immediately after processing) are shown in Table 1 below. The evaluation results (performance after water washing) are shown in Table 2 below. Further, the evaluation results (performance after dry cleaning treatment) are shown in Table 3 below.

ミクロバーナー法においては、１分加熱、着炎後３秒加熱後に残炎（秒）、残塵（秒）、炭化面積（ｃｍ³）を測定し、コイル法では接炎回数を測定した（表２及び表３において同じ）。表中、∞は殆ど炭化したことを示す（表２及び表３において同じ）。

In the micro-burner method, after flame was heated for 1 minute, and after heating for 3 seconds, after flame (second), residual dust (second) and carbonized area (cm ³ ) were measured, and in the coil method, the number of flame contact was measured (Table 2 and Table 3). In the table, ∞ indicates almost carbonized (same in Tables 2 and 3).

Claims (11)

1) may have a substituent group C ₁ ~ ₆ alkylene group, 2) o-phenylene group, 3) m-phenylene group, 4) p-phenylene group, and 5) the following general formula (1)

[In the formula, A represents —C (CH ₃ ) ₂ —, —SO ₂ —, —S— or —O—. a represents 0 or 1; ]
The following general formula (2), which is cross-linked by at least one cross-linking group selected from the group consisting of:

[In formula, n shows the integer of 3-25. X and Y are the same or different, -O -, - S- or -NR ³ - and (R ³ represents an alkyl group optionally C ₁ ~ ₄ have a hydrogen atom or a substituent) Show. R ¹ and R ² are the same or different, a hydrogen atom, which may have a substituent C ₁ ~ ₂₀ alkyl group, a cycloalkyl group optionally C ₃ ~ ₈ may have a substituent or an aryl group which may C ₅ ~ ₂₂ have a substituent. ]
A flame retardant processing agent for polyester fibers, in which fine particles of a cyclic phosphazene compound represented by the formula (1) are dispersed in a dispersion medium.   The flame retardant processing agent for polyester fibers according to claim 1, wherein the fine particles have an average particle diameter of 0.2 to 2 μm.   The flame-retardant processing agent for polyester fibers according to claim 1 or 2, comprising at least one selected from the group consisting of a nonionic surfactant and an anionic surfactant.   The flame-retardant processing agent for polyester fibers according to claim 1 or 2, comprising an emulsification aid.   The flame retardant processing agent for polyester fibers according to claim 1 or 2, comprising at least one selected from the group consisting of a nonionic surfactant, an anionic surfactant and an emulsifying aid. 1) may have a substituent group C ₁ ~ ₆ alkylene group, 2) o-phenylene group, 3) m-phenylene group, 4) p-phenylene group, and 5) the following general formula (1)

[In the formula, A represents —C (CH ₃ ) ₂ —, —SO ₂ —, —S— or —O—. a represents 0 or 1; ]
The following general formula (2), which is cross-linked by at least one cross-linking group selected from the group consisting of:

[In formula, n shows the integer of 3-25. X and Y are the same or different, -O -, - S- or -NR ³ - and (R ³ represents an alkyl group optionally C ₁ ~ ₄ have a hydrogen atom or a substituent) Show. R ¹ and R ² are the same or different, a hydrogen atom, which may have a substituent C ₁ ~ ₂₀ alkyl group, a cycloalkyl group optionally C ₃ ~ ₈ may have a substituent or an aryl group which may C ₅ ~ ₂₂ have a substituent. ]
Is melted by heating in the presence of at least one selected from the group consisting of a nonionic surfactant, an anionic surfactant and an emulsifying aid, and then the melt is stirred. A method for producing a flame retardant processing agent for polyester fibers, wherein the method is dripped in hot water at 70 to 100 ° C.   The flame retardant processing agent for polyester fibers manufactured by the manufacturing method of Claim 6.   After making the flame-retardant processing agent for polyester fibers according to any one of claims 1 to 5 and 7 contact with polyester fibers, the polyester fibers are dried, and then the polyester fibers are heat-treated at 150 to 200 ° C. A method for producing a flame retardant polyester fiber, wherein fine particles in the processing agent are exhausted.   The flame retardant processing agent for polyester fibers according to any one of claims 1 to 5 and 7, wherein the polyester fiber is brought into contact with a polyester fiber heated to 100 to 150 ° C, and the fine particles in the processing agent are polyester. A method for producing a flame-retardant polyester fiber, wherein the fiber is exhausted. 1) may have a substituent group C ₁ ~ ₆ alkylene group, 2) o-phenylene group, 3) m-phenylene group, 4) p-phenylene group, and 5) the following general formula (1)

[In the formula, A represents —C (CH ₃ ) ₂ —, —SO ₂ —, —S— or —O—. a represents 0 or 1; ]
The following general formula (2), which is cross-linked by at least one cross-linking group selected from the group consisting of:

[In formula, n shows the integer of 3-25. X and Y are the same or different, -O -, - S- or -NR ³ - and (R ³ represents an alkyl group optionally C ₁ ~ ₄ have a hydrogen atom or a substituent) Show. R ¹ and R ² are the same or different, a hydrogen atom, which may have a substituent C ₁ ~ ₂₀ alkyl group, a cycloalkyl group optionally C ₃ ~ ₈ may have a substituent or an aryl group which may C ₅ ~ ₂₂ have a substituent. ]
A flame retardant polyester fiber obtained by exhausting fine particles of a cyclic phosphazene compound represented by the formula:   A flame-retardant polyester fiber produced by the production method according to claim 8 or 9.