JP2014193941A - Flame retardant aid and fiber composite product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a flame retardant aid excellent in flame retardancy and a fiber composite product excellent in flame retardancy and fiber dispersibility.SOLUTION: There are provided: a flame retardant aid which contains a vinyl chloride-based polymer latex composition having a core part and a shell part for forming an outer layer of the core part in which the core part is a vinyl chloride-based polymer having an average particle diameter of 0.12 μm or less and an average degree of polymerization of 400 to 2000 and the shell part is 1 to 300 pts.wt. of a polymer having at least one repeating unit selected from a poly(meth)acrylic acid ester, a polyglycidylvinyl ether, a poly(meth)acrylic acid glycidyl ester and a poly(meth)acrylic acid based on 100 pts.wt. of the vinyl chloride-based polymer, wherein the vinyl chloride-based polymer has an average particle diameter of 0.30 μm or less; and a fiber composite product using the flame retardant aid.

Description

  The present invention relates to a flame retardant aid and a fiber composite, and more specifically to a flame retardant aid excellent in flame retardancy and a fiber composite using the same.

  Conventionally, with respect to plastic materials used as vehicle interior materials and interior materials, there has been a strong demand for flame retardance due to safety problems, and various flame retardancy standards have been established. In response to this, various methods for imparting flame retardancy to fibers have been proposed (Patent Document 1).

  One of them is a method of blending a halogen-based flame retardant. Although brominated flame retardants have excellent flame retardancy, they have a problem in handling performance at the time of processing because they need to be constantly stirred and shaken due to poor stability of the flame retardant treatment solution and settling.

  As a method not using a brominated flame retardant, a method of adding a hydrated metal compound such as aluminum hydroxide or magnesium hydroxide to a fiber is known. It was necessary to add a large amount of a metal compound, which had the disadvantage that the original properties of the fiber were lost.

JP 2001-31824 A

  The present invention has been made in view of the above problems, and is a flame retardant aid (vinyl chloride polymer latex) excellent in flame retardancy obtained by polymerization using a vinyl chloride polymer latex having specific physical properties. Composition) and a fiber composite having excellent flame retardance and excellent dispersibility, which is adhered to the fiber.

  As a result of intensive studies to solve the above problems, the present inventors have found that a flame retardant aid (vinyl chloride polymer latex composition) obtained by polymerizing a specific vinyl chloride polymer latex is a fiber. The fiber composite adhering to is found to be excellent in flame retardancy and also excellent in fiber dispersibility, and has led to the completion of the present invention. That is, the present invention has a core part and a shell part that forms an outer layer of the core part, and the core part has an average particle diameter of 0.12 μm or less and an average degree of polymerization of 400 to 2000. The shell part is represented by the following general formulas (1), (2), (3), (4), (5) and (6) with respect to 100 parts by weight of the vinyl chloride polymer. 1 to 300 parts by weight of a polymer having at least one repeating unit, and 1.0 to 5.0 of an organic compound having a sulfonate salt or a sulfate ester salt with respect to 100 parts by weight of the vinyl chloride polymer. Average particle size of vinyl chloride polymer containing 10 parts by weight or less of an emulsifier with respect to 100 parts by weight of the vinyl chloride polymer, containing 0.05 parts by weight and 0.05 to 2.5 parts by weight of a higher fatty acid salt. The diameter is 0.30 μm or less A flame retardant aid containing a vinyl chloride polymer latex composition, and a fiber composite obtained using the flame retardant aid.

  The present invention is described in detail below.

  The flame retardant aid of the present invention contains a specific vinyl chloride polymer latex composition.

  The vinyl chloride polymer latex composition contained in the flame retardant aid of the present invention has a core part and a shell part that forms an outer layer of the core part, and the core part has an average particle size of 0.12 μm. Hereinafter, it is a vinyl chloride polymer having an average degree of polymerization of 400 to 2000, and the shell portion contains at least one repeating unit represented by a specific general formula with respect to 100 parts by weight of the vinyl chloride polymer. 1 to 300 parts by weight of the polymer, and 1.0 to 5.0 parts by weight of an organic compound having a sulfonate or a sulfate ester salt and 0.1% of a higher fatty acid salt with respect to 100 parts by weight of the vinyl chloride polymer. Containing 0.5 to 2.5 parts by weight, and containing 100 parts by weight of the vinyl chloride polymer, containing 10 parts by weight or less of an emulsifier, and having an average particle size of the vinyl chloride polymer of 0.30 μm or less so is there.

  The vinyl chloride polymer latex composition contained in the flame retardant aid of the present invention has a core part and a shell part that forms an outer layer of the core part.

  The core part of the vinyl chloride polymer latex composition is a vinyl chloride polymer having an average particle size of 0.12 μm or less, and preferably a 0.10 μm or less vinyl chloride polymer. When the average particle diameter exceeds 0.12 μm, the dispersion state of the fiber composite in which the flame retardant aid (vinyl chloride polymer latex composition) adheres to the fibers becomes unfavorable.

  The core part of the vinyl chloride polymer latex composition is a vinyl chloride polymer having an average degree of polymerization of 400 to 2000. Whether the average polymerization degree is less than 400 or more than 2000, there are many precipitates in the state after the production of the vinyl chloride polymer latex composition, and the flame retardant aid (vinyl chloride polymer latex composition) is a fiber. The dispersion state of the fiber composite adhering to the resin deteriorates, which is not preferable.

  The vinyl chloride polymer constituting the core part can be obtained by using a vinyl chloride polymer latex obtained by the method described below, and adding a predetermined monomer described later to perform polymerization. .

  Specifically, this vinyl chloride polymer latex is composed of a vinyl chloride monomer alone, or 100 parts by weight of a vinyl chloride monomer and a monomer copolymerizable therewith, and an organic compound having a sulfonate salt or a sulfate ester salt of 1.0 to It can be obtained by polymerization in the presence of 5.0 parts by weight, preferably 1.5 to 4.5 parts by weight, and 0.05 to 2.5 parts by weight of a higher fatty acid salt. Polymerization is carried out using water as a dispersion medium, 10 to 140% by weight of vinyl chloride monomer alone, or a vinyl chloride monomer and a copolymerization monomer, an organic compound having a predetermined amount of sulfonate or sulfate ester salt, and a higher grade. The polymerization is carried out using a polymerization initiator in the presence of a fatty acid salt while stirring.

  Examples of the organic compound having a sulfonate include alkylbenzenesulfonates such as sodium dodecylbenzenesulfonate and ammonium dodecylbenzenesulfonate, dialkylsulfosuccinates such as sodium dioctylsulfosuccinate and sodium dihexylsulfosuccinate, and alkyls. Examples thereof include alkyl naphthalene sulfonates such as sodium naphthalene sulfonate, alkyl diphenyl ether disulfonates such as sodium alkyl diphenyl ether disulfonate, and organic compounds having a sulfate ester salt include, for example, sodium lauryl sulfate, myristyl sulfate. Examples thereof include alkyl sulfates such as sodium and polyoxyethylene alkylaryl sulfates. When the amount of the organic compound having a sulfonate or sulfate ester salt is less than 1.0 part by weight based on 100 parts by weight of the monomer, the amount of precipitates increases during the production of the vinyl chloride polymer latex, which is not preferable. When the amount exceeds 5.0 parts by weight, impurities in the vinyl chloride polymer latex composition obtained by polymerizing the vinyl chloride polymer latex increase, resulting in a decrease in flame retardancy.

  Examples of the higher fatty acid salt include salts of lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid and the like with an alkali. From the viewpoint of availability, a salt with sodium, potassium, ammonia, or triethanolamine is preferable. When the amount of the higher fatty acid salt used is less than 0.05 parts by weight with respect to 100 parts by weight of the monomer, the amount of precipitates increases during the production of the vinyl chloride polymer latex, which is not preferable. When the amount exceeds 2.5 parts by weight, impurities in the vinyl chloride polymer latex composition obtained by polymerizing the vinyl chloride polymer latex increase, resulting in a decrease in flame retardancy.

  Examples of monomers copolymerizable with vinyl chloride monomer include vinyl esters such as vinyl acetate, vinyl propionate, vinyl myristate, vinyl oleate, vinyl benzoate, acrylic acid, methacrylic acid, fumaric acid, cinnamic acid, etc. Unsaturated carboxylic acids or anhydrides thereof, esters of acrylic acid such as methyl, ethyl, butyl, octyl, benzyl, etc., esters of maleic acid such as methyl, ethyl, butyl, octyl, benzyl, maleic acid esters, fumaric acid esters, cinnamon Unsaturated carboxylic acid esters such as acid esters, vinyl ethers such as vinyl methyl ether, vinyl amyl ether, vinyl phenyl ether, monoolefins such as ethylene, ethylene, propylene, butene, pentene, vinylidene chloride, styrene or derivatives thereof, acrylic Nitrile, one or more methacrylonitrile conventional vinyl compounds vinyl chloride and may radical copolymerization such as nitriles.

  Examples of the polymerization initiator used include water-soluble initiators such as potassium persulfate and ammonium persulfate, 2,2′-azobisisobutyronitrile, 2,2′-azobis-2-methylbutyronitrile, lauroyl. Examples thereof include oil-soluble initiators such as peroxide, t-butylperoxypivalate, diacyl peroxide, peroxyester, and peroxydicarbonate. The addition method of the polymerization initiator used at this time is usually one of batch addition, intermittent addition, continuous addition, or a combination thereof. The polymerization rate of the vinyl chloride monomer is preferably 80 to 97% by weight based on the total monomers.

  The polymerization temperature is 10 to 85 ° C, preferably 30 to 80 ° C, and more preferably 40 to 80 ° C. When the polymerization temperature is less than 10 ° C., the average degree of polymerization of the vinyl chloride polymer increases, and when it exceeds 85 ° C., the average degree of polymerization of the vinyl chloride polymer decreases.

  The polymerization time is not particularly limited, but is preferably 3 to 24 hours.

  The polymerization is terminated by recovering the monomer by reducing the pressure in the vessel to normal pressure and further reducing the pressure. A polymerization inhibitor may be added to terminate the polymerization.

  If necessary, in the latex after completion of the polymerization, 1.0 to 5.0 parts by weight of an organic compound having a sulfonate or sulfate ester salt and 100 to 2 parts by weight of a higher fatty acid salt with respect to 100 parts by weight of the vinyl chloride polymer. These emulsifiers can be additionally added to contain 5 parts by weight.

  In addition, when producing this vinyl chloride polymer latex, other than organic compounds having chain transfer agents, reducing agents, buffering agents, sulfonates or sulfates for the purpose of stabilizing polymerization and reducing the amount of scale generated. An emulsifier or the like can also be added.

  The vinyl chloride polymer latex produced in this manner has an amount of 1.0 to 5.0 parts by weight of an organic compound having a sulfonate or sulfate ester salt and a higher fatty acid salt of 0 to 100 parts by weight of the vinyl chloride polymer. 0.05 to 2.5 parts by weight, the average particle size of the vinyl chloride polymer is 0.12 μm or less, and the average degree of polymerization is 400 to 2000. When the organic compound having a sulfonate or sulfate ester salt is less than 1.0 part by weight, the amount of precipitates increases during the production of the vinyl chloride polymer latex composition, and further, a flame retardant aid (vinyl chloride type) The dispersion state of the fiber composite in which the polymer latex composition) adheres to the fibers is not preferable. When the amount exceeds 5.0 parts by weight, the impurities of the vinyl chloride polymer latex composition obtained by polymerizing the vinyl chloride polymer latex increase, and the flame retardancy decreases. When the higher fatty acid salt is less than 0.05 parts by weight, there are many precipitates at the time of production of the vinyl chloride polymer latex composition, and further, a flame retardant aid (vinyl chloride polymer latex composition) is added to the fiber. The dispersion state of the adhered fiber composite is deteriorated, which is not preferable. When the amount exceeds 2.5 parts by weight, impurities in the vinyl chloride polymer latex composition obtained by polymerizing the vinyl chloride polymer latex increase, resulting in a decrease in flame retardancy. When the average particle diameter exceeds 0.12 μm, the storage stability of the vinyl chloride polymer latex composition obtained by polymerizing the vinyl chloride polymer latex is lowered, and further, a flame retardant aid (vinyl chloride heavy polymer) The dispersion state of the fiber composite in which the combined latex composition) adheres to the fibers is not preferable. If the average degree of polymerization is outside the range of 400 to 2000, scale is generated during the synthesis of the vinyl chloride polymer latex composition obtained by polymerizing the vinyl chloride polymer latex, and further, a flame retardant aid (vinyl chloride heavy polymer) The dispersion state of the fiber composite in which the combined latex composition) adheres to the fibers is not preferable.

  These vinyl chloride polymer latexes can be used alone or in the form of a blend of two or more types without problems.

  The shell part of the vinyl chloride polymer latex composition has the following general formulas (1), (2), (3), (4), (4) with respect to 100 parts by weight of the vinyl chloride polymer constituting the core part. 5) and 1 to 300 parts by weight of a polymer having at least one repeating unit represented by (6).

（式中、Ｒ_１は炭素数２〜８のアルキル基を表し、Ｒ_２は水素またはメチル基を表す。）

(In the formula, R ₁ represents an alkyl group having 2 to 8 carbon atoms, and R ₂ represents hydrogen or a methyl group.)

（式中、Ｒ_３は炭素数１〜４のアルキレン基を表し、Ｒ_４は炭素数１〜４のアルキル基もしくはアルコキシルアルキル基、または水素を表し、Ｒ_５は水素またはメチル基を表す。）

(In the formula, R ₃ represents an alkylene group having 1 to ₄ carbon atoms, R ₄ represents an alkyl group or alkoxylalkyl group having 1 to ₄ carbon atoms, or hydrogen, and R ₅ represents hydrogen or a methyl group.)

（式中、Ｒ_６はメチル基またはエチル基を表す。）

(In the formula, R ₆ represents a methyl group or an ethyl group.)

（式中、Ｒ_７は水素またはメチル基を表す。）

(Wherein R ₇ represents hydrogen or a methyl group.)

（式中、Ｒ_８は水素またはメチル基を表す。）

(In the formula, R ₈ represents hydrogen or a methyl group.)

（式中、Ｒ_９は水素またはメチル基を表す。）
一般式（１）で表される繰返し単位をもつポリマーとしては、例えば、ポリ（メタ）アクリル酸エチル、ポリ（メタ）アクリル酸ｎ−プロピル、ポリ（メタ）アクリル酸イソプロピル、ポリ（メタ）アクリル酸ｎ−ブチル、ポリ（メタ）アクリル酸イソブチル、ポリ（メタ）アクリル酸ｎ−ヘキシル、ポリ（メタ）アクリル酸２−エチルヘキシル、ポリ（メタ）アクリル酸ｎ−オクチル等が挙げられる。

(In the formula, R ₉ represents hydrogen or a methyl group.)
Examples of the polymer having the repeating unit represented by the general formula (1) include poly (meth) acrylate ethyl, poly (meth) acrylate n-propyl, poly (meth) acrylate isopropyl, and poly (meth) acrylic. Examples include n-butyl acid, isobutyl poly (meth) acrylate, n-hexyl poly (meth) acrylate, 2-ethylhexyl poly (meth) acrylate, and n-octyl poly (meth) acrylate.

  Examples of the polymer having a repeating unit represented by the general formula (2) include methoxyethyl poly (meth) acrylate, ethoxyethyl poly (meth) acrylate, propoxyethyl poly (meth) acrylate, and poly (meth) acrylic acid. n-butoxyethyl, poly (meth) acrylic acid methoxypropyl, poly (meth) acrylic acid ethoxypropyl, poly (meth) acrylic acid n-propoxypropyl, poly (meth) acrylic acid n-butoxypropyl, poly (meth) acrylic Examples include hydroxyethyl acid and hydroxypropyl poly (meth) acrylate, and one or more copolymers of these repeating units may be used.

  Examples of the polymer having a repeating unit represented by the general formula (3) include polyvinyl acetate and polyvinyl propionate, and one or more kinds of copolymers of these repeating units may be used.

  Examples of the polymer having a repeating unit represented by the general formula (4) include polyglycidyl methacrylate and polyglycidyl acrylate, and one or more kinds of copolymers of these repeating units may be used.

  Examples of the polymer having a repeating unit represented by the general formula (5) include polyallyl glycidyl ether.

  Examples of the polymer having a repeating unit represented by the general formula (6) include polyacrylic acid and polymethacrylic acid. One or more types of copolymers of these repeating units may be used.

  The vinyl chloride polymer latex composition contained in the flame retardant aid of the present invention is an organic compound having a sulfonate salt or a sulfate ester salt of 1.0 to 5.0 weight with respect to 100 parts by weight of the vinyl chloride polymer. Part and higher fatty acid salt 0.05 to 2.5 parts by weight, and 10 parts by weight or less of emulsifier with respect to 100 parts by weight of vinyl chloride polymer.

  Examples of the organic compound having a sulfonate or a sulfate ester salt include alkylbenzene sulfonates such as sodium dodecylbenzenesulfonate and ammonium dodecylbenzenesulfonate, dialkylsulfosuccinates such as sodium dioctylsulfosuccinate and sodium dihexylsulfosuccinate, Alkyl naphthalene sulfonates such as sodium alkyl naphthalene sulfonate, alkyl diphenyl ether disulfonates such as sodium alkyl diphenyl ether disulfonate, alkyl sulfate esters such as sodium lauryl sulfate and sodium myristyl sulfate, polyoxyethylene alkyl sulfates, poly Examples thereof include oxyethylene alkylaryl sulfate esters. The content of the organic compound having a sulfonate or sulfate ester salt is 1.0 to 5.0 parts by weight with respect to 100 parts by weight of the vinyl chloride polymer. When the amount is less than 1.0 part by weight, the amount of precipitate in the state after the production of the vinyl chloride polymer latex composition increases, and further, the flame retardant aid (vinyl chloride polymer latex composition) adheres to the fiber. This is not preferable because the dispersed state of the fiber composite is deteriorated. When the amount exceeds 5.0 parts by weight, the amount of impurities in the vinyl chloride polymer latex composition increases and flame retardancy decreases. In order to further improve the flame retardancy, 2.0 to 4.0 parts by weight is preferable.

  Examples of the higher fatty acid salt include salts of lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid and the like with an alkali. From the viewpoint of availability, a salt with sodium, potassium, ammonia, or triethanolamine is preferable. The content of the higher fatty acid salt is 0.05 to 2.5 parts by weight with respect to 100 parts by weight of the vinyl chloride polymer. If the amount is less than 0.05 parts by weight, the amount of precipitate in the state after production of the vinyl chloride polymer latex composition increases, and further, a flame retardant aid (vinyl chloride polymer latex composition) adheres to the fiber. This is not preferable because the dispersed state of the fiber composite is deteriorated. When it exceeds 2.5 parts by weight, the impurities of the vinyl chloride polymer latex composition increase, and the flame retardancy decreases. In order to improve a flame retardance more, 0.1-1.0 weight part is preferable.

  When the amount of the emulsifier exceeds 10 parts by weight, the impurities of the vinyl chloride polymer latex composition increase, and the flame retardancy decreases, which is not preferable. Here, the emulsifier refers to an emulsifier used in the polymerization of the shell portion described later, in addition to the organic compound having a sulfonate or sulfate ester salt and a higher fatty acid salt.

  The average particle diameter of the vinyl chloride polymer in the vinyl chloride polymer latex composition contained in the flame retardant aid of the present invention is 0.30 μm or less. When the average particle diameter exceeds 0.30 μm, the storage stability of the vinyl chloride polymer latex composition is deteriorated, and the dispersion state of the fibers of the fiber composite is also deteriorated.

  The vinyl chloride polymer latex composition contained in the flame retardant aid of the present invention is a chain transfer agent, a reducing agent, a buffering agent, a thickener, a condensed phosphoric acid, as long as the object of the present invention is not impaired. A salt, a surfactant, a dispersant, a tackifier, a pH adjuster, an antifoaming agent, a preservative, a film-forming aid, an antiaging agent, an antifreezing agent, and the like may be contained.

  Examples of the thickener include methyl cellulose, carboxymethyl cellulose, polyvinyl alcohol, polyacrylate, polyacrylamide, polyvinyl pyrrolidone and the like, and examples of the condensed phosphate include tripolyphosphate and hexametaphosphate. Examples of the dispersant include a styrene-maleic acid monoester salt copolymer.

  The vinyl chloride polymer latex composition contained in the flame retardant aid of the present invention is an organic compound having a sulfonate salt or a sulfate ester salt of 1.0 to 5.0 weight with respect to 100 parts by weight of the vinyl chloride polymer. In the presence of a vinyl chloride polymer latex having an average particle size of 0.12 μm or less and an average degree of polymerization of 400 to 2000. , Monomers represented by the following general formulas (7), (8), (9), (10) and (11), methacrylic acid and acrylic acid with respect to 100 parts by weight of the vinyl chloride polymer in the latex 1 to 300 parts by weight of at least one monomer selected from the above, and 10 parts by weight or less of an emulsifier are added and polymerized. When the amount of the monomer is less than 1 part by weight, the dispersibility of the fiber of the fiber composite of the present invention is deteriorated, which is not preferable. When it exceeds 300 parts by weight, the flame retardancy of the fiber composite of the present invention is lowered, which is not preferable.

（式中、Ｒ_９は炭素数２〜８のアルキル基を表し、Ｒ_１０は水素またはメチル基を表す。）

(In the formula, R ₉ represents an alkyl group having 2 to 8 carbon atoms, and R ₁₀ represents hydrogen or a methyl group.)

（式中、Ｒ_１１は炭素数１〜４のアルキレン基を表し、Ｒ_１２は炭素数１〜４のアルキル基もしくはアルコキシルアルキル基、または水素を表し、Ｒ_１３は水素またはメチル基を表す。）

(In the formula, R ₁₁ represents an alkylene group having 1 to 4 carbon atoms, R ₁₂ represents an alkyl group or alkoxylalkyl group having 1 to 4 carbon atoms, or hydrogen, and R ₁₃ represents hydrogen or a methyl group.)

（式中、Ｒ_１４はメチル基またはエチル基を表す。）

(In the formula, R ₁₄ represents a methyl group or an ethyl group.)

（式中、Ｒ_１５は水素またはメチル基を表す。）

(In the formula, R ₁₅ represents hydrogen or a methyl group.)

（式中、Ｒ_１６は水素またはメチル基を表す。）
一般式（７）で表される（メタ）アクリル酸エステルとしては、例えば、（メタ）アクリル酸エチル、（メタ）アクリル酸ｎ−プロピル、（メタ）アクリル酸イソプロピル、（メタ）アクリル酸ｎ−ブチル、（メタ）アクリル酸イソブチル、（メタ）アクリル酸ｎ−ヘキシル、（メタ）アクリル酸２−エチルヘキシル、（メタ）アクリル酸ｎ−オクチル等が挙げられる。

(In the formula, R ₁₆ represents hydrogen or a methyl group.)
Examples of the (meth) acrylic acid ester represented by the general formula (7) include, for example, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n- (meth) acrylate. Examples include butyl, isobutyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and n-octyl (meth) acrylate.

  Examples of the (meth) acrylic acid ester represented by the general formula (8) include methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, propoxyethyl (meth) acrylate, and (meth) acrylic acid n. -Butoxyethyl, methoxypropyl (meth) acrylate, ethoxypropyl (meth) acrylate, n-propoxypropyl (meth) acrylate, n-butoxypropyl (meth) acrylate, hydroxyethyl (meth) acrylate, (meth ) Hydroxypropyl acrylate and the like.

  Examples of the monomer represented by the general formula (9) include vinyl acetate and vinyl propionate.

  Examples of the monomer represented by the general formula (10) include glycidyl methacrylate and glycidyl acrylate.

  Examples of the monomer represented by the general formula (11) include allyl glycidyl ether.

  If methyl methacrylate is used during the synthesis of the vinyl chloride polymer latex composition, the cause is unknown, but a precipitate is generated during the synthesis of the vinyl chloride polymer latex composition, which is not preferable.

  Other than the monomers represented by the general formulas (7) to (11), examples of vinyl monomers copolymerizable with these include methyl acrylate, n-pentyl methacrylate, and (meth). N-decyl acrylate, n-dodecyl (meth) acrylate, n-octadecyl (meth) acrylate, cyanomethyl (meth) acrylate, 1-cyanoethyl (meth) acrylate, 2-cyanoethyl (meth) acrylate, ( 1-cyanopropyl (meth) acrylate, 2-cyanopropyl (meth) acrylate, 3-cyanopropyl (meth) acrylate, 4-cyanobutyl (meth) acrylate, 6-cyanohexyl (meth) acrylate, (meth ) 2-ethyl-6-cyanohexyl acrylate, 8-cyanooctyl (meth) acrylate, methoxymethyl (meth) acrylate, (meth) ) Can be exemplified acrylic acid ethoxymethyl, methacrylic acid n- propoxy-propyl, methacrylic acid n- butoxy propyl, vinyl acetate, vinyl propionate and the like.

  Further, 1,1-dihydroperfluoroethyl (meth) acrylate, 1,1-dihydroperfluoropropyl (meth) acrylate, 1,1,5-trihydroperfluorohexyl (meth) acrylate, (meth) acrylic acid 1 , 1,2,2-tetrahydroperfluoropropyl, 1,1,7-trihydroperfluoroheptyl (meth) acrylate, 1,1-dihydroperfluorooctyl (meth) acrylate, 1,1-dihydro (meth) acrylate Perfluorodecyl, 1-hydroxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, hydroxyethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dibutylaminoethyl (meth) acrylate, (meth ) As ingredients other than acrylic esters, Alkyl vinyl ketone compounds such as ru vinyl ketone, alkyl vinyl ether compounds such as vinyl ethyl ether, allyl ether compounds such as allyl methyl ether, styrene, α-methyl styrene, chlorostyrene, vinyl toluene, p-chloromethyl styrene, p-acetoxy styrene, p-acetoxystyrene, p-butoxystyrene, 4-vinylbenzoic acid, 2-vinylpyridine, 4-vinylpyridine, vinyl aromatic compounds such as vinylnaphthalene, vinylnitrile compounds such as acrylonitrile and methacrylonitrile, acrylamide, budadiene, 2,3-dichloro-1,3-butadiene, 2-cyano-1,3-butadiene, 1-chloro-1,3-butadiene, 2- (N-piperidimethyl) -1,3-butadiene, 2-triethoxy Methyl 1,3-butadiene compounds such as -1,3-butadiene, 2- (N, N-dimethylamino) -1,3-butadiene, N- (2-methylene-3-butenoyl) morpholine, isoprene, pentadiene, chloride Vinyl, vinylidene chloride, vinyl fluoride, vinylidene fluoride, vinyl propionate, maleic anhydride, citraconic anhydride, itaconic anhydride, maleic acid, maleic acid ester, fumaric acid ester, crotonic acid, itaconic acid, fumaric acid, methacrylate Roxyxypropyltrimethoxysilane, acrolein, diacetone acrylamide, vinyl methyl ketone, vinyl ethyl ketone, diacetone methacrylate, vinyl sulfonic acid, 2-acrylamido-1-methyl sulfonic acid, 2-methacrylamide-2-methylpropane sulfonic acid Etc. In order to obtain a fiber composite having excellent dispersibility, it is preferably added in an amount of 1 to 200 parts by weight, more preferably 5 to 150 parts by weight, based on 100 parts by weight of the vinyl chloride polymer. be able to.

  As a method for adding the monomer represented by the general formulas (7), (8), (9), (10) and (11) and at least one monomer selected from methacrylic acid and acrylic acid Is usually performed by any one method of batch addition, intermittent addition, continuous addition, or a combination thereof. Further, the monomer can be added by emulsifying all or part of the monomer.

  To polymerize the monomer represented by the general formulas (7), (8), (9), (10) and (11) and at least one monomer selected from methacrylic acid and acrylic acid. Examples of the polymerization initiator used include water-soluble initiators such as potassium persulfate, ammonium persulfate, sodium persulfate, hydrogen peroxide, and t-butyl hydroperoxide, 2,2′-azobisisobutyronitrile, 2, 2′-azobis-2-methylbutyronitrile, lauroyl peroxide, t-butyl peroxypivalate, diacyl peroxide, peroxy ester, peroxydicarbonate, and other oil-soluble initiators, and the like. In some cases, a polymerization is initiated by adding a reducing agent such as ferrous salt such as ferrous sulfate, sodium hydrosulfite, or L-alcorbic acid. . The addition method of the polymerization initiator used at this time is usually one of batch addition, intermittent addition, continuous addition, or a combination thereof. In the method for producing a vinyl chloride polymer latex composition, a mixture of the above monomer and, if necessary, a molecular weight regulator can be used. As the molecular weight regulator, alkyl mercaptans such as n-dodecyl mercaptan, t-dodecyl mercaptan, octyl mercaptan are usually used.

  The emulsifier used when polymerizing the monomer is not particularly limited, and examples thereof include alkyl benzene sulfonic acids such as sodium dodecyl benzene sulfonate, potassium dodecyl benzene sulfonate, ammonium dodecyl benzene sulfonate, and sodium lauryl sulfate. Anionic surfactants such as alkyl sulfates such as sodium myristyl sulfate, sodium dioctyl sulfosuccinate, sulfosuccinates such as sodium dihexyl sulfosuccinate, polyoxyethylene alkyl sulfates, polyoxyethylene alkylaryl sulfates, Sorbitan esters such as sorbitan monooleate, polyoxyethylene sorbitan monostearate, polyoxyethylene alkylphenyl ethers, polyoxyethylene Nonions such as ethylene alkyl esters, polyoxyethylene alkyl ethers such as polyoxyethylene alkyl ether, polyalkylene glycols, polyvinyl alcohol, partially saponified polyvinyl alcohol, partially saponified polymethyl methacrylate, polyacrylic acid and salts thereof And surface active agents. These may be used alone or in combination of two or more. As the addition method, it is usually performed by any one of batch addition, intermittent addition, continuous addition, or a combination thereof.

  The polymerization temperature is not particularly limited, but is preferably 30 to 100 ° C, more preferably 40 to 80 ° C.

  The polymerization time is not particularly limited, but is preferably 3 to 24 hours.

  The polymerization is completed by cooling the reaction solution. In some cases, a polymerization inhibitor may be added to terminate the polymerization.

  Chain transfer agent, reducing agent, buffering agent, thickener for the purpose of stabilizing polymerization and reducing the amount of scale generated when producing the vinyl chloride polymer latex composition contained in the flame retardant aid of the present invention , Condensed phosphates, dispersants, tackifiers, pH adjusters, antifoaming agents, preservatives, film-forming aids, anti-aging agents, anti-freezing agents, and the like can also be added.

  In the fiber composite of the present invention, the flame retardant aid of the present invention (vinyl chloride polymer latex composition) is adhered to the fiber. The fiber composite of the present invention is excellent in flame retardancy because the flame retardant aid (vinyl chloride polymer latex composition) is adhered to the fiber. Examples of fibers include polyester fibers, polyethylene fibers, polypropylene fibers, polyamide fibers, acrylic fibers, urethane fibers, polyvinyl chloride fibers, polyvinylidene chloride fibers, and acetate fibers; pulp, cotton, wool, palm fibers, Examples thereof include natural fibers such as hemp fiber and bamboo fiber; inorganic fibers such as glass fiber, ceramic fiber, carbon fiber, and metal fiber.

  The fiber composite of the present invention can be obtained by attaching a flame retardant aid (vinyl chloride polymer latex composition) to the fiber. There is no restriction | limiting in particular as an adhesion method, Although it can adhere by the method selected suitably from well-known impregnation methods, For example, a dipping method, a froth method, etc. are mentioned suitably.

  In the present invention, a fiber composite having excellent flame retardancy and excellent fiber dispersibility can be provided.

  The present invention will be described more specifically with reference to the following examples and comparative examples, but the present invention is not limited by these.

  In addition, the evaluation methods in the following examples and comparative examples are as follows.

<Storage stability of flame retardant aid (vinyl chloride polymer latex composition)>
A flame retardant aid (vinyl chloride polymer latex composition) was diluted with water to adjust the solid content to 30% by weight. Put 500g of flame retardant aid (vinyl chloride polymer latex composition) in a transparent glass bottle, let stand at room temperature for 1 month, and visually confirm the presence or absence of sediment in the latex composition. evaluated.

    ○: No sediment is generated.

    Δ: Slight precipitation was observed.

    X: Generation of a large amount of sediment was observed.

<Film stability>
A flame retardant aid (vinyl chloride polymer latex composition) was coated on a PET film to a thickness of 20 μm with a bar coater. Furthermore, it dried at 110 degreeC * 30 second, and the state of the obtained coating film was confirmed visually.

<Amount of sodium dodecylbenzenesulfonate and potassium laurate in vinyl chloride polymer latex>
The vinyl chloride polymer latex after completion of the polymerization is collected from the polymerization vessel, the polymerization conversion rate of the vinyl monomer is obtained by measuring the solid content after vacuum drying at 40 ° C. for 24 hours, and the amount of sodium dodecylbenzenesulfonate in the polymer from the charged composition And the amount of potassium laurate was calculated | required.

<Amount of polymer in shell portion in vinyl chloride polymer latex composition>
For butyl acrylate, glycidyl acrylate, 2-hydroxyethyl methacrylate, and ethyl acrylate, DB-5 (manufactured by Agilent Technologies) is used as a column in gas chromatography GC-14A (Shimadzu Corporation). Used and determined from the monomer conversion. About acrylic acid, it calculated | required from the monomer conversion rate using Inertsil ODS-3 for the column with the liquid chromatography.

<Amount of emulsifier in the vinyl chloride polymer latex composition>
After obtaining the monomer conversion rate by gas chromatography and liquid chromatography, the solid content obtained by the same operation as the measurement of sodium dodecylbenzenesulfonate amount and potassium laurate amount in the vinyl chloride polymer latex Obtained from measurement.

<Measurement method of average particle diameter>
The average particle size was measured using a particle size distribution measuring machine (Microtrac UPA150, manufactured by Nikkiso Co., Ltd.), the refractive index of the dispersion medium was set to 1.33, the particle size distribution was measured, and the median particle size was obtained. The average particle size of the particles was used.

<Average polymerization degree>
After drying the vinyl chloride polymer latex, 5 times the amount of methanol is stirred and added to the THF solution to precipitate the vinyl chloride polymer, and after filtration and drying, the K value is measured according to JIS K7367-2. The average degree of polymerization was calculated.

<Dispersibility of fiber>
The test piece obtained by measuring the burning rate was observed with a scanning electron microscope (SEM), and the dispersibility of the fiber was determined as follows.

  5: A vinyl chloride polymer was dispersed throughout the fiber.

  4: The vinyl chloride polymer was dispersed in 2/3 or more of the fibers, but aggregates were observed in 1/3 or less of the fibers.

  3: Vinyl chloride polymer was dispersed in 1/2 or more of the fiber, but aggregates were observed in 1/2 or less of the fiber.

  2: The vinyl chloride polymer was dispersed in 1/3 or more of the fibers, but aggregates were observed in 2/3 or less of the fibers.

  1: A vinyl chloride polymer aggregated over the entire fiber was observed.

<Measurement of burning rate>
A polyester fiber woven fabric cut to 100 × 350 mm was prepared.

120 ml of flame retardant aid (vinyl chloride polymer latex composition) was prepared and poured into a tray. Thereafter, the woven fabric was immersed in the tray for 1 minute. Thereafter, the woven fabric was turned over and immersed for another 1 minute. Thereafter, the woven fabric was taken out from the tray, and the squeezing operation was performed by hand. The drawing operation was performed four times with the upper end of the woven fabric. Next, the squeezing operation was performed 4 times with the woven fabric reversed. Then, it dried at 130 degreeC for 5 minutes, and the adhesion amount was 100 g / m < ² >. This was used as a test piece.

  The combustibility of the obtained test piece was measured. In the combustion test, a test piece (350 × 100 mm) was held horizontally, a 38 mm flame was indirectly flamed for 15 seconds, and a determination was made based on the burning speed with respect to 254 mm between the A and B mark lines ( Combustion test method FMVSS-302 method).

Judgment ○: Combustion rate is 100 mm / min or less ×: Combustion rate exceeds 100 mm / min Production Example 1
As shown in Table 1, 830.0 g of deionized water, 750.0 g of vinyl chloride monomer, 6.8 g of 3 wt% potassium persulfate and 75.0 g of 5 wt% aqueous sodium dodecylbenzenesulfonate in a 2.5 L autoclave (monomer 0.50 parts by weight with respect to the mixture) and the temperature was raised to 66 ° C. to initiate polymerization. The temperature was kept at 66 ° C. and the polymerization proceeded. After the pressure in the autoclave at 66 ° C. dropped to 0.7 MPa, the polymerization was stopped, unreacted vinyl chloride monomer was recovered, and 270.0 g of a 5 wt% sodium dodecylbenzenesulfonate aqueous solution (1.80 to the monomer). Parts by weight) and 46.0 g of a 5% by weight aqueous potassium laurate solution (0.34 parts by weight with respect to the monomer) were added to obtain a vinyl chloride polymer latex (dodecylbenzenesulfonic acid with respect to 100 parts by weight of the vinyl chloride polymer). Amount of sodium: 2.56 parts by weight, amount of potassium laurate: 0.34 parts by weight, average particle size: 0.08 μm, average degree of polymerization: 750).

製造例２〜３
表１に示す通り、ドデシルベンゼンスルホン酸ナトリウム量を変えた以外は製造例１と同様の操作で、塩化ビニル系ポリマーラテックスを得た（塩化ビニル系ポリマー１００重量部に対するドデシルベンゼンスルホン酸ナトリウムの量及びラウリン酸カリウムの量、平均粒子径、平均重合度を表１に示す）。

Production Examples 2-3
As shown in Table 1, a vinyl chloride polymer latex was obtained in the same manner as in Production Example 1 except that the amount of sodium dodecylbenzenesulfonate was changed (the amount of sodium dodecylbenzenesulfonate relative to 100 parts by weight of the vinyl chloride polymer). And the amount of potassium laurate, the average particle diameter, and the average degree of polymerization are shown in Table 1).

Production Examples 4-5
As shown in Table 1, a vinyl chloride polymer latex was obtained in the same manner as in Production Example 1 except that the amount of potassium laurate was changed (the amount of sodium dodecylbenzenesulfonate and laurin relative to 100 parts by weight of the vinyl chloride polymer). The amount of potassium acid, the average particle diameter, and the average degree of polymerization are shown in Table 1).

Production Example 6
As shown in Table 2, a vinyl chloride polymer latex was obtained in the same manner as in Production Example 1 except that the polymerization temperature was changed to 70 ° C. and 0.75 g of dodecyl mercaptan was added (100 parts by weight of vinyl chloride polymer). Table 2 shows the amount of sodium dodecylbenzenesulfonate and the amount of potassium laurate, the average particle diameter, and the average degree of polymerization with respect to the above).

Production Example 7
As shown in Table 2, a vinyl chloride polymer latex was obtained in the same manner as in Production Example 1 except that the polymerization temperature was changed to 45 ° C. (the amount of sodium dodecylbenzenesulfonate relative to 100 parts by weight of the vinyl chloride polymer and The amount of potassium laurate, the average particle size, and the average degree of polymerization are shown in Table 2).

Comparative production example 1
<Preparation of vinyl chloride polymer latex by fine suspension polymerization method>
A 1 m ³ autoclave was charged with 360.0 kg of deionized water, 300.0 kg of vinyl chloride monomer, 5.7 kg of lauroyl peroxide, and 30.0 kg of a 15 wt% sodium dodecylbenzenesulfonate aqueous solution, and this polymerization solution was used for 3 hours using a homogenizer. After the homogenization treatment, the temperature was raised to 45 ° C. to proceed the polymerization. After the pressure has dropped, the polymerization is stopped, the unreacted vinyl chloride monomer is recovered, the solid content 35% by weight particles have an average particle size of 0.55 μm, and the polymer has an excess of 2% by weight. A seed latex 1 containing lauroyl oxide was obtained.

In a 2.5 L autoclave, 500 g of deionized water, 500.0 g of vinyl chloride monomer, 16.0 g of 5 wt% sodium lauryl sulfate aqueous solution, 95.0 g of seed latex 1 and 4.0 g of 0.1 wt% copper sulfate aqueous solution The temperature of the charged reaction mixture was raised to 48 ° C., and 150.0 g of 0.05 wt% aqueous ascorbic acid solution was continuously added throughout the entire polymerization time. Further, 0.7 parts by weight of sodium lauryl sulfate was continuously added to 100 parts by weight of the vinyl chloride monomer from the start of the polymerization to a polymerization conversion rate of 85%. The polymerization was stopped when the polymerization pressure dropped from the saturated vapor pressure of vinyl chloride at 48 ° C. by 2 kg / cm ² , and the unreacted vinyl chloride monomer was recovered, and 46.0 g of 5 wt% aqueous potassium laurate solution (0% relative to the monomer). .46 parts by weight) was added to obtain a vinyl chloride polymer latex (amount of sodium dodecylbenzenesulfonate with respect to 100 parts by weight of vinyl chloride polymer: 0.12 parts by weight, amount of potassium laurate: 0.50 parts by weight). Part, average particle size: 1.52 μm, average degree of polymerization: 1400).

Comparative Production Examples 2-6
As shown in Table 3, a vinyl chloride polymer latex was obtained in the same manner as in Production Example 1 except that the amount of sodium dodecylbenzenesulfonate and potassium laurate were changed (dodecylbenzene with respect to 100 parts by weight of vinyl chloride polymer). The amount of sodium sulfonate, the amount of potassium laurate, the average particle size, and the average degree of polymerization are shown in Table 3).

比較製造例７
表４に示す通り、重合温度を９０℃に変更し、ドデシルメルカプタンを７．５０ｇ仕込んだ以外は製造例１と同様の操作で、塩化ビニル系ポリマーラテックスを得た（塩化ビニル系ポリマー１００重量部に対するドデシルベンゼンスルホン酸ナトリウムの量及びラウリン酸カリウムの量、平均粒子径、平均重合度を表４に示す）。

Comparative Production Example 7
As shown in Table 4, a vinyl chloride polymer latex was obtained in the same manner as in Production Example 1 except that the polymerization temperature was changed to 90 ° C. and 7.50 g of dodecyl mercaptan was added (100 parts by weight of vinyl chloride polymer). Table 4 shows the amount of sodium dodecylbenzenesulfonate and the amount of potassium laurate, the average particle size, and the average degree of polymerization with respect to the amount)

比較製造例８
表４に示す通り、重合温度を５℃に変更し、重合中にピロ亜硫酸カリウムの１０重量％水溶液３．５８ｇを連続添加した以外は、製造例１と同様の操作で、塩化ビニル系ポリマーラテックスを得た（塩化ビニル系ポリマー１００重量部に対するドデシルベンゼンスルホン酸ナトリウムの量及びラウリン酸カリウムの量、平均粒子径、平均重合度を表４に示す）。

Comparative Production Example 8
As shown in Table 4, the polymerization temperature was changed to 5 ° C., and a vinyl chloride polymer latex was prepared in the same manner as in Production Example 1, except that 3.58 g of a 10 wt% aqueous solution of potassium pyrosulfite was continuously added during the polymerization. (The amount of sodium dodecylbenzenesulfonate, the amount of potassium laurate, the average particle size, and the average degree of polymerization are shown in Table 4 with respect to 100 parts by weight of the vinyl chloride polymer).

Example 1
As shown in Table 5, using the vinyl chloride polymer latex obtained in Production Example 1, 67.6 g of vinyl chloride polymer latex and 164.1 g of deionized water were placed in a 0.5 L separable flask under a nitrogen atmosphere. First, the internal temperature was raised to 60 ° C., followed by continuous addition of a mixture of 12.5 g of butyl acrylate and 0.125 g of dodecyl mercaptan (continuous addition during polymerization-1), and simultaneously 0.14 g of ammonium persulfate as an emulsifier 0.1 g of sodium lauryl sulfate and 20.0 g of deionized water were continuously added (continuous addition during polymerization-2), and after the reaction for 6 hours, the reaction solution was cooled and a flame retardant aid (vinyl chloride polymer latex) Composition) was obtained (average particle size: 0.09 μm). Table 5 shows the average particle size, production stability, state after production, storage stability, and coating film stability of the obtained flame retardant aid (vinyl chloride polymer latex composition). Foamability during the reaction was good, almost no scale was generated, and storage stability and coating film stability were also good.

得られた難燃助剤（塩化ビニル系重合体ラテックス組成物）を使用して試験片を作製し、走査型電子顕微鏡（ＳＥＭ）で分散状態を判定したところ、繊維全体に塩化ビニル系重合体が分散していた（点数５）。また、燃焼速度を測定した結果、５４ｍｍ／ｍｉｎであり、○であった。

A test piece was prepared using the obtained flame retardant aid (vinyl chloride polymer latex composition), and the dispersion state was judged by a scanning electron microscope (SEM). Was dispersed (score 5). Moreover, as a result of measuring a combustion rate, it was 54 mm / min and was (circle).

Examples 2-5
As shown in Table 5, the procedure was the same as in Example 1 except that the vinyl chloride polymer latex obtained in Production Example 1 was replaced with the vinyl chloride polymer latex obtained in Production Example 2 to Production Example 5. A combustion aid (vinyl chloride polymer latex composition) was obtained. Table 5 shows the average particle size, production stability, state after production, storage stability, and coating film stability of the obtained flame retardant aid (vinyl chloride polymer latex composition). From the results of Table 5, the flame retardant aid (vinyl chloride polymer latex composition) of the present invention does not produce a precipitate after production, has excellent foaming properties, and provides a uniform coating film, storage stability, Excellent coating film stability.

  Test pieces were prepared using each of the obtained flame retardant aids (vinyl chloride polymer latex composition), and the dispersion state was determined by a scanning electron microscope (SEM). The system polymer was dispersed (score 5). Moreover, as a result of measuring a combustion rate, they are 67 mm / min (Example 2), 70 mm / min (Example 3), 65 mm / min (Example 4), and 82 mm / min (Example 5). Met.

Example 6
A flame retardant aid (vinyl chloride polymer latex composition) was obtained in the same manner as in Example 1 except that the changes were made as shown in Table 5. Table 5 shows the average particle size, production stability, state after production, storage stability, and coating film stability of the obtained vinyl chloride polymer latex composition. From the results of Table 5, the flame retardant aid (vinyl chloride polymer latex composition) of the present invention does not produce a precipitate after production, has excellent foaming properties, and provides a uniform coating film, storage stability, Excellent coating film stability.

  A test piece was prepared using the obtained flame retardant aid (vinyl chloride polymer latex composition), and the dispersion state was judged by a scanning electron microscope (SEM). Was dispersed (score 5). Moreover, as a result of measuring a combustion rate, it was 78 mm / min and was (circle).

Examples 7-11
A flame retardant aid (vinyl chloride polymer latex composition) was obtained in the same manner as in Example 1 except that the changes were made as shown in Table 6. Table 6 shows the average particle diameter, production stability, state after production, storage stability, and coating film stability of the obtained vinyl chloride polymer latex composition. From the results of Table 6, the flame retardant aid of the present invention (vinyl chloride polymer latex composition) does not produce a precipitate after production, has excellent foaming properties, and provides a uniform coating film, storage stability, Excellent coating film stability.

得られた難燃助剤（塩化ビニル系重合体ラテックス組成物）をそれぞれ使用して試験片を作製し、走査型電子顕微鏡（ＳＥＭ）で分散状態を判定したところ、いずれも繊維全体に塩化ビニル系重合体が分散していた（点数５）。また、燃焼速度を測定した結果、８０ｍｍ／ｍｉｎ（実施例７）、７４ｍｍ／ｍｉｎ（実施例８）、６８ｍｍ／ｍｉｎ（実施例９）、６６ｍｍ／ｍｉｎ（実施例１０）、７７ｍｍ／ｍｉｎ（実施例１１）であり、いずれも○であった。

Test pieces were prepared using each of the obtained flame retardant aids (vinyl chloride polymer latex composition), and the dispersion state was determined by a scanning electron microscope (SEM). The system polymer was dispersed (score 5). Moreover, as a result of measuring a combustion rate, 80 mm / min (Example 7), 74 mm / min (Example 8), 68 mm / min (Example 9), 66 mm / min (Example 10), 77 mm / min (implementation) Example 11) and all were good.

Examples 12-14
A flame retardant aid (vinyl chloride polymer latex composition) was obtained in the same manner as in Example 1 except that the changes were made as shown in Table 7. Table 7 shows the average particle size, production stability, state after production, storage stability, and coating film stability of the obtained vinyl chloride polymer latex composition. From the results in Table 7, the flame retardant aid (vinyl chloride polymer latex composition) of the present invention does not produce a precipitate after production, has excellent foaming properties, and a uniform coating film is obtained, storage stability, Excellent coating film stability.

得られた難燃助剤（塩化ビニル系重合体ラテックス組成物）をそれぞれ使用して試験片を作製し、走査型電子顕微鏡（ＳＥＭ）で分散状態を判定したところ、いずれも繊維全体に塩化ビニル系重合体が分散していた（点数５）。また、燃焼速度を測定した結果、７１ｍｍ／ｍｉｎ（実施例１２）、８３ｍｍ／ｍｉｎ（実施例１３）、７９ｍｍ／ｍｉｎ（実施例１４）であり、いずれも○であった。

Test pieces were prepared using each of the obtained flame retardant aids (vinyl chloride polymer latex composition), and the dispersion state was determined by a scanning electron microscope (SEM). The system polymer was dispersed (score 5). Moreover, as a result of measuring a combustion rate, they were 71 mm / min (Example 12), 83 mm / min (Example 13), and 79 mm / min (Example 14), and all were (circle).

Example 15
The flame retardant aid (vinyl chloride) was changed in the same manner as in Example 1 except that polyoxyethylene alkyl ether (Kao, Emulgen 1108) was used as an emulsifier instead of sodium lauryl sulfate. System polymer latex composition). Table 7 shows the average particle size, production stability, state after production, storage stability, and coating film stability of the obtained vinyl chloride polymer latex composition. From the results in Table 7, the flame retardant aid (vinyl chloride polymer latex composition) of the present invention does not produce a precipitate after production, has excellent foaming properties, and a uniform coating film is obtained, storage stability, Excellent coating film stability.

  A test piece was prepared using the obtained flame retardant aid (vinyl chloride polymer latex composition), and the dispersion state was judged by a scanning electron microscope (SEM). Was dispersed (score 5). Moreover, as a result of measuring a combustion rate, it was 72 mm / min and it was (circle).

Comparative Example 1
As shown in Table 8, 67.6 g of vinyl chloride polymer latex and 164.1 g of deionized water were placed in a 0.5 L separable flask using the vinyl chloride polymer latex obtained in Comparative Production Example 1 in a nitrogen atmosphere. The internal temperature was raised to 60 ° C., followed by continuous addition of a mixture of 12.5 g of butyl acrylate and 0.125 g of dodecyl mercaptan, and at the same time 0.14 g of ammonium persulfate, 0.1 g of sodium lauryl sulfate, deionized water 20.0 g was continuously added (continuous addition during polymerization-2), and after the reaction for 6 hours, the reaction solution was cooled to obtain a flame retardant aid (vinyl chloride polymer latex composition) (average particle diameter). : 1.53 μm). Table 8 shows the average particle size, production stability, state after production, storage stability, and coating film stability of the obtained flame retardant aid (vinyl chloride polymer latex composition). Although the foaming property during the reaction was good, a large amount of scale was generated, and there were many precipitates, so the coating film stability could not be measured. A large amount of sediment was observed (storage stability).

得られた難燃助剤（塩化ビニル系重合体ラテックス組成物）を使用して試験片を作製し、走査型電子顕微鏡（ＳＥＭ）で分散状態を判定したところ、繊維全体に凝集した塩ビ系ポリマーが見られた（点数１）。また、燃焼速度を測定した結果、８８ｍｍ／ｍｉｎであり、○であった。

A test piece was prepared using the obtained flame retardant aid (vinyl chloride polymer latex composition), and the dispersion state was judged by a scanning electron microscope (SEM). (Score 1). Moreover, as a result of measuring a combustion rate, it was 88 mm / min and was (circle).

Comparative Example 2
As shown in Table 8, a flame retardant aid (vinyl chloride polymer latex composition) was obtained in the same manner as in Comparative Example 1 except that the vinyl chloride polymer latex obtained in Comparative Production Example 2 was used. (Average particle diameter: 0.18 μm). Table 8 shows the average particle size, production stability, state after production, storage stability, and coating film stability of the obtained flame retardant aid (vinyl chloride polymer latex composition). There are many foams during the reaction, scale is generated, there are many precipitates, and the coating stability of the obtained flame retardant aid (vinyl chloride polymer latex composition) is inferior to the examples, and a large amount of precipitates Was observed (storage stability).

  Using the obtained flame retardant aid (vinyl chloride polymer latex composition), a test piece was prepared and the dispersion state was judged by a scanning electron microscope (SEM). Although the vinyl polymer was dispersed, aggregates were observed in 2/3 or less of the fibers (score 2). Moreover, as a result of measuring a combustion rate, it was 83 mm / min and was (circle).

Comparative Example 3
As shown in Table 8, a flame retardant aid (vinyl chloride polymer latex composition) was obtained in the same manner as in Comparative Example 1 except that the vinyl chloride polymer latex obtained in Comparative Production Example 3 was used. (Average particle diameter: 0.08 μm). Table 8 shows the average particle size, production stability, state after production, storage stability, and coating film stability of the obtained flame retardant aid (vinyl chloride polymer latex composition). There was much foaming during the reaction. Although the coating stability of the obtained flame retardant aid (vinyl chloride polymer latex composition) was good, slight precipitation was observed (storage stability).

  Using the obtained flame retardant aid (vinyl chloride polymer latex composition), a test piece was prepared and the dispersion state was judged by a scanning electron microscope (SEM). Although the vinyl polymer was dispersed, aggregates were observed in 2/3 or less of the fibers (score 2). Moreover, as a result of measuring a combustion rate, it was 125 mm / min and was x.

Comparative Example 4
As shown in Table 8, a flame retardant aid (vinyl chloride polymer latex composition) was obtained in the same manner as in Comparative Example 1 except that the vinyl chloride polymer latex obtained in Comparative Production Example 4 was used. (Average particle diameter: 0.10 μm). Table 8 shows the average particle size, production stability, state after production, storage stability, and coating film stability of the obtained flame retardant aid (vinyl chloride polymer latex composition). The foaming property during the reaction was good, but scale was generated and there were many precipitates. Although the coating stability of the obtained flame retardant aid (vinyl chloride polymer latex composition) was good, a large amount of precipitate was observed (storage stability).

  Using the obtained flame retardant aid (vinyl chloride polymer latex composition), a test piece was prepared and the dispersion state was judged by a scanning electron microscope (SEM). Although the vinyl polymer was dispersed, aggregates were observed in 2/3 or less of the fibers (score 2). Moreover, as a result of measuring a combustion rate, it was 91 mm / min and was (circle).

Comparative Example 5
As shown in Table 8, a flame retardant aid (vinyl chloride polymer latex composition) was obtained in the same manner as in Comparative Example 1 except that the vinyl chloride polymer latex obtained in Comparative Production Example 5 was used. (Average particle diameter: 0.09 μm). Table 8 shows the average particle size, production stability, state after production, storage stability, and coating film stability of the obtained flame retardant aid (vinyl chloride polymer latex composition). Some bubbling occurred during the reaction. Although the coating stability of the obtained flame retardant aid (vinyl chloride polymer latex composition) was good, slight precipitation was observed (storage stability).

  Using the obtained flame retardant aid (vinyl chloride polymer latex composition), a test piece was prepared and the dispersion state was judged by a scanning electron microscope (SEM). Although the vinyl polymer was dispersed, aggregates were observed in 2/3 or less of the fibers (score 2). Moreover, as a result of measuring a combustion rate, it was 134 mm / min and was x.

Comparative Example 6
As shown in Table 9, a flame retardant aid (vinyl chloride polymer latex composition) was obtained in the same manner as in Comparative Example 1 except that the vinyl chloride polymer latex obtained in Comparative Production Example 6 was used. (Average particle diameter: 0.33 μm). Table 9 shows the average particle size, production stability, state after production, storage stability, and coating film stability of the obtained flame retardant aid (vinyl chloride polymer latex composition). There was much foaming during the reaction, scale was generated, and there were many precipitates. The obtained flame retardant aid (vinyl chloride polymer latex composition) was inferior in coating film stability, and a large amount of sediment was generated (storage stability).

得られた難燃助剤（塩化ビニル系重合体ラテックス組成物）を使用して試験片を作製し、走査型電子顕微鏡（ＳＥＭ）で分散状態を判定したところ、繊維全体に凝集した塩化ビニル系重合体が見られた（点数１）。また、燃焼速度を測定した結果、８９ｍｍ／ｍｉｎであり、○であった。

A test piece was prepared using the obtained flame retardant aid (vinyl chloride polymer latex composition), and the dispersion state was judged by a scanning electron microscope (SEM). A polymer was found (1 point). Moreover, as a result of measuring a combustion rate, it was 89 mm / min and it was (circle).

Comparative Example 7
As shown in Table 9, a flame retardant aid (vinyl chloride) was prepared in the same manner as in Comparative Example 1, except that the vinyl chloride polymer latex obtained in Production Example 1 was used and butyl acrylate was changed to methyl methacrylate. System polymer latex composition) was obtained (average particle size: 0.09 μm). Table 9 shows the average particle size, production stability, state after production, storage stability, and coating film stability of the obtained flame retardant aid (vinyl chloride polymer latex composition). The foaming property during the reaction was good, but there were many precipitates. The film stability of the obtained flame retardant aid (vinyl chloride polymer latex composition) was inferior to that of the Examples, and a large amount of precipitate was observed (storage stability).

  A test piece was prepared using the obtained flame retardant aid (vinyl chloride polymer latex composition), and the dispersion state was judged by a scanning electron microscope (SEM). A polymer was found (1 point). Moreover, as a result of measuring a combustion rate, it was 154 mm / min and was x.

Comparative Example 8
As shown in Table 9, a flame retardant aid (vinyl chloride polymer latex composition) was obtained in the same manner as in Comparative Example 1 except that the vinyl chloride polymer latex obtained in Comparative Production Example 7 was used. (Average particle diameter: 0.09 μm). Table 9 shows the average particle size, production stability, state after production, storage stability, and coating film stability of the obtained flame retardant aid (vinyl chloride polymer latex composition). The foaming property during the reaction was good, but there were many precipitates. The resulting flame retardant aid (vinyl chloride polymer latex composition) was inferior in coating film stability, and a large amount of sediment was generated (storage stability).

  A test piece was prepared using the obtained flame retardant aid (vinyl chloride polymer latex composition), and the dispersion state was judged by a scanning electron microscope (SEM). A polymer was found (1 point). Moreover, as a result of measuring a combustion rate, it was 85 mm / min and was (circle).

Comparative Example 9
As shown in Table 9, a flame retardant aid (vinyl chloride polymer latex composition) was obtained in the same manner as in Comparative Example 1 except that the vinyl chloride polymer latex obtained in Comparative Production Example 8 was used. (Average particle diameter: 0.12 μm). Table 9 shows the average particle size, production stability, state after production, storage stability, and coating film stability of the obtained flame retardant aid (vinyl chloride polymer latex composition). The foaming property during the reaction was good, but there were many precipitates. The obtained flame retardant aid (vinyl chloride polymer latex composition) was inferior in coating film stability, and a large amount of sediment was generated (storage stability).

  A test piece was prepared using the obtained flame retardant aid (vinyl chloride polymer latex composition), and the dispersion state was judged by a scanning electron microscope (SEM). A polymer was found (1 point). Moreover, as a result of measuring a combustion rate, it was 79 mm / min and was (circle).

Comparative Example 10
As shown in Table 10, using the vinyl chloride polymer latex obtained in Production Example 1, the same procedure as in Comparative Example 1 was conducted except that the amount of butyl acrylate was changed. Polymer latex composition) was obtained (average particle size: 0.13 μm). Table 10 shows the average particle size, production stability, state after production, storage stability, and coating film stability of the obtained flame retardant aid (vinyl chloride polymer latex composition). The production stability during the reaction was good. Although the coating stability of the obtained flame retardant aid (vinyl chloride polymer latex composition) was good, slight precipitation was observed (storage stability).

得られた難燃助剤（塩化ビニル系重合体ラテックス組成物）を使用して試験片を作製し、走査型電子顕微鏡（ＳＥＭ）で分散状態を判定したところ、繊維の１／２以上に塩化ビニル系重合体が分散しているが繊維の１／２以下は凝集物が見られた（点数３）。また、燃焼速度を測定した結果、１３９ｍｍ／ｍｉｎであり、×であった。

Using the obtained flame retardant aid (vinyl chloride polymer latex composition), a test piece was prepared and the dispersion state was judged by a scanning electron microscope (SEM). Although vinyl-based polymer was dispersed, aggregates were found in 1/2 or less of the fibers (score 3). Moreover, as a result of measuring a combustion rate, it was 139 mm / min and was x.

Comparative Example 11
As shown in Table 10, using the vinyl chloride polymer latex obtained in Production Example 1, the same procedure as in Comparative Example 1 was conducted except that the amount of butyl acrylate was changed. Polymer latex composition) was obtained (average particle size: 0.08 μm). Table 10 shows the average particle size, production stability, state after production, storage stability, and coating film stability of the obtained flame retardant aid (vinyl chloride polymer latex composition). The obtained flame retardant aid (vinyl chloride polymer latex composition) had good coating film stability and no precipitate was generated (storage stability).

  Using the obtained flame retardant aid (vinyl chloride polymer latex composition), a test piece was prepared and the dispersion state was judged by a scanning electron microscope (SEM). Although vinyl-based polymer was dispersed, aggregates were found in 1/2 or less of the fibers (score 3). Moreover, as a result of measuring a combustion rate, it was 94 mm / min and was (circle).

Comparative Example 12
As shown in Table 10, using the vinyl chloride polymer latex obtained in Production Example 1, the same procedure as in Comparative Example 1 was conducted except that the amount of sodium lauryl sulfate was changed. Polymer latex composition) was obtained (average particle size: 0.09 μm). Table 10 shows the average particle size, production stability, state after production, storage stability, and coating film stability of the obtained flame retardant aid (vinyl chloride polymer latex composition). There was much foaming during the reaction. Although the coating stability of the obtained flame retardant aid (vinyl chloride polymer latex composition) was good, slight precipitation was observed (storage stability).

  A test piece was prepared using the obtained flame retardant aid (vinyl chloride polymer latex composition), and the dispersion state was judged by a scanning electron microscope (SEM). A polymer was found (1 point). Moreover, as a result of measuring a combustion rate, it was 145 mm / min and was x.

  The flame retardant aid of the present invention has a possibility that a fiber composite obtained using the same will be widely used as a material for flame retardant clothing.

Claims (5)

A vinyl chloride polymer having a core part and a shell part that forms an outer layer of the core part, wherein the core part has an average particle size of 0.12 μm or less and an average degree of polymerization of 400 to 2000; At least one repeating unit represented by the following general formulas (1), (2), (3), (4), (5) and (6) with respect to 100 parts by weight of the vinyl chloride polymer. 1 to 300 parts by weight of a polymer having a unit, and 1.0 to 5.0 parts by weight of an organic compound having a sulfonate or a sulfate ester salt and a higher fatty acid salt with respect to 100 parts by weight of the vinyl chloride polymer 0.05 to 2.5 parts by weight, and 10 parts by weight or less of an emulsifier with respect to 100 parts by weight of the vinyl chloride polymer, and the average particle size of the vinyl chloride polymer is 0.30 μm or less. Is a vinyl chloride polymer A flame retardant aid comprising a tex composition.

(In the formula, R ₁ represents an alkyl group having 2 to 8 carbon atoms, and R ₂ represents hydrogen or a methyl group.)

(In the formula, R ₃ represents an alkylene group having 1 to ₄ carbon atoms, R ₄ represents an alkyl group or alkoxylalkyl group having 1 to ₄ carbon atoms, or hydrogen, and R ₅ represents hydrogen or a methyl group.)

(In the formula, R ₆ represents a methyl group or an ethyl group.)

(Wherein R ₇ represents hydrogen or a methyl group.)

(In the formula, R ₈ represents hydrogen or a methyl group.)

(In the formula, R ₉ represents hydrogen or a methyl group.) The vinyl chloride polymer latex composition comprises 1.0 to 5.0 parts by weight of an organic compound having a sulfonate or sulfate ester salt and 0.05 to 2 parts of a higher fatty acid salt with respect to 100 parts by weight of the vinyl chloride polymer. 100 parts by weight of a vinyl chloride polymer in the latex in the presence of a vinyl chloride polymer latex having an average particle size of 0.12 μm or less and an average degree of polymerization of 400 to 2000. In contrast, the monomer represented by the following general formulas (7), (8), (9), (10) and (11), and at least one monomer selected from methacrylic acid and acrylic acid The flame retardant aid according to claim 1, wherein the flame retardant aid is obtained by adding 1 to 300 parts by weight of a body and 10 parts by weight or less of an emulsifier and polymerizing the mixture.

(In the formula, R ₉ represents an alkyl group having 2 to 8 carbon atoms, and R ₁₀ represents hydrogen or a methyl group.)

(In the formula, R ₁₁ represents an alkylene group having 1 to 4 carbon atoms, R ₁₂ represents an alkyl group or alkoxylalkyl group having 1 to 4 carbon atoms, or hydrogen, and R ₁₃ represents hydrogen or a methyl group.)

(In the formula, R ₁₄ represents a methyl group or an ethyl group.)

(In the formula, R ₁₅ represents hydrogen or a methyl group.)

(In the formula, R ₁₆ represents hydrogen or a methyl group.) The organic compound having a sulfonate or sulfate ester salt is a potassium salt, sodium salt, ammonium salt, or triethanolamine salt of sulfonic acid or sulfate ester. Flame retardant aid. The flame retardant aid according to any one of claims 1 to 3, wherein the higher fatty acid salt is a potassium salt, sodium salt, ammonium salt, or triethanolamine salt of a higher fatty acid. A fiber composite comprising the flame retardant aid according to any one of claims 1 to 4 attached to a fiber.