JPWO2005111283A1 - Polyvinyl chloride fiber, method for producing the same, and artificial hair - Google Patents
Polyvinyl chloride fiber, method for producing the same, and artificial hair Download PDFInfo
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- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
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- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
- D01F6/48—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polymers of halogenated hydrocarbons
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Abstract
ポリ塩化ビニル樹脂１００質量部とマレイミド共重合体１〜２０質量部とを有する樹脂組成物から構成されているポリ塩化ビニル繊維とする。前記マレイミド共重合体は、好ましくは、芳香族ビニル単量体１５〜７０質量部と不飽和ジカルボン酸イミド誘導体３０〜８５質量部とを共重合させて得たマレイミド共重合体であが、ここで用いられる芳香族ビニル単量体は、好ましくは、スチレンであり、不飽和ジカルボン酸イミド誘導体は、好ましくは、Ｎ−フェニルマレイミドであり、そして、不飽和ジカルボン酸無水物は、好ましくは、無水マレイン酸である。このようなポリ塩化ビニル繊維は、好ましくは、人工毛髪とされる。Let it be the polyvinyl chloride fiber comprised from the resin composition which has 100 mass parts of polyvinyl chloride resins, and 1-20 mass parts of maleimide copolymers. The maleimide copolymer is preferably a maleimide copolymer obtained by copolymerizing 15 to 70 parts by mass of an aromatic vinyl monomer and 30 to 85 parts by mass of an unsaturated dicarboxylic imide derivative. The aromatic vinyl monomer used in is preferably styrene, the unsaturated dicarboxylic imide derivative is preferably N-phenylmaleimide, and the unsaturated dicarboxylic acid anhydride is preferably anhydrous. Maleic acid. Such polyvinyl chloride fibers are preferably artificial hair.
Description
本発明は、ウィッグ、ヘアピース、ブレード、エクステンションヘアー等の頭髪装飾用の人工毛髪、防虫網、及び、ブラシにおいて用いられるポリ塩化ビニル繊維及びその製造方法に関するものである。 The present invention relates to polyvinyl chloride fibers used in artificial hair for hair decoration such as wigs, hairpieces, blades, extension hairs, insect screens, and brushes, and a method for producing the same.
本発明者らは、ポリ塩化ビニル系樹脂１００質量部と、塩素含有率５７．０〜６２．０％且つ平均重合度５５０〜７５０の塩素化ポリ塩化ビニル樹脂５〜２０重量部と、塩素含有率６５．０〜６７．０％且つ平均重合度５５０〜７５０の塩素化ポリ塩化ビニル樹脂５〜３０重量部を有する樹脂組成物からなるポリ塩化ビニル繊維（特許文献１を参照。）を提案した。
しかし、前記ポリ塩化ビニル繊維の製造においては、耐熱性を発現させるために添加する二種の塩素化ポリ塩化ビニル樹脂の添加量が多くなると、前記樹脂組成物の溶融粘度が高くなって、紡糸性が低下するという問題があった。 However, in the production of the polyvinyl chloride fiber, if the amount of the two kinds of chlorinated polyvinyl chloride resins to be added in order to develop heat resistance increases, the melt viscosity of the resin composition increases, and spinning is performed. There was a problem that the performance decreased.
本発明は、かかる問題を解決することを目的としている。 The present invention aims to solve this problem.
即ち、本発明は、溶融紡糸時における紡糸性を良好に維持しつつ、１００℃以上の熱を加えて二次加工処理を施しても熱収縮が少ないポリ塩化ビニル繊維及びその製造方法を提供することを目的としている。 That is, the present invention provides a polyvinyl chloride fiber and a method for producing the same that maintain good spinnability at the time of melt spinning and have little heat shrinkage even when subjected to secondary processing by applying heat of 100 ° C. or higher. The purpose is that.
請求項１に記載された発明は、ポリ塩化ビニル樹脂１００質量部とマレイミド共重合体１〜２０質量部とを有する樹脂組成物から構成されていることを特徴とするポリ塩化ビニル繊維である。 The invention described in claim 1 is a polyvinyl chloride fiber comprising a resin composition having 100 parts by mass of a polyvinyl chloride resin and 1 to 20 parts by mass of a maleimide copolymer.
請求項２に記載された発明は、請求項１に記載された発明において、前記マレイミド共重合体が、芳香族ビニル単量体１５〜７０質量部と不飽和ジカルボン酸イミド誘導体３０〜８５質量部とを共重合させて得たマレイミド共重合体であることを特徴とするものである。 The invention described in claim 2 is the invention described in claim 1, wherein the maleimide copolymer comprises 15 to 70 parts by mass of an aromatic vinyl monomer and 30 to 85 parts by mass of an unsaturated dicarboxylic imide derivative. Is a maleimide copolymer obtained by copolymerization of
請求項３に記載された発明は、請求項１に記載された発明において、前記マレイミド共重合体が、芳香族ビニル単量体１５〜７０質量部と、不飽和ジカルボン酸イミド誘導体３０〜８５質量部と、不飽和ジカルボン酸無水物０．１〜２５質量部と、これらの単量体と共重合可能なこれらの単量体以外のビニル単量体０．１〜４０質量部とを共重合させて得たマレイミド共重合体であることを特徴とするものである。 The invention described in claim 3 is the invention described in claim 1, wherein the maleimide copolymer comprises 15 to 70 parts by mass of an aromatic vinyl monomer and 30 to 85 parts by mass of an unsaturated dicarboxylic imide derivative. Copolymer, 0.1 to 25 parts by weight of unsaturated dicarboxylic acid anhydride, and 0.1 to 40 parts by weight of vinyl monomer other than these monomers copolymerizable with these monomers It is the maleimide copolymer obtained by making it carry out.
請求項４に記載された発明は、請求項２又は３に記載された発明において、前記芳香族ビニル単量体が、スチレンであるであることを特徴とするものである。 The invention described in claim 4 is the invention described in claim 2 or 3, characterized in that the aromatic vinyl monomer is styrene.
請求項５に記載された発明は、請求項２〜４のいずれか１項に記載された発明において、前記不飽和ジカルボン酸イミド誘導体が、Ｎ−フェニルマレイミドであることを特徴とするものである。 The invention described in claim 5 is the invention described in any one of claims 2 to 4, wherein the unsaturated dicarboxylic acid imide derivative is N-phenylmaleimide. .
請求項６に記載された発明は、請求項３〜５のいずれか１項に記載された発明において、前記不飽和ジカルボン酸無水物が、無水マレイン酸であることを特徴とするものである。 The invention described in claim 6 is the invention described in any one of claims 3 to 5, characterized in that the unsaturated dicarboxylic acid anhydride is maleic anhydride.
請求項７に記載された発明は、請求項１〜６のいずれか１項に記載された発明において、前記マレイミド共重合体の質量平均分子量が、６００００〜１４００００であることを特徴とするものである。 The invention described in claim 7 is the invention described in any one of claims 1 to 6, wherein the maleimide copolymer has a mass average molecular weight of 60,000 to 140,000. is there.
請求項８に記載された発明は、ポリ塩化ビニル樹脂１００質量部と、マレイミド共重合体１〜２０質量部と、ビニル共重合体１〜３０質量部とを有する樹脂組成物から構成されているポリ塩化ビニル繊維において、該ビニル共重合体が、芳香族ビニル単量体４０〜９０質量部とシアン化ビニル単量体１０〜６０質量部とを共重合させて得たビニル共重合体であることを特徴とするポリ塩化ビニル繊維である。 The invention described in claim 8 is composed of a resin composition having 100 parts by mass of a polyvinyl chloride resin, 1 to 20 parts by mass of a maleimide copolymer, and 1 to 30 parts by mass of a vinyl copolymer. In the polyvinyl chloride fiber, the vinyl copolymer is a vinyl copolymer obtained by copolymerizing 40 to 90 parts by mass of an aromatic vinyl monomer and 10 to 60 parts by mass of a vinyl cyanide monomer. It is a polyvinyl chloride fiber characterized by this.
請求項９に記載された発明は、請求項８に記載された発明において、前記ビニル共重合体が、芳香族ビニル単量体４０〜９０質量部と、シアン化ビニル単量体１０〜６０質量部と、これらの単量体と共重合可能なこれらの単量体以外のビニル単量体０．１〜４０質量部とを共重合させて得たビニル共重合体であることを特徴とするものである。 The invention described in claim 9 is the invention described in claim 8, wherein the vinyl copolymer is composed of 40 to 90 parts by mass of an aromatic vinyl monomer and 10 to 60 parts by mass of a vinyl cyanide monomer. Part and a vinyl copolymer obtained by copolymerizing 0.1 to 40 parts by weight of a vinyl monomer other than these monomers copolymerizable with these monomers Is.
請求項１０に記載された発明は、請求項８又は９に記載された発明において、前記芳香族ビニル単量体が、スチレンであることを特徴とするものである。 The invention described in claim 10 is the invention described in claim 8 or 9, characterized in that the aromatic vinyl monomer is styrene.
請求項１１に記載された発明は、請求項８〜１０のいずれかに記載された発明において、前記シアン化ビニル単量体が、アクリロニトリルであることを特徴とするものである。 The invention described in claim 11 is the invention described in any one of claims 8 to 10, wherein the vinyl cyanide monomer is acrylonitrile.
請求項１２に記載された発明は、請求項８〜１１のいずれかに記載された発明において、前記ビニル共重合体が、スチレン７５〜９０質量部とアクリロニトリル１０〜２５質量部とを共重合させて得たビニル共重合体であることを特徴とするものである。 The invention described in claim 12 is the invention described in any of claims 8 to 11, wherein the vinyl copolymer is obtained by copolymerizing 75 to 90 parts by mass of styrene and 10 to 25 parts by mass of acrylonitrile. It is a vinyl copolymer obtained by the above.
請求項１３に記載された発明は、請求項８〜１２のいずれかに記載された発明において、前記ビニル共重合体の質量平均分子量が、５００００〜１１００００であることを特徴とするものである。 The invention described in claim 13 is the invention described in any one of claims 8 to 12, wherein the vinyl copolymer has a mass average molecular weight of 50,000 to 110,000.
請求項１４に記載された発明は、ポリ塩化ビニル樹脂１００質量部とマレイミド共重合体１〜２０質量部とを有してなる樹脂組成物を溶融紡糸することを特徴とするものである。 The invention described in claim 14 is characterized in that a resin composition comprising 100 parts by mass of a polyvinyl chloride resin and 1 to 20 parts by mass of a maleimide copolymer is melt-spun.
請求項１５に記載された発明は、請求項１〜１３のいずれか記載のポリ塩化ビニル繊維で構成されていることを特徴とする人工毛髪である。 The invention described in claim 15 is an artificial hair comprising the polyvinyl chloride fiber according to any one of claims 1 to 13.
請求項１〜７，１４に記載された発明によれば、ポリ塩化ビニル繊維がポリ塩化ビニル樹脂１００質量部とマレイミド共重合体１〜２０質量部とを有する樹脂組成物から構成されているので、その溶融紡糸時における紡糸性を良好に維持しつつ、１００℃以上の熱を加えて二次加工処理を施しても熱収縮が少ないポリ塩化ビニル繊維とすることができる。 According to the invention described in claims 1 to 7, 14, the polyvinyl chloride fiber is composed of a resin composition having 100 parts by mass of polyvinyl chloride resin and 1 to 20 parts by mass of maleimide copolymer. Further, it is possible to obtain a polyvinyl chloride fiber having little heat shrinkage even when a secondary processing treatment is performed by applying heat at 100 ° C. or higher while maintaining the spinnability at the time of melt spinning.
請求項８〜１３に記載された発明によれば、ポリ塩化ビニル樹脂１００質量部と、マレイミド共重合体１〜２０質量部と、ビニル共重合体１〜３０質量部とを有する樹脂組成物から構成されているポリ塩化ビニル繊維において、該ビニル共重合体が、芳香族ビニル単量体４０〜９０質量部とシアン化ビニル単量体１０〜６０質量部とを共重合させて得たビニル共重合体であるので、前記ポリ塩化ビニル樹脂とマレイミド共重合体とビニル共重合体との相溶性がさらに向上してガラス転位温度が下がり、そのために、流動性が向上し、よって、押出安定性、即ち、紡糸性が向上して、溶融紡糸時における紡糸性を維持しつつ、１００℃以上の熱を加えて二次加工処理を施しても熱収縮が少ないポリ塩化ビニル繊維とすることができる。 According to the invention described in claims 8 to 13, from a resin composition having 100 parts by mass of a polyvinyl chloride resin, 1 to 20 parts by mass of a maleimide copolymer, and 1 to 30 parts by mass of a vinyl copolymer. In the constituted polyvinyl chloride fiber, the vinyl copolymer is a vinyl copolymer obtained by copolymerizing 40 to 90 parts by mass of an aromatic vinyl monomer and 10 to 60 parts by mass of a vinyl cyanide monomer. Since it is a polymer, the compatibility of the polyvinyl chloride resin, the maleimide copolymer and the vinyl copolymer is further improved and the glass transition temperature is lowered, thereby improving the fluidity and thus the extrusion stability. That is, it is possible to obtain a polyvinyl chloride fiber with improved heat-spinning properties and low heat shrinkage even when subjected to secondary processing by applying heat at 100 ° C. or higher while maintaining spinnability during melt spinning. .
請求項８〜１３に記載された発明によれば、請求項１〜１３のいずれか記載のポリ塩化ビニル繊維で構成されているので、１００℃以上の熱を加えて二次加工処理を施しても熱収縮の少ない人工毛髪とすることができる。 According to the invention described in claims 8 to 13, since it is constituted by the polyvinyl chloride fiber according to any one of claims 1 to 13, a secondary processing treatment is performed by applying heat of 100 ° C or higher. Can be made into artificial hair with less heat shrinkage.
本発明のポリ塩化ビニル繊維は、ポリ塩化ビニル樹脂１００質量部とマレイミド共重合体１〜２０質量部とを有する樹脂組成物からなる。このよに、ポリ塩化ビニル繊維がポリ塩化ビニル樹脂１００質量部とマレイミド共重合体１〜２０質量部とを有する樹脂組成物からなっていると、溶融紡糸時における紡糸性を維持しつつ、１００℃以上の熱を加えて二次加工処理を施しても熱収縮が少ないポリ塩化ビニル繊維とすることができる。 The polyvinyl chloride fiber of this invention consists of a resin composition which has 100 mass parts of polyvinyl chloride resins, and 1-20 mass parts of maleimide copolymers. Thus, when the polyvinyl chloride fiber is made of a resin composition having 100 parts by mass of a polyvinyl chloride resin and 1 to 20 parts by mass of a maleimide copolymer, the spinnability at the time of melt spinning is maintained. Even if heat treatment at a temperature of 0 ° C. or higher is applied to carry out a secondary processing treatment, a polyvinyl chloride fiber with little heat shrinkage can be obtained.
本発明におけるポリ塩化ビニル樹脂は、塩化ビニル単独重合体、塩素化塩化ビニル重合体、塩化ビニルと塩化ビニル以外の他のモノマーとの共重合体、又は、これらを２種以上混合したものである。前記「塩化ビニル以外の他のモノマー」は、例えば、エチレン、プロピレン、アルキルビニルエーテル、ビニリデンクロライド、酢酸ビニル、アクリル酸エステル、及び、マレイン酸エステルがあるが、本発明の目的に反しないかぎり、これら以外のモノマーであってもかまわない。本発明におけるポリ塩化ビニル樹脂の平均重合度は、好ましくは、６００〜１３００である。平均重合度が６００未満であると、溶融粘度が低下して紡糸性が悪くなることとなり、また、平均重合度が１３００を越えると、溶融粘度が上昇するので、紡糸温度を高くする必要があり、そのために、塩化ビニル繊維に着色が発生することとなる。 The polyvinyl chloride resin in the present invention is a vinyl chloride homopolymer, a chlorinated vinyl chloride polymer, a copolymer of vinyl chloride and another monomer other than vinyl chloride, or a mixture of two or more thereof. . Examples of the “monomer other than vinyl chloride” include, for example, ethylene, propylene, alkyl vinyl ether, vinylidene chloride, vinyl acetate, acrylic acid ester, and maleic acid ester. Other monomers may be used. The average degree of polymerization of the polyvinyl chloride resin in the present invention is preferably 600 to 1300. When the average degree of polymerization is less than 600, the melt viscosity is lowered and the spinnability is deteriorated. When the average degree of polymerization is more than 1300, the melt viscosity is increased, so it is necessary to increase the spinning temperature. For this reason, the vinyl chloride fiber is colored.
本発明におけるマレイミド共重合体は、溶融紡糸時における紡糸性を維持しつつ、１００℃以上の熱を加えて二次加工処理を施しても熱収縮が少ないポリ塩化ビニル繊維とするために、ポリ塩化ビニル樹脂に配合されるが、そのポリ塩化ビニル樹脂１００質量部に対するマレイミド共重合体の配合量は、好ましくは、１〜２０質量部であり、さらに好ましくは、３〜１５質量部である。マレイミド共重合体は、その配合量が１質量部未満であると、ポリ塩化ビニル繊維の熱収縮を低下させることができなくなり、また、その配合量が２０質量部を越えると、紡糸性が悪くなることとなる。 The maleimide copolymer according to the present invention is a poly (vinyl chloride) fiber that maintains the spinnability during melt spinning and is made into a polyvinyl chloride fiber that has low heat shrinkage even when subjected to secondary processing by applying heat of 100 ° C. or higher. Although it mix | blends with a vinyl chloride resin, the compounding quantity of the maleimide copolymer with respect to 100 mass parts of the polyvinyl chloride resin becomes like this. Preferably it is 1-20 mass parts, More preferably, it is 3-15 mass parts. If the blending amount of the maleimide copolymer is less than 1 part by mass, the thermal shrinkage of the polyvinyl chloride fiber cannot be reduced, and if the blending amount exceeds 20 parts by weight, the spinnability is poor. Will be.
前記マレイミド共重合体は、好ましくは、芳香族ビニル単量体１５〜７０質量部と不飽和ジカルボン酸イミド誘導体３０〜８５質量部とを共重合させて得たマレイミド共重合体である。前記マレイミド共重合体は、その不飽和ジカルボン酸イミド誘導体が３０質量部未満であると、塩化ビニル樹脂との溶融混合時において相溶性が低下するので、押出安定性が悪くなり、また、その不飽和ジカルボン酸イミド誘導体が８５質量部を越えると、ポリ塩化ビニル繊維の熱収縮を低下させることができなくなる。よって、本発明のように、マレイミド共重合体が芳香族ビニル単量体１５〜７０質量部と不飽和ジカルボン酸イミド誘導体３０〜８５質量部とを共重合させて得たマレイミド共重合体であると、前記ポリ塩化ビニル樹脂とマレイミド共重合体との相溶性をさらに向上し、しかも、耐熱性効果が向上し、それらのために、溶融紡糸時における紡糸性を維持しつつ、１００℃以上の熱を加えて二次加工処理を施しても熱収縮が少ないポリ塩化ビニル繊維とすることができる。 The maleimide copolymer is preferably a maleimide copolymer obtained by copolymerizing 15 to 70 parts by mass of an aromatic vinyl monomer and 30 to 85 parts by mass of an unsaturated dicarboxylic imide derivative. If the unsaturated dicarboxylic imide derivative is less than 30 parts by mass, the maleimide copolymer has poor compatibility during melt-mixing with the vinyl chloride resin, resulting in poor extrusion stability. When the saturated dicarboxylic acid imide derivative exceeds 85 parts by mass, the thermal shrinkage of the polyvinyl chloride fiber cannot be reduced. Therefore, as in the present invention, the maleimide copolymer is a maleimide copolymer obtained by copolymerizing 15 to 70 parts by mass of an aromatic vinyl monomer and 30 to 85 parts by mass of an unsaturated dicarboxylic imide derivative. And the compatibility between the polyvinyl chloride resin and the maleimide copolymer is further improved, and the heat resistance effect is improved. For these reasons, while maintaining the spinnability at the time of melt spinning, the temperature is 100 ° C. or higher. Even if heat treatment is applied to perform secondary processing, a polyvinyl chloride fiber with little heat shrinkage can be obtained.
本発明における前記マレイミド共重合体は、さらに好ましくは、芳香族ビニル単量体１５〜７０質量部と、不飽和ジカルボン酸イミド誘導体３０〜８５質量部と、不飽和ジカルボン酸無水物０．１〜２５質量部と、これらの単量体と共重合可能なこれらの単量体以外のビニル単量体０．１〜４０質量部とを共重合させて得たマレイミド共重合体である。前記不飽和ジカルボン酸無水物は、その添加量が０．１質量部未満でであると、前記ポリ塩化ビニル樹脂とマレイミド共重合体との相溶性が低下するので、押出安定性を維持できなくなり、また、その添加量が２５質量部を越えると、耐熱付与効果をさらに向上させることができなくなる。よって、本発明のように、ビニル共重合体に前記「これらの単量体と共重合可能なこれらの単量体以外のビニル単量体０．１〜４０質量部」を重合含有させると、耐熱付与効果を維持しながら前記ポリ塩化ビニル樹脂とマレイミド共重合体との相溶性をさらに向上させることができるので、溶融紡糸時における紡糸性を維持しつつ、１００℃以上の熱を加えて二次加工処理を施しても熱収縮が少ないポリ塩化ビニル繊維とすることができる。 The maleimide copolymer in the present invention is more preferably 15 to 70 parts by weight of an aromatic vinyl monomer, 30 to 85 parts by weight of an unsaturated dicarboxylic imide derivative, and 0.1 to 10 parts of an unsaturated dicarboxylic acid anhydride. It is a maleimide copolymer obtained by copolymerizing 25 parts by mass and 0.1 to 40 parts by mass of vinyl monomers other than these monomers copolymerizable with these monomers. If the amount of the unsaturated dicarboxylic acid anhydride is less than 0.1 parts by mass, the compatibility between the polyvinyl chloride resin and the maleimide copolymer is lowered, and thus the extrusion stability cannot be maintained. Moreover, when the addition amount exceeds 25 parts by mass, the heat resistance imparting effect cannot be further improved. Therefore, as in the present invention, when the vinyl copolymer is polymerized to contain the above "0.1 to 40 parts by mass of a vinyl monomer other than these monomers copolymerizable with these monomers", Since the compatibility between the polyvinyl chloride resin and the maleimide copolymer can be further improved while maintaining the heat resistance imparting effect, heat at 100 ° C. or higher can be applied while maintaining spinnability during melt spinning. Even if the next processing is applied, the polyvinyl chloride fiber can be obtained with little heat shrinkage.
本発明における芳香族ビニル単量体は、スチレン、α−メチルスチレン、ビニルトルエン、エチルスチレン、ｔ−ブチルスチレン、クロロスチレン、ジクロロスチレン、及び、その置換体から選ばれる芳香族ビニル単量体であが、好ましくは、反応によって増える分子量の数値制御が容易となるスチレンである。また、本発明における芳香族ビニル単量体は、本発明の目的に反しないかぎり、ここ挙げた芳香族ビニル単量体以外の芳香族ビニル単量体であってもかまわない。 The aromatic vinyl monomer in the present invention is an aromatic vinyl monomer selected from styrene, α-methylstyrene, vinyltoluene, ethylstyrene, t-butylstyrene, chlorostyrene, dichlorostyrene, and substituted products thereof. However, it is preferably styrene that facilitates numerical control of the molecular weight that is increased by the reaction. Further, the aromatic vinyl monomer in the present invention may be an aromatic vinyl monomer other than the aromatic vinyl monomers listed here unless it is contrary to the object of the present invention.
本発明における不飽和ジカルボン酸イミド誘導体は、マレイミド、Ｎ−メチルマレイミド、Ｎーエチルマレイミド、及び、Ｎ−シクロヘキシルマレイミドＮ−フェニルマレイミドから選ばれる芳香族ビニル単量体であるが、好ましくは、耐熱性の高いＮ−フェニルマレイミドである。また、本発明における不飽和ジカルボン酸イミド誘導体は、本発明の目的に反しないかぎり、ここ挙げた不飽和ジカルボン酸イミド誘導体以外の不飽和ジカルボン酸イミド誘導体であってもかまわない。 The unsaturated dicarboxylic acid imide derivative in the present invention is an aromatic vinyl monomer selected from maleimide, N-methylmaleimide, N-ethylmaleimide, and N-cyclohexylmaleimide N-phenylmaleimide. It is highly N-phenylmaleimide. Further, the unsaturated dicarboxylic imide derivative in the present invention may be an unsaturated dicarboxylic imide derivative other than the unsaturated dicarboxylic imide derivatives listed here as long as it does not contradict the purpose of the present invention.
本発明における不飽和ジカルボン酸無水物は、マレイン酸、イコタン酸、シトラコン酸、及び、アコニット酸から選ばれる不飽和ジカルボン酸無水物であるが、好ましくは、反応によって増える分子量の数値制御が容易となるマレイン酸無水物である。また、本発明における不飽和ジカルボン酸無水物は、本発明の目的に反しないかぎり、ここ挙げた不飽和ジカルボン酸無水物以外の不飽和ジカルボン酸無水物であってもかまわない。 The unsaturated dicarboxylic acid anhydride in the present invention is an unsaturated dicarboxylic acid anhydride selected from maleic acid, itonic acid, citraconic acid, and aconitic acid. Preferably, the numerical control of the molecular weight increased by the reaction is easy. Is maleic anhydride. In addition, the unsaturated dicarboxylic acid anhydride in the present invention may be an unsaturated dicarboxylic acid anhydride other than the unsaturated dicarboxylic acid anhydrides mentioned here as long as the object of the present invention is not violated.
本発明におけるビニル単量体は、例えば、アクリロニトリル、メタクリロニトリル、クロロアクリロニトニル等のシアン化ビニル、メチルアクリレート、エチルアクリレート、ブチルアクリレート等のアクリル酸エステル、メチルメタクリレート、エチルメタクリレート等のメタクリル酸エステル、アクリル酸、及び、メタクリル酸等のビニルカルボン酸である。 The vinyl monomer in the present invention is, for example, vinyl cyanide such as acrylonitrile, methacrylonitrile, chloroacrylonitrile, acrylic acid esters such as methyl acrylate, ethyl acrylate, butyl acrylate, methacrylic acid such as methyl methacrylate, ethyl methacrylate, etc. Vinyl carboxylic acids such as esters, acrylic acid, and methacrylic acid.
そして、本発明におけるマレイミド共重合体の質量平均分子量は、好ましくは、６００００〜１４００００であるが、さらに好ましくは、８００００〜１２００００である。マレイミド共重合体の重量平均分子量が６００００未満又は１４００００を越えると、ポリ塩化ビニルとの相溶性が低下するので、紡糸性が悪くなる。 And the mass average molecular weight of the maleimide copolymer in the present invention is preferably 60000 to 140000, more preferably 80000 to 120,000. If the weight average molecular weight of the maleimide copolymer is less than 60,000 or more than 140000, the compatibility with polyvinyl chloride is lowered, so that the spinnability is deteriorated.
また、本発明のポリ塩化ビニル繊維は、ポリ塩化ビニル樹脂１００質量部と、マレイミド共重合体１〜２０質量部と、ビニル共重合体１〜３０質量部とを有する樹脂組成物から構成されており、そして、そのビニル共重合体は、芳香族ビニル単量体４０〜９０質量部とシアン化ビニル単量体１０〜６０質量部とを共重合させて得たビニル共重合体からなる。このように、ポリ塩化ビニル樹脂１００質量部と、マレイミド共重合体１〜２０質量部と、ビニル共重合体１〜３０質量部とを有する樹脂組成物から構成されているポリ塩化ビニル繊維において、該ビニル共重合体が、芳香族ビニル単量体４０〜９０質量部とシアン化ビニル単量体１０〜６０質量部とを共重合させて得たビニル共重合体であると、前記ポリ塩化ビニル樹脂とマレイミド共重合体とビニル共重合体との相溶性がさらに向上してガラス転位温度が下がり、そのために、流動性が向上し、よって、押出安定性、即ち、紡糸性が向上するので、溶融紡糸時における紡糸性を維持しつつ、１００℃以上の熱を加えて二次加工処理を施しても熱収縮が少ないポリ塩化ビニル繊維とすることができる。 Moreover, the polyvinyl chloride fiber of this invention is comprised from the resin composition which has 100 mass parts of polyvinyl chloride resins, 1-20 mass parts of maleimide copolymers, and 1-30 mass parts of vinyl copolymers. The vinyl copolymer comprises a vinyl copolymer obtained by copolymerizing 40 to 90 parts by mass of an aromatic vinyl monomer and 10 to 60 parts by mass of a vinyl cyanide monomer. Thus, in the polyvinyl chloride fiber comprised from the resin composition which has 100 mass parts of polyvinyl chloride resins, 1-20 mass parts of maleimide copolymers, and 1-30 mass parts of vinyl copolymers, When the vinyl copolymer is a vinyl copolymer obtained by copolymerizing 40 to 90 parts by mass of an aromatic vinyl monomer and 10 to 60 parts by mass of a vinyl cyanide monomer, the polyvinyl chloride Since the compatibility of the resin, maleimide copolymer and vinyl copolymer is further improved and the glass transition temperature is lowered, thereby improving the fluidity, and thus improving the extrusion stability, that is, the spinnability. While maintaining the spinning property at the time of melt spinning, it is possible to obtain a polyvinyl chloride fiber with little heat shrinkage even when a secondary processing treatment is performed by applying heat of 100 ° C. or higher.
前記ビニル共重合体の含有量は、好ましくは、１〜３０質量部であるが、さらに好ましくは、５〜２５質量部である。前記ビニル共重合体の含有量が１質量部未満又は３０質量部を越えると紡糸性が悪くなる。 The content of the vinyl copolymer is preferably 1 to 30 parts by mass, and more preferably 5 to 25 parts by mass. If the content of the vinyl copolymer is less than 1 part by mass or exceeds 30 parts by mass, the spinnability is deteriorated.
本発明におけるビニル共重合体は、好ましくは、芳香族ビニル単量体４０〜９０質量部と、シアン化ビニル単量体１０〜６０質量部と、これらの単量体と共重合可能なこれらの単量体以外のビニル単量体０．１〜４０質量部とを共重合させて得たビニル共重合体である。このように、ビニル共重合体に前記「これらの単量体と共重合可能なこれらの単量体以外のビニル単量体０．１〜４０質量部」を重合含有させると、耐熱付与効果を維持しながら前記ポリ塩化ビニル樹脂とマレイミド共重合体との相溶性をさらに向上させることができるので、溶融紡糸時における紡糸性を維持しつつ、１００℃以上の熱を加えて二次加工処理を施しても熱収縮が少ないポリ塩化ビニル繊維とすることができる。 The vinyl copolymer in the present invention is preferably 40 to 90 parts by mass of an aromatic vinyl monomer, 10 to 60 parts by mass of a vinyl cyanide monomer, and those copolymerizable with these monomers. It is a vinyl copolymer obtained by copolymerizing 0.1 to 40 parts by mass of a vinyl monomer other than the monomer. Thus, when the vinyl copolymer is polymerized to contain the above "0.1 to 40 parts by weight of a vinyl monomer other than these monomers copolymerizable with these monomers", the effect of imparting heat resistance is obtained. The compatibility between the polyvinyl chloride resin and the maleimide copolymer can be further improved while maintaining the temperature, and the secondary processing is performed by applying heat of 100 ° C. or higher while maintaining the spinnability at the time of melt spinning. Even if applied, a polyvinyl chloride fiber with little heat shrinkage can be obtained.
前記芳香族ビニル単量体は、例えば、スチレン、α−メチルスチレン、ビニルトルエン、エチルスチレン、ｔ−ブチルスチレン、クロロスチレン、ジクロロスチレン及びその置換体から選ばれる芳香族ビニル単量体であが、好ましくは、スチレンである。前記スチレンは、紡糸時の樹脂圧の調整が容易であること、スクリュー負荷を下げることができること、長時間のロングラン性を確保することができること、等の利点を有している。また、前記芳香族ビニル単量体は、本発明の目的に反しないかぎり、ここ挙げた芳香族ビニル単量体以外の芳香族ビニル単量体であってもかまわない。 The aromatic vinyl monomer is, for example, an aromatic vinyl monomer selected from styrene, α-methylstyrene, vinyltoluene, ethylstyrene, t-butylstyrene, chlorostyrene, dichlorostyrene, and substituted products thereof. Styrene is preferred. The styrene has advantages such as easy adjustment of the resin pressure at the time of spinning, the ability to reduce the screw load, and long long run properties. Further, the aromatic vinyl monomer may be an aromatic vinyl monomer other than the aromatic vinyl monomers listed here unless it is contrary to the object of the present invention.
前記シアン化ビニル単量体は、例えば、アクリロニトリル、メタクリロニトリル、クロロアクリロニトリルら選ばれるシアン化ビニル単量体であが、好ましくは、アクリロニトリルである。前記アクリロニトリルは、紡糸時の樹脂圧の調整が容易であること、スクリュー負荷を下げることができること、長時間のロングラン性を確保することができること、等の利点を有している。 The vinyl cyanide monomer is, for example, a vinyl cyanide monomer selected from acrylonitrile, methacrylonitrile, chloroacrylonitrile, and is preferably acrylonitrile. The acrylonitrile has advantages such as easy adjustment of the resin pressure at the time of spinning, the ability to reduce the screw load, and long long run properties.
前記ビニル単量体は、例えば、メチルアクリレート、エチルアクリレート、ブチルアクリレートのアクリル酸エステル、メチルメタクリレート、エチルメタクリレートのメタクリル酸エステル、アクリル酸、及び、メタクリル酸から選ばれるビニルカルボン酸である。 The vinyl monomer is, for example, vinyl carboxylic acid selected from methyl acrylate, ethyl acrylate, butyl acrylate acrylic ester, methyl methacrylate, ethyl methacrylate methacrylic ester, acrylic acid, and methacrylic acid.
前記ビニル共重合体は、好ましくは、スチレン７５〜９０質量部とアクリロニトリル１０〜２５質量部とを共重合させて得たビニル共重合体である。このように、前記ビニル共重合体に「アクリロニトリル１０〜２５質量部」を重合含有させると、紡糸性が良好となる。 The vinyl copolymer is preferably a vinyl copolymer obtained by copolymerizing 75 to 90 parts by mass of styrene and 10 to 25 parts by mass of acrylonitrile. Thus, when “10-25 parts by mass of acrylonitrile” is polymerized and contained in the vinyl copolymer, the spinnability is improved.
そして、前記ビニル共重合体の質量平均分子量は、好ましくは、５００００〜１１００００、さらに好ましくは、６００００〜１０００００である。このように、前記ビニル共重合体の質量平均分子量が５００００〜１１００００であると、塩化ビニル重合体とマレイミド共重合体との相溶性がさらに向上する。 And the mass mean molecular weight of the said vinyl copolymer becomes like this. Preferably, it is 50000-110,000, More preferably, it is 60000-100000. Thus, the compatibility of a vinyl chloride polymer and a maleimide copolymer further improves that the weight average molecular weight of the said vinyl copolymer is 50000-110,000.
本発明のポリ塩化ビニル繊維は、塩化ビニル樹脂１００質量部とマレイミド共重合体１〜２０質量部とを有してなる樹脂組成物を溶融紡糸することにより製造されるが、具体的には、（Ａ）塩化ビニル樹脂１００質量部とマレイミド共重合体１〜２０質量部とを有してなる樹脂組成物をヘンシェルミキサー、リボンブレンダー等の混合機で混合する工程、（Ｂ）前記混合した樹脂組成物を単軸押出機、異方向二軸押出機、コニカル二軸押出機等の溶融押出機で溶融紡糸して繊維とする工程、（Ｃ）前記溶融紡糸した繊維を延伸する工程、そして、（Ｄ）前記延伸した繊維に熱弛緩処理を施す工程、を順次経て製造される。本発明のポリ塩化ビニル繊維の製造においては、本発明の目的に反しない限り、塩化ビニル樹脂組成物に使用可能な公知の添加剤を配合することができる。これらの添加剤は、例えば、滑剤、熱安定剤、加工助剤、強化剤、紫外線吸収剤、酸化防止剤、帯電防止剤、充填剤、難燃剤、顔料、初期着色改善剤、導電性付与剤、表面処理剤、光安定剤、及び、香料である。 The polyvinyl chloride fiber of the present invention is produced by melt spinning a resin composition comprising 100 parts by mass of a vinyl chloride resin and 1 to 20 parts by mass of a maleimide copolymer. Specifically, (A) A step of mixing a resin composition comprising 100 parts by mass of a vinyl chloride resin and 1 to 20 parts by mass of a maleimide copolymer with a mixer such as a Henschel mixer or a ribbon blender, (B) the mixed resin A step of melt spinning the composition into a fiber by a melt extruder such as a single screw extruder, a different direction twin screw extruder, a conical twin screw extruder, and the like (C) a step of drawing the melt-spun fiber; and (D) It is manufactured through the steps of subjecting the drawn fibers to a thermal relaxation treatment. In the production of the polyvinyl chloride fiber of the present invention, known additives that can be used in the vinyl chloride resin composition can be blended as long as the object of the present invention is not adversely affected. These additives include, for example, lubricants, heat stabilizers, processing aids, reinforcing agents, ultraviolet absorbers, antioxidants, antistatic agents, fillers, flame retardants, pigments, initial color improvers, and conductivity imparting agents. , Surface treatment agents, light stabilizers, and perfumes.
本発明の人工毛髪は、請求項１〜１３のいずれか記載のポリ塩化ビニル繊維で構成される。このように、本発明の人工毛髪は、請求項１〜１３のいずれか記載のポリ塩化ビニル繊維で構成されているので、１００℃以上の熱を加えて二次加工処理を施しても熱収縮が少ないものとなる。 The artificial hair of this invention is comprised with the polyvinyl chloride fiber in any one of Claims 1-13. Thus, since the artificial hair of this invention is comprised with the polyvinyl chloride fiber in any one of Claims 1-13, even if it heats 100 degreeC or more and performs a secondary processing process, it is heat-shrinkable Will be less.
（実施例１）
（ａ）ポリ塩化ビニル樹脂（大洋塩ビ株式会社製、ＴＨ−１０００）１００質量部、マレイミド共重合体（電気化学工業株式会社製、ＡＸ−４０（参考例１を参照。））１０質量部、ハイドロタルサイト熱安定剤及びＣａ−Ｚｎ金属石鹸熱安定剤にポリエチレンワックス及び特殊脂肪酸エステルの滑剤をパック化して得た複合安定剤・滑剤（日産化学工業株式会社製、ＣＰ−４１０Ａ）８質量部、並びに、亜リン酸エステル熱安定剤（旭電化工業株式会社製、アデカスタブ１５００）１質量部を有してなる樹脂組成物をヘンシェルミキサーで混合する工程、（ｂ）前記混合した樹脂組成物をノズル断面積０．０６ｍｍ2 、孔数１２０、及び、金型温度１８０℃の紡糸金型から押出量１０Ｋｇ／時間で溶融紡糸して１５０デシテックスの繊維とする工程、（ｃ）前記溶融紡糸した繊維を１００℃の空気雰囲気下で３００％に延伸して５０デシテックスの繊維とする工程、そして、（ｄ）前記延伸した繊維に１２０℃の空気雰囲気下で繊維全長が処理前の７５％の長さに収縮するまで熱弛緩処理を施す工程、を順次経て平均繊度６６．７デシテックスのポリ塩化ビニル繊維を得た。(Example 1)
(A) 100 parts by mass of a polyvinyl chloride resin (manufactured by Taiyo PVC Co., Ltd., TH-1000), 10 parts by mass of a maleimide copolymer (manufactured by Denki Kagaku Kogyo Co., Ltd., AX-40 (see Reference Example 1)), 8 parts by mass of a composite stabilizer / lubricant (CP-410A, manufactured by Nissan Chemical Industries, Ltd.) obtained by packing a hydrotalcite heat stabilizer and a Ca-Zn metal soap heat stabilizer with polyethylene wax and a special fatty acid ester lubricant And a step of mixing a resin composition comprising 1 part by mass of a phosphite ester heat stabilizer (Asahi Denka Kogyo Co., Ltd., ADK STAB 1500) with a Henschel mixer, (b) the mixed resin composition nozzle cross-sectional area 0.06 mm 2, number of pores 120, and the fibers in the extrusion amount 10 Kg / time from a spinning die mold temperature 180 ° C. melt spinning to 150 dtex (C) stretching the melt-spun fiber to 300% in an air atmosphere at 100 ° C. to make a 50 dtex fiber; and (d) applying the stretched fiber to an air atmosphere at 120 ° C. A step of performing a thermal relaxation treatment until the total length of the fiber contracted to 75% of the length before the treatment was successively obtained to obtain a polyvinyl chloride fiber having an average fineness of 66.7 dtex.
（参考例１）
スチレン１０．０ｋｇ、メチルエチルケトン１５．０ｋｇ、及び、α−メチルスチレンダイマー１４ｇを攪拌機付きのオートクレーブに仕込み、オートクレーブの内部を窒素ガスで置換した後、オートクレーブの内部の温度を８０℃に昇温し、この状態に維持したオートクレーブ中に無水マレイン酸６．２ｋｇとベンゾイルパーオキサイド４０ｇとをメチルエチルケトン９．０ｋｇに溶解した溶液を８時間かけて連続的に添加し、続いて、オートクレーブの温度を８０℃とした状態で３時間保持してマレイミド共重合溶液を得た。そして、このマレイミド共重合溶液にアニリン５．８ｋｇ、及び、トリエチルアミン０．１ｋｇを加えて１４０℃で７時間反応させた後、この反応液をベント付き二軸押出機に供給し、そこで脱気して平均分子量１０００００のマレイミド共重合体とした。(Reference Example 1)
10.0 kg of styrene, 15.0 kg of methyl ethyl ketone, and 14 g of α-methylstyrene dimer were charged into an autoclave equipped with a stirrer, the inside of the autoclave was replaced with nitrogen gas, and then the temperature inside the autoclave was raised to 80 ° C. A solution prepared by dissolving 6.2 kg of maleic anhydride and 40 g of benzoyl peroxide in 9.0 kg of methyl ethyl ketone was continuously added to the autoclave maintained in this state over 8 hours, and then the temperature of the autoclave was set to 80 ° C. This state was maintained for 3 hours to obtain a maleimide copolymer solution. Then, 5.8 kg of aniline and 0.1 kg of triethylamine were added to the maleimide copolymer solution and reacted at 140 ° C. for 7 hours, and then the reaction solution was supplied to a vented twin screw extruder where it was deaerated. Thus, a maleimide copolymer having an average molecular weight of 100,000 was obtained.
（実施例２）
実施例１の（ａ）工程における樹脂組成物にアクリロニトリル割合３０質量％のビニル共重合体（参考例２を参照。）２０質量部をさらに添加した以外は、実施例１と同様にしてポリ塩化ビニル繊維を得た。(Example 2)
Polychlorination was carried out in the same manner as in Example 1 except that 20 parts by mass of a vinyl copolymer having an acrylonitrile ratio of 30% by mass (see Reference Example 2) was further added to the resin composition in the step (a) of Example 1. A vinyl fiber was obtained.
（参考例２）
純水５０ｋｇ、過硫酸カリウム８３ｇ、第三リン酸カルシウム４００ｇ、ｔ−ドデシルメルカプタン４００ｇ、スチレン４０ｋｇ、アクリロニトニル１６ｋｇ及びベンゾイルパーオキサイド１０５ｇを攪拌機付きオートクレーブに仕込み、オートクレーブの内部を窒素ガスで置換した後、オートクレーブの内部の温度を１００℃に昇温してオートクレーブ中にスチレン５．３ｋｇを２時間かけて添加し、続いて、オートクレーブの内部の温度を１０３℃に昇温してオートクレーブ中にスチレン８ｋｇを３時間かけて添加した。そして、オートクレーブの内部の温度を１１０℃に昇温し、この状態で１時間重合させた後、オートクレーブの内部の温度を１２０℃に昇温し、この状態で１時間重合させせて重合を完了させた。この重合を完了させた重合液を冷却し、ここに塩酸を加えて中和した後、この中和した重合液を脱水、乾燥して平均分子量８００００のビニル重合体を得た。(Reference Example 2)
50 kg of pure water, 83 g of potassium persulfate, 400 g of tricalcium phosphate, 400 g of t-dodecyl mercaptan, 40 kg of styrene, 16 kg of acrylonitrile and 105 g of benzoyl peroxide were charged into an autoclave with a stirrer, and the inside of the autoclave was replaced with nitrogen gas. The internal temperature was raised to 100 ° C., and 5.3 kg of styrene was added to the autoclave over 2 hours. Subsequently, the internal temperature of the autoclave was increased to 103 ° C. and 8 kg of styrene was added to the autoclave for 3 hours. Added over time. Then, the temperature inside the autoclave is raised to 110 ° C. and polymerized in this state for 1 hour, and then the temperature inside the autoclave is raised to 120 ° C. and polymerized in this state for 1 hour to complete the polymerization. I let you. The polymer solution after completion of the polymerization was cooled and neutralized by adding hydrochloric acid thereto, and then the neutralized polymer solution was dehydrated and dried to obtain a vinyl polymer having an average molecular weight of 80000.
（実施例３）
ビニル共重合体中のアクリロニトリル量を１５質量部（即ち、参考例２のにおけるアクリロニトニル量を９．４ｋｇ）にしてアクリロニトリル割合が１５質量％のビニル共重合体とした以外は、実施例２と同様にしてポリ塩化ビニル繊維を得た。(Example 3)
Example 2 except that the amount of acrylonitrile in the vinyl copolymer was 15 parts by mass (that is, the amount of acrylonitrile in Reference Example 2 was 9.4 kg) and the vinyl copolymer had an acrylonitrile ratio of 15% by mass. Thus, a polyvinyl chloride fiber was obtained.
（比較例１）
実施例１の（ａ）工程の樹脂組成物におけるマレイミド共重合体の配合量を０．５質量部とした以外は、実施例１と同様にしてポリ塩化ビニル繊維を得た。(Comparative Example 1)
A polyvinyl chloride fiber was obtained in the same manner as in Example 1 except that the blending amount of the maleimide copolymer in the resin composition in the step (a) of Example 1 was 0.5 part by mass.
（比較例２）
実施例１の（ａ）工程の樹脂組成物におけるマレイミド共重合体の配合量を３０質量部とした以外は、実施例１と同様にしてポリ塩化ビニル繊維を得た。(Comparative Example 2)
A polyvinyl chloride fiber was obtained in the same manner as in Example 1, except that the blending amount of the maleimide copolymer in the resin composition in the step (a) of Example 1 was 30 parts by mass.
（比較例３）
実施例１の（ａ）工程の樹脂組成物におけるマレイミド共重合体の重量平均分子量を４００００とした以外は、実施例１と同様にしてポリ塩化ビニル繊維を得た。(Comparative Example 3)
A polyvinyl chloride fiber was obtained in the same manner as in Example 1 except that the weight-average molecular weight of the maleimide copolymer in the resin composition in the step (a) of Example 1 was 40000.
（比較例４）
実施例１の（ａ）工程の樹脂組成物におけるマレイミド共重合体の重量平均分子量を１６００００とした以外は、実施例１と同様にしてポリ塩化ビニル繊維を得た。(Comparative Example 4)
A polyvinyl chloride fiber was obtained in the same manner as in Example 1 except that the weight average molecular weight of the maleimide copolymer in the resin composition in the step (a) of Example 1 was changed to 160000.
（比較例５）
アクリロニトリル割合２０質量％のビニル共重合体の配合量を６０質量部とした以外は、実施例２と同様にしてポリ塩化ビニル繊維を得た。(Comparative Example 5)
A polyvinyl chloride fiber was obtained in the same manner as in Example 2 except that the amount of the vinyl copolymer having an acrylonitrile ratio of 20% by mass was changed to 60 parts by mass.
（比較例６）
ビニル共重合体のアクリロニトリル割合を５質量％とした以外は、実施例３と同様にしてポリ塩化ビニル繊維を得た。(Comparative Example 6)
A polyvinyl chloride fiber was obtained in the same manner as in Example 3 except that the acrylonitrile ratio of the vinyl copolymer was changed to 5% by mass.
（比較例７）
ビニル共重合体のアクリロニトリル割合を４０質量％とした以外は、実施例３と同様にしてポリ塩化ビニル繊維を得た。(Comparative Example 7)
A polyvinyl chloride fiber was obtained in the same manner as in Example 3 except that the acrylonitrile ratio of the vinyl copolymer was 40% by mass.
（比較例８）
ビニル共重合体の重量平均分子量を３００００とした以外は、実施例３と同様にしてポリ塩化ビニル繊維を得た。(Comparative Example 8)
A polyvinyl chloride fiber was obtained in the same manner as in Example 3 except that the weight average molecular weight of the vinyl copolymer was 30000.
（比較例９）
ビニル共重合体の重量平均分子量を１３００００とした以外は、実施例３と同様にしてポリ塩化ビニル繊維を得た。(Comparative Example 9)
A polyvinyl chloride fiber was obtained in the same manner as in Example 3 except that the weight average molecular weight of the vinyl copolymer was 130000.
以上、実施例１〜３及び比較例１〜９で得たポリ塩化ビニル繊維を次の方法で評価した。 As described above, the polyvinyl chloride fibers obtained in Examples 1 to 3 and Comparative Examples 1 to 9 were evaluated by the following methods.
（１）熱収縮性
熱収縮性は、試験体を熱処理した際に発生する熱収縮率を測定して評価した。即ち、前記熱収縮率は、長さ１００ｍｍに調整したポリ塩化ビニル繊維の試験体１２本を１００℃のギアオーブン中で１５分間放置し、その放置前後における試験体の長さの比（（放置前の長さ−放置後の長さ）／放置前の長さ）を算出したものであって、１２本のうち、最大値、最小値を排除した中間値１０本の平均値を算出して得たものである。(1) Heat-shrinkability Heat-shrinkability was evaluated by measuring the heat shrinkage rate generated when the specimen was heat-treated. That is, the heat shrinkage ratio was determined by leaving 12 test pieces of polyvinyl chloride fiber adjusted to a length of 100 mm in a gear oven at 100 ° C. for 15 minutes, and the ratio of the test sample length before and after the test ((Leave The previous length−the length after being left) / the length before being left) was calculated, and the average value of 10 intermediate values excluding the maximum value and the minimum value was calculated out of 12 pieces. It is obtained.
評価基準は、
○：熱収縮率が５％未満のもの
×：が熱収縮率が５％以上もの
とした。Evaluation criteria are
○: Heat shrinkage rate of less than 5% ×: Heat shrinkage rate of 5% or more.
（２）紡糸性
紡糸性は、樹脂組成物を溶融紡糸する際の紡糸性により評価した。即ち、前記紡糸性の試験は、紡糸金型から同時に１２０本の繊維状体を９０分間（測定時間３０分間×測定回数３回）押出成形した際の糸切れ（溶融押出中に、数本の繊維状体が途切れる現象）発生回数を測定することにより行った。(2) Spinnability Spinnability was evaluated by the spinnability when melt spinning the resin composition. That is, the spinnability test was performed by cutting 120 filaments simultaneously from a spinning die for 90 minutes (measurement time 30 minutes × measurement number 3 times). The phenomenon in which the fibrous body was interrupted) was performed by measuring the number of occurrences.
評価基準は、
○：糸切れ発生回数０回
△：糸切れ発生回数１回
×：糸切れが２回以上発生
とした。Evaluation criteria are
○: Number of occurrences of yarn breakage 0 times Δ: Number of occurrences of yarn breakage 1 time ×: Thread breakage occurred 2 times or more.
（３）ロングラン安定性
ロングラン安定性は、連続紡糸した際に長時間(２４時間以上)安定した状態で紡糸を行える目安を押出機の樹脂圧によって評価した。(3) Long run stability The long run stability was evaluated based on the resin pressure of the extruder as a guideline for spinning in a stable state for a long time (24 hours or more) when continuously spinning.
評価基準は、
○：押出機の樹脂圧が３０ＭＰａ以下
△：押出機の樹脂圧が３０〜４０ＭＰａ
×：押出機の樹脂圧が４０ＭＰａ以上
とした。Evaluation criteria are
○: Resin pressure of the extruder is 30 MPa or less Δ: Resin pressure of the extruder is 30 to 40 MPa
X: The resin pressure of the extruder was 40 MPa or more.
評価結果は、次の表１に示される。 The evaluation results are shown in the following Table 1.
本発明のポリ塩化ビニル繊維は、人工毛髪、防虫網、ブラシ等において用いられるが、好適には、頭髪装飾用の人工毛髪、又は、ドールヘアー用の人工毛髪として用いられる。 The polyvinyl chloride fiber of the present invention is used in artificial hair, insect repellent nets, brushes, and the like, but is preferably used as artificial hair for hair decoration or artificial hair for doll hair.
本発明の人工毛髪は、例えば、これを束ね、整えることによって、かつら、ヘアピース、ブレード、エクステンションヘアー、アクセサリーヘアーとされる。 The artificial hair of the present invention is made into a wig, a hair piece, a blade, an extension hair, and an accessory hair, for example, by bundling and arranging the artificial hair.
Claims (15)
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|---|---|---|---|
| PCT/JP2004/006627 WO2005111283A1 (en) | 2004-05-17 | 2004-05-17 | Polyvinyl chloride fiber, process for producing the same, and artificial hair |
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| US20230263253A1 (en) * | 2019-11-07 | 2023-08-24 | Denka Company Limited | Fibers for artificial hair and headdress product |
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS512109B1 (en) * | 1971-03-29 | 1976-01-23 | ||
| JPS61181853A (en) * | 1985-02-06 | 1986-08-14 | Shin Etsu Chem Co Ltd | Heat-resistant vinyl chloride resin composition |
| JPH03182536A (en) * | 1989-12-12 | 1991-08-08 | Nippon Shokubai Kagaku Kogyo Co Ltd | Vinyl chloride resin composition |
| JPH04122759A (en) * | 1990-09-14 | 1992-04-23 | Sekisui Chem Co Ltd | Vinyl chloride resin composition |
| JPH11209424A (en) * | 1998-01-28 | 1999-08-03 | Tokuyama Sekisui Ind Corp | Chlorinated vinyl chloride resin |
| JP2000154293A (en) * | 1998-11-20 | 2000-06-06 | Kanegafuchi Chem Ind Co Ltd | Resin composition for polyvinyl chloride fiber and fiber made of that |
| JP2000328355A (en) * | 1999-05-20 | 2000-11-28 | Kanegafuchi Chem Ind Co Ltd | Vinyl chloride-based fiber and its production |
| JP3804954B2 (en) * | 2003-01-20 | 2006-08-02 | 電気化学工業株式会社 | Polyvinyl chloride fiber |
-
2004
- 2004-05-17 JP JP2006513475A patent/JP4496214B2/en not_active Expired - Lifetime
- 2004-05-17 WO PCT/JP2004/006627 patent/WO2005111283A1/en active Application Filing
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS512109B1 (en) * | 1971-03-29 | 1976-01-23 | ||
| JPS61181853A (en) * | 1985-02-06 | 1986-08-14 | Shin Etsu Chem Co Ltd | Heat-resistant vinyl chloride resin composition |
| JPH03182536A (en) * | 1989-12-12 | 1991-08-08 | Nippon Shokubai Kagaku Kogyo Co Ltd | Vinyl chloride resin composition |
| JPH04122759A (en) * | 1990-09-14 | 1992-04-23 | Sekisui Chem Co Ltd | Vinyl chloride resin composition |
| JPH11209424A (en) * | 1998-01-28 | 1999-08-03 | Tokuyama Sekisui Ind Corp | Chlorinated vinyl chloride resin |
| JP2000154293A (en) * | 1998-11-20 | 2000-06-06 | Kanegafuchi Chem Ind Co Ltd | Resin composition for polyvinyl chloride fiber and fiber made of that |
| JP2000328355A (en) * | 1999-05-20 | 2000-11-28 | Kanegafuchi Chem Ind Co Ltd | Vinyl chloride-based fiber and its production |
| JP3804954B2 (en) * | 2003-01-20 | 2006-08-02 | 電気化学工業株式会社 | Polyvinyl chloride fiber |
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