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WO2023277034A1 - Copolymer emulsion, thermoplastic resin emulsion, composition for fiber binding, resin-impregnated fiber using same, thermoplastic resin composition and molded article - Google Patents

Copolymer emulsion, thermoplastic resin emulsion, composition for fiber binding, resin-impregnated fiber using same, thermoplastic resin composition and molded article Download PDF

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Publication number
WO2023277034A1
WO2023277034A1 PCT/JP2022/025818 JP2022025818W WO2023277034A1 WO 2023277034 A1 WO2023277034 A1 WO 2023277034A1 JP 2022025818 W JP2022025818 W JP 2022025818W WO 2023277034 A1 WO2023277034 A1 WO 2023277034A1
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Prior art keywords
fiber
thermoplastic resin
composition
weight
emulsion
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
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PCT/JP2022/025818
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French (fr)
Japanese (ja)
Inventor
和代 藤田
雅典 伊藤
雛乃 田村
皇雄 三崎
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Nippon A&L Inc
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Nippon A&L Inc
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Publication of WO2023277034A1 publication Critical patent/WO2023277034A1/en
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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
    • B29C70/06—Fibrous reinforcements only
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
    • B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
    • B32B5/28—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer impregnated with or embedded in a plastic substance
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/04—Acids; Metal salts or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F257/00—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00
    • C08F257/02—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00 on to polymers of styrene or alkyl-substituted styrenes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/06—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/08—Ingredients agglomerated by treatment with a binding agent
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C08L101/06—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing oxygen atoms
    • C08L101/08—Carboxyl groups
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/58—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives
    • D04H1/587—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives characterised by the bonding agents used
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/227—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of hydrocarbons, or reaction products thereof, e.g. afterhalogenated or sulfochlorinated
    • D06M15/233—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of hydrocarbons, or reaction products thereof, e.g. afterhalogenated or sulfochlorinated aromatic, e.g. styrene
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/31—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated nitriles

Definitions

  • the present invention relates to a copolymer emulsion, a thermoplastic resin emulsion, a composition for bundling fibers, a resin-impregnated fiber bundled with the composition for bundling, and the It relates to a thermoplastic resin composition and a molded product using.
  • Fiber materials typified by carbon fiber, have excellent characteristics such as high strength, high elasticity, and electrical conductivity. It is widely used in various industrial fields such as machinery and sporting goods.
  • the fibers are bundled to form fiber strands, which are then compounded with the thermoplastic resin by methods such as kneading and coating.
  • the bundling process integrates hundreds to tens of thousands of independent fibers with a bundling agent to form a strand, and is an essential process for the subsequent process of combining with thermoplastic resin.
  • This sizing agent not only imparts abrasion resistance to the strands and affects workability in the composite process, but also wettability and adhesiveness between the essentially incompatible fibers and the thermoplastic resin matrix. etc., and is important because it greatly affects the performance and quality of the final fiber-containing thermoplastic resin composite material.
  • Patent Document 1 discloses a method for improving the strength of a composite material by attaching an aqueous emulsion containing a copolymerized nylon resin as a main component to a fiber bundle to improve the adhesiveness between the fiber bundle and the matrix resin.
  • Patent Document 2 discloses a method of treating with a styrene emulsion having a specific amount of carboxyl groups.
  • Patent Document 3 a continuous reinforcing fiber sheet made of carbon fiber or the like and a resin sheet made of a thermoplastic resin are alternately laminated, and a heat press treatment (heating and pressurizing treatment) is performed to continuously strengthen the sheet.
  • a fiber-reinforced composite material is disclosed in which interstices between fibers are impregnated with a thermoplastic resin.
  • Patent Document 4 proposes a fiber-reinforced composite material formed by laminating sheet-like prepregs impregnated with a thermoplastic resin in the gaps between continuous reinforcing fibers made of carbon fibers or the like. Reinforced composite materials are produced by laminating prepregs, which have been cut into predetermined shapes (lengths) in advance, with the reinforcing fibers of the prepregs oriented in a predetermined direction, and are adhered (melted and bonded) by a hot press. It is disclosed that a fiber-reinforced composite material having excellent productivity and high performance can be obtained.
  • the present invention 1 solves the above first problem and includes the following [1] and [2].
  • [1] In the production of a fiber-reinforced thermoplastic resin composite material in which a resin-impregnated fiber and a thermoplastic resin are combined, it is blended in a fiber bundling composition for bundling a plurality of fibers to produce the resin-impregnated fiber.
  • a copolymer emulsion comprising 40 to 98.5% by weight of an aromatic vinyl monomer and 1.5 to 60% by weight of another monomer copolymerizable with the aromatic vinyl monomer. and wherein the copolymer has a number average molecular weight of 0.5 ⁇ 10 4 to 4 ⁇ 10 4 .
  • a fiber bundling composition comprising the copolymer emulsion of [1].
  • the present invention 2 solves the above second problem, and includes the following [3] to [5].
  • a fiber bundling composition containing a thermoplastic resin emulsion and having a surface tension of 25 to 45 mN/m as measured by the ring method at 30° C. when the solid content is 30%.
  • the thermoplastic resin emulsion contains 0.1 to 20% by weight of an ethylenically unsaturated carboxylic acid monomer and 80 to 80% of another monomer copolymerizable with the ethylenically unsaturated carboxylic acid monomer.
  • the composition for fiber bundling according to [3] characterized by containing a copolymer with 99.9% by weight.
  • Invention 3 solves the first problem described above and includes the following [6] and [7].
  • a fiber bundling composition containing a thermoplastic resin emulsion and at least one of an acetylene glycol-based nonionic surfactant and a dialkylsulfosuccinate-based anionic surfactant, and having a dynamic surface tension of 25 to A composition for fiber bundling, characterized in that it is 55 mN/m.
  • the thermoplastic resin emulsion contains 40 to 98.5% by weight of an aromatic vinyl monomer and 1.5 to 60% by weight of another monomer copolymerizable with the aromatic vinyl monomer. % of the fiber bundling composition of [6].
  • the present invention 4 solves the above first problem and includes the following [8] and [9].
  • [8] In the production of a fiber-reinforced thermoplastic resin composite material in which a resin-impregnated fiber and a thermoplastic resin are combined, it is blended in a fiber bundling composition for bundling a plurality of fibers to produce the resin-impregnated fiber.
  • a thermoplastic resin emulsion comprising 40 to 98.5% by weight of an aromatic vinyl monomer and 1.5 to 60% by weight of another monomer copolymerizable with the aromatic vinyl monomer.
  • a thermoplastic resin emulsion comprising a copolymer of (1) and having an average particle size of 70 nm or more and 150 nm or less.
  • a fiber bundling composition comprising the thermoplastic resin emulsion of [8].
  • the present invention 5 is to solve the above third problem, and includes the following [10] to [13].
  • a fiber bundling composition containing a thermoplastic resin emulsion and having a pH of 4 to 7.
  • the thermoplastic resin emulsion contains 0.1 to 20% by weight of an ethylenically unsaturated carboxylic acid monomer and 80 to 80% of another monomer copolymerizable with the ethylenically unsaturated carboxylic acid monomer.
  • the composition for fiber bundling according to [10] characterized by containing a copolymer with 99.9% by weight.
  • [12] Contains at least one selected from linear alkylbenzenesulfonates, polyoxyethylene alkyl ether sulfates, ⁇ -olefinsulfonates, alkanesulfonates, dialkylsulfosuccinates and alkyl sulfates [10] Or the fiber bundling composition of [11]. [13] The fiber bundling composition according to any one of [10] to [12], which contains a nonionic surfactant.
  • each of the present inventions 1 to 5 includes the following [14] to [17].
  • [14] A resin-impregnated fiber bundled with the fiber bundling composition according to any one of [2] to [7] and [9] to [13].
  • [15] A fiber-reinforced thermoplastic resin composition comprising the resin-impregnated fibers of [14] and a thermoplastic resin.
  • [16] A molded article obtained by molding the fiber-reinforced thermoplastic resin composition of [15].
  • [17] A molded article obtained by molding a laminate comprising a layer made of the resin-impregnated fiber of [14] and a thermoplastic resin layer.
  • a copolymer emulsion, a composition for fiber bundling, and a resin-impregnated fiber, a thermoplastic resin composition, and a molded product using the same can improve the flexural strength and impact resistance properties of a molded product.
  • the second aspect of the invention it is possible to provide a fiber bundling composition that is excellent in handleability and dispersibility, and a resin-impregnated fiber, a thermoplastic resin composition, and a molded product using the composition.
  • thermoplastic resin emulsion and a fiber bundling composition that can improve the bending strength of molded articles, and resin-impregnated fibers and molded articles using the same.
  • thermoplastic resin emulsion that suppresses hydrolysis of a polyester resin, and a resin-impregnated fiber, a thermoplastic resin composition, and a molded product using the same.
  • the copolymer emulsion contained in the fiber bundling composition of the present invention 1 contains a copolymer obtained by polymerizing a plurality of monomers.
  • a plurality of monomers contain an aromatic vinyl-based monomer as an essential component.
  • the aromatic vinyl-based monomer include styrene, ⁇ -methylstyrene, vinyltoluene, divinylbenzene, and the like, and one or more of these can be used. Styrene and ⁇ -methylstyrene are particularly preferred.
  • the content of the aromatic vinyl-based monomer in the total monomers must be 40 to 98.5% by weight, and if the content of the aromatic vinyl-based monomer is less than 40% by weight, The dispersibility of the obtained resin-impregnated fibers in the thermoplastic resin is lowered, and if it exceeds 98.5% by weight, the adhesiveness between the resin-impregnated fibers and the thermoplastic resin is deteriorated, which is not preferable.
  • the range is preferably 45-95% by weight, more preferably 47-90% by weight.
  • the copolymer emulsion contained in the fiber bundling composition of the present invention 1 contains another monomer copolymerizable with the aromatic vinyl monomer, and is copolymerizable with the aromatic vinyl monomer.
  • Other monomers include ethylenically unsaturated carboxylic acid monomers, vinyl cyanide monomers, alkyl ester monomers, unsaturated monomers containing hydroxyalkyl groups, and unsaturated carboxylic acid amides. monomers, vinylpyridine-based monomers, conjugated diene-based monomers, etc., and each may be used alone or in combination of two or more depending on the purpose.
  • ethylenically unsaturated carboxylic acid monomers include mono- or dicarboxylic acids (anhydrides) such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, and itaconic acid.
  • vinyl cyanide-based monomers examples include acrylonitrile, methacrylonitrile, ⁇ -chloroacrylonitrile, ⁇ -ethylacrylonitrile and the like.
  • Alkyl ester monomers include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, glycidyl methacrylate, dimethyl fumarate, diethyl fumarate, dimethyl maleate, diethyl malate, dimethyl itaconate, and monomethyl fumarate. , monoethyl fumarate, 2-ethylhexyl acrylate and the like.
  • Unsaturated monomers containing hydroxyalkyl groups include ⁇ -hydroxyethyl acrylate, ⁇ -hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, hydroxybutyl methacrylate, 3-chloro-2-hydroxypropyl Methacrylate, di-(ethylene glycol) maleate, di-(ethylene glycol) itaconate, 2-hydroxyethyl maleate, bis(2-hydroxyethyl) maleate, 2-hydroxyethyl methyl fumarate and the like.
  • unsaturated carboxylic acid amide-based monomers include acrylamide, methacrylamide, N-methylol acrylamide, N-methylol methacrylamide, and N,N-dimethylacrylamide.
  • vinylpyridine-based monomers examples include 2-vinylpyridine, 3-vinylpyridine, 4-vinylpyridine, and 2-methyl-5-vinylpyridine.
  • Conjugated diene-based monomers include 1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 2-chloro-1,3-butadiene, substituted linear Conjugated pentadienes, substituted and side chain conjugated hexadienes, and the like.
  • other monomers copolymerizable with aromatic vinyl monomers include acrylic acid, methacrylic acid, fumaric acid, itaconic acid, acrylonitrile, methacrylonitrile, methyl methacrylate, butyl acrylate, and ⁇ -hydroxyethyl. Preference is given to using acrylates, acrylamides or methacrylamides, 2-vinylpyridine, 1,3-butadiene.
  • the content of "other monomers copolymerizable with the aromatic vinyl monomer” in all monomers must be 1.5% by weight or more, and less than 1.5% by weight. If it exceeds 60% by weight, the dispersibility of the resin-impregnated fiber in the thermoplastic resin is poor, which is not preferable. It is preferably in the range of 5 to 55% by weight, more preferably 10 to 53% by weight.
  • a preferable composition ratio of each monomer is 60 to 95% by weight of aromatic vinyl monomer, 4 to 39% by weight of vinyl cyanide monomer, and 1 to 15% by weight of ethylenically unsaturated carboxylic acid monomer. %, and more preferred composition ratios are 80 to 94% by weight of aromatic vinyl monomer, 5 to 15% by weight of vinyl cyanide monomer, and 1 to 5% of ethylenically unsaturated carboxylic acid monomer. % by weight.
  • the copolymer emulsion contained in the fiber bundling composition of the present invention 1 is obtained by emulsion polymerization, and is not particularly limited as long as the object of the present invention 1 is not impaired.
  • a batch addition method, a divided addition method, a continuous addition method, a multistage polymerization method, a seed polymerization method, a power feed polymerization method, and the like may be employed.
  • the continuous addition method is preferable from the standpoint of stability during polymerization and ease of adjustment of the molecular weight.
  • n-hexylmercaptan, n-octylmercaptan, t-octylmercaptan, n-dodecylmercaptan, t-dodecylmercaptan, n - alkyl mercaptans such as stearyl mercaptan
  • xanthogen compounds such as dimethylxanthogen disulfide and diisopropyl xanthogen disulfide
  • thiuram compounds such as tetramethylthiuram disulfide, tetraethylthiuram disulfide and tetramethylthiuram monosulfide
  • Phenolic compounds such as butyl-4-methylphenol and styrenated phenol, allyl compounds such as allyl alcohol, halogenated hydrocarbon compounds such as dichlorome
  • the emulsifier used for emulsion polymerization of the copolymer emulsion contained in the fiber bundling composition of the present invention 1 is not particularly limited. Salts, aliphatic sulfonates, aliphatic carboxylates, anionic surfactants such as sulfuric acid ester salts of nonionic surfactants, or nonions such as alkyl ester types, alkylphenyl ether types, and alkyl ether types of polyethylene glycol One or more of these may be used, and it is preferable to use them in the range of 0.05 to 10 parts by weight per 100 parts by weight of the total monomers.
  • the range is preferably 0.1 to 8 parts by weight, more preferably 0.5 to 5 parts by weight.
  • electrolytes can be used during polymerization.
  • polymerization accelerators can be used during polymerization.
  • chelating agents can be used during polymerization.
  • the molecular weight of the copolymer emulsion contained in the fiber bundling composition of the present invention 1 is adjusted by changing the amount of the chain transfer agent and polymerization initiator used in the emulsion polymerization, and the polymerization time and polymerization temperature. It is also possible to The chain transfer agent is preferably used in an amount of 0.3 to 2.1 parts by weight per 100 parts by weight of all monomers. It is preferable to use the polymerization initiator in the range of 0.1 to 0.3 parts by weight with respect to 100 parts by weight of all the monomers.
  • the polymerization time and polymerization temperature are not particularly limited, and the polymerization temperature can be adjusted within a range that does not impair the object of the present invention 1, such as polymerization at a constant temperature or a method of ramping the polymerization temperature during polymerization. be.
  • the polymerization time is preferably in the range of 3 to 15 hours, and the polymerization temperature is preferably in the range of 40 to 90°C, more preferably in the range of 70 to 85°C. .
  • the glass transition temperature of the copolymer emulsion contained in the fiber bundling composition of the present invention 1 is preferably 110°C or less from the viewpoint of impregnation between fibers. Particularly preferably, it is 105° C. or less. Incidentally, the glass transition temperature can be measured by a normal DSC method.
  • the number-average molecular weight of the copolymer emulsion contained in the fiber bundling composition of the present invention 1 must be in the range of 0.5 ⁇ 10 4 to 4 ⁇ 10 4 . If the number average molecular weight is lower than 0.5 ⁇ 10 4 , the strength of the final product, which is the object of the present invention 1, is inferior, and if it exceeds 4 ⁇ 10 4 , the impregnation between fibers, which is the feature of the present invention 1, is poor. descend.
  • the range is preferably 0.6 ⁇ 10 4 to 3.5 ⁇ 10 4 , more preferably 0.8 ⁇ 10 4 to 3 ⁇ 10 4 .
  • the number average molecular weight was measured using a commercially available gel permeation chromatogram (GPC) measurement device equipped with a UV detector and a column (Agilent MIXD-B 50°C) using tetrahydrofuran (THF) as the solvent and a flow rate of 1 ml. /min, the polystyrene-equivalent molecular weight measured under the conditions of a detection wavelength of 254 nm.
  • GPC gel permeation chromatogram
  • the tetrahydrofuran-insoluble portion of the copolymer emulsion contained in the fiber bundling composition of the present invention 1 is preferably less than 10% by weight in the solid content of the copolymer emulsion from the viewpoint of impregnation between fibers. . More preferably less than 5% by weight.
  • the tetrahydrofuran-insoluble portion can be obtained as follows.
  • a film was produced by drying the copolymer emulsion adjusted to pH 8 using sodium hydroxide at 23°C for 12 hours and then drying it under reduced pressure at 23°C for 24 hours.
  • the obtained film is cut into 5 mm squares, and weighed about 1 g to be X g. After immersing this in 100 ml of tetrahydrofuran for 24 hours, it is filtered using a 300-mesh wire mesh, and then the weight of the dried tetrahydrofuran is subtracted from the weight of the wire mesh.
  • the glass transition temperature and the amount of the tetrahydrofuran-insoluble portion can be adjusted by adjusting the mixing ratio of the monomers, the type and amount of additives used during polymerization, the polymerization temperature, additives added after polymerization, and the like.
  • composition for fiber bundling of the present invention 1 contains other resin emulsions, dispersants, leveling agents, lubricants, antifoaming agents, wetting agents, preservatives, antioxidants, ultraviolet absorbers, light stabilizers, A coloring agent, an antistatic agent, a plasticizer, etc. can be mixed and used within a range that does not impair the effects of the first invention.
  • thermoplastic resin emulsions such as urethane emulsions, acrylic emulsions, vinyl acetate emulsions, vinylidene chloride emulsions, and olefin resin emulsions are used for fiber bundling in Invention 1. It is preferable from the viewpoint of the properties of the composition.
  • the content of the copolymer emulsion in the fiber bundling composition of the first invention is preferably 80% by weight or more, more preferably 90% by weight or more.
  • the content of the other resin emulsion in the fiber bundling composition is preferably 20% by weight or less, more preferably 10% by weight or less.
  • the method for impregnating fibers with the fiber bundling composition of the present invention 1 is not particularly limited, and it is possible to select one or a combination of two or more from methods such as a spray method, a coating method, and an impregnation method.
  • fibers to be impregnated with the fiber bundling composition of the present invention 1 include carbon fiber, glass fiber, boron fiber, silicon carbide fiber, metal fiber such as aluminum fiber, stainless fiber, copper fiber, nickel fiber, polyamide fiber, and polyester.
  • Organic fibers such as fibers, polyarylate fibers, polyimide fibers, and (nano)cellulose fibers can be used.
  • these fibers can be used singly or in combination of two or more.
  • carbon fiber is most preferred.
  • carbon fibers include carbon fibers coated with metal such as nickel, and there are no particular restrictions on the form thereof, and may be continuous fibers, chopped fibers, milled shapes, non-woven fabrics, etc. Any form can be selected according to the requirements.
  • the fiber bundling composition is 1 to 20 in terms of solid content. It is preferable to impregnate in the range of 99 to 80 parts by weight of fibers.
  • the method of evaporating water after impregnating the fiber with the fiber bundling composition is not particularly limited, and for example, a method using a dryer, a method of irradiating infrared rays, and a continuous method.
  • a method of passing through a dryer or the like can be employed depending on the purpose.
  • the glass transition temperature of the fiber bundling composition + 1 m or more adjusted to 60 ° C. or higher It is preferable to dry while continuously passing through a dryer having tracks at a speed of 0.5 m/min or more.
  • the resin-impregnated fiber of the present invention 1 can be melt-kneaded with a thermoplastic resin and used as a fiber-reinforced thermoplastic resin composition. Furthermore, it can also be used as a laminate laminated with a thermoplastic resin sheet or film.
  • thermoplastic resin to be combined with the resin-impregnated fiber of the present invention 1 examples include polystyrene (PS), high-impact polystyrene (HIPS), acrylonitrile-butadiene rubber-styrene copolymer (ABS), acrylonitrile-ethylene propylene rubber-styrene.
  • PS polystyrene
  • HIPS high-impact polystyrene
  • ABS acrylonitrile-butadiene rubber-styrene copolymer
  • ABS acrylonitrile-ethylene propylene rubber-styrene
  • AES acrylonitrile-acrylic rubber-styrene copolymer
  • ASA acrylonitrile-styrene copolymer
  • AS acrylonitrile-styrene copolymer
  • PC polycarbonate
  • PET polyethylene terephthalate
  • PBT polybutylene terephthalate
  • PA polymethyl methacrylate
  • TPU thermoplastic polyurethane resin
  • PES polylactic acid resin
  • PES polyether
  • the thermoplastic resin to be combined with the resin-impregnated fiber of the present invention 1 includes, for example, a light stabilizer, an antioxidant, a heat stabilizer, an ultraviolet absorber, a lubricant, a flame retardant, a flame retardant aid, a plasticizer, a pigment, and a dye.
  • a light stabilizer for example, an antioxidant, a heat stabilizer, an ultraviolet absorber, a lubricant, a flame retardant, a flame retardant aid, a plasticizer, a pigment, and a dye.
  • a light stabilizer for example, a light stabilizer, an antioxidant, a heat stabilizer, an ultraviolet absorber, a lubricant, a flame retardant, a flame retardant aid, a plasticizer, a pigment, and a dye.
  • Various additives such as can also be included.
  • the fiber-reinforced thermoplastic resin composition obtained by melt-kneading the resin-impregnated fiber of the present invention 1 and a thermoplastic resin can be, for example, injection molding, multilayer extrusion molding, film molding, sheet molding, inflation molding, press molding,
  • a molded article can be obtained by adopting a processing method according to the purpose, such as the SMC molding method and the LFT-D method. In some cases, it is also possible to interpose a step of pre-shaping.
  • a laminate obtained by laminating a layer made of the resin-impregnated fiber of the present invention 1 with a thermoplastic resin sheet or film can be molded by press molding or the like. In some cases, it is also possible to interpose a step of pre-shaping.
  • thermoplastic resin used for molding molded product.
  • the fiber bundling composition of the present invention 2 contains a thermoplastic resin emulsion.
  • thermoplastic resin emulsion contained in the fiber bundling composition of the present invention 2 is not particularly limited as long as it is an aqueous dispersion of a thermoplastic resin.
  • examples include polyester resin emulsion, polyurethane resin emulsion, vinyl acetate resin emulsion, Examples include vinylidene chloride resin emulsions, polyamide resin emulsions, aromatic vinyl resin emulsions, acrylic resin emulsions, and olefin resin emulsions.
  • thermoplastic resin emulsion is preferably a copolymer obtained by polymerizing a plurality of monomers containing an ethylenically unsaturated carboxylic acid monomer, from the viewpoint of ease of handling of bundled fibers and performance of the final product. Contains coalescence.
  • Ethylenically unsaturated carboxylic acid monomers include monocarboxylic acid monomers such as acrylic acid, methacrylic acid and crotonic acid, dicarboxylic acid monomers such as maleic acid, fumaric acid and itaconic acid, and their anhydrides. mentioned. These monomers can be used individually by 1 type or in combination of 2 or more types. The use of acrylic acid, methacrylic acid and itaconic acid is particularly preferred.
  • Other monomers copolymerizable with ethylenically unsaturated carboxylic acid monomers include aromatic vinyl monomers, vinyl cyanide monomers, alkyl ester monomers, and hydroxyalkyl group-containing monomers.
  • unsaturated monomers, unsaturated carboxylic acid amide-based monomers, vinylpyridine-based monomers, oxazoline-based monomers, and conjugated diene-based monomers It is possible to use a mixture of more than one species.
  • the aromatic vinyl-based monomers include styrene, ⁇ -methylstyrene, vinyltoluene, divinylbenzene, and the like, and one or more of these can be used.
  • vinyl cyanide-based monomers examples include acrylonitrile, methacrylonitrile, ⁇ -chloroacrylonitrile, ⁇ -ethylacrylonitrile, and the like, and one or more of these can be used.
  • Alkyl ester monomers include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, glycidyl methacrylate, dimethyl fumarate, diethyl fumarate, dimethyl maleate, diethyl malate, dimethyl itaconate, and monomethyl fumarate. , monoethyl fumarate, 2-ethylhexyl acrylate and the like, and one or more of these can be used.
  • Unsaturated monomers containing hydroxyalkyl groups include ⁇ -hydroxyethyl acrylate, ⁇ -hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, hydroxybutyl methacrylate, 3-chloro-2-hydroxypropyl methacrylate, di-(ethylene glycol) maleate, di-(ethylene glycol) itaconate, 2-hydroxyethyl maleate, bis(2-hydroxyethyl) maleate, 2-hydroxyethyl methyl fumarate and the like, one of which Or 2 or more types can be used.
  • unsaturated carboxylic acid amide-based monomers include acrylamide, methacrylamide, N-methylol acrylamide, N-methylol methacrylamide, N,N-dimethylacrylamide and the like, and one or more of these may be used. can be done.
  • Vinylpyridine-based monomers include 2-vinylpyridine, 3-vinylpyridine, 4-vinylpyridine, 2-methyl-5-vinylpyridine and the like, and one or more of these may be used. .
  • oxazoline-based monomers examples include 2-vinyl-2-oxazoline and 4,4-dimethyl-2-vinyl-2-oxazoline-5-one, and one or more of these may be used. can be done.
  • Conjugated diene monomers include 1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 2-chloro-1,3-butadiene and the like. , these can be used alone or in combination of two or more.
  • other monomers copolymerizable with ethylenically unsaturated carboxylic acid monomers include styrene, ⁇ -methylstyrene, acrylonitrile, methyl methacrylate, butyl acrylate, ⁇ -hydroxyethyl acrylate, acrylamide or methacrylamide, 2 -Vinylpyridine, 1,3-butadiene is preferred.
  • the content of the ethylenically unsaturated carboxylic acid monomer in all monomers is preferably 0.1 to 20% by weight, more preferably 0.5 to 18% by weight, and 1 to 16% by weight. More preferred. Adjustment within this range tends to provide an excellent balance between bundling properties and fiber dispersibility in the final product.
  • the preferable composition ratio of each monomer in the thermoplastic resin emulsion is 60 to 95% by weight of aromatic vinyl monomer, 4 to 39% by weight of vinyl cyanide monomer, and ethylenically unsaturated carboxylic acid monomer. 1 to 15% by weight of aromatic vinyl monomers, 5 to 15% by weight of vinyl cyanide monomers, and ethylenically unsaturated carboxylic acid monomers. from 1 to 5% by weight.
  • thermoplastic resin emulsion contained in the fiber bundling composition of the present invention 2 is obtained by emulsion polymerization
  • known emulsion polymerization methods such as batch addition method, divided addition method, continuous addition method, multistage polymerization method, Either a seed polymerization method, a power feed polymerization method, or the like may be employed.
  • the continuous addition method is preferable from the standpoint of stability during polymerization and ease of adjustment of the molecular weight.
  • Examples of the emulsifier used in the emulsion polymerization of the thermoplastic resin emulsion contained in the fiber bundling composition of the present invention 2 include sulfuric acid ester salts of higher alcohols, alkylbenzenesulfonates, alkyldiphenylether disulfonates, and aliphatic Anionic surfactants such as sulfonates, aliphatic carboxylates, dehydroabietic acid salts, formalin condensates of naphthalenesulfonic acid, sulfate ester salts of nonionic surfactants, alkyl esters of polyethylene glycol, alkylphenyls nonionic surfactants such as ether type and alkyl ether type; These can be used individually by 1 type or in combination of 2 or more types.
  • the amount of the emulsifier to be blended can be appropriately adjusted in consideration of the combination with other additives.
  • alkylbenzenesulfonates, alkyldiphenylether disulfonates, aliphatic sulfonates, and nonionic surfactants are preferred from the viewpoint of emulsion stability.
  • the emulsifier used during emulsion polymerization is preferably used in the range of 0.05 to 10 parts by weight with respect to 100 parts by weight of all the monomers. If it is less than 0.05 part by weight, the stability of the emulsion is poor and the yield at the time of impregnation treatment is lowered. Product strength tends to decrease.
  • the range is preferably 0.06 to 8 parts by weight, more preferably 0.08 to 5 parts by weight.
  • polymerization initiators used in emulsion polymerization of the thermoplastic resin emulsion contained in the fiber bundling composition of the present invention 2 include water-soluble agents such as lithium persulfate, potassium persulfate, sodium persulfate and ammonium persulfate.
  • Oil-soluble polymerization initiators such as cumene hydroperoxide, benzoyl peroxide, t-butyl hydroperoxide, acetyl peroxide, diisopropylbenzene hydroperoxide, and 1,1,3,3-tetramethylbutyl hydroperoxide initiators. These can be used individually by 1 type or in combination of 2 or more types.
  • potassium persulfate sodium persulfate
  • cumene hydroperoxide or t-butyl hydroperoxide.
  • the amount of the polymerization initiator to be blended is appropriately adjusted in consideration of the monomer composition, the pH of the polymerization reaction system, the combination of other additives, and the like.
  • Examples of the chain transfer agent used in emulsion polymerization of the thermoplastic resin emulsion contained in the fiber bundling composition of the present invention 2 include n-hexylmercaptan, n-octylmercaptan, t-octylmercaptan, and n-dodecyl.
  • Alkyl mercaptans such as mercaptan, t-dodecyl mercaptan and n-stearyl mercaptan; xanthogen compounds such as dimethylxanthogen disulfide and diisopropyl xanthogen disulfide; thiuram compounds such as tetramethylthiuram disulfide, tetraethylthiuram disulfide and tetramethylthiuram monosulfide; Phenolic compounds such as 2,6-di-t-butyl-4-methylphenol and styrenated phenol; Allyl compounds such as allyl alcohol; Dichloromethane, dibromomethane, halogenated hydrocarbon compounds such as carbon tetrabromide; Vinyl ethers such as benzyloxystyrene, ⁇ -benzyloxyacrylonitrile, ⁇ -benzyloxyacrylamide; Chain transfer agents such as methylstyrene dim
  • Examples of the reducing agent used in the emulsion polymerization of the thermoplastic resin emulsion contained in the fiber bundling composition of the present invention 2 include sulfite, hydrogen sulfite, pyrosulfite, nitionite, and nitionate. , thiosulfate, formaldehyde sulfonate, benzaldehyde sulfonate; L-ascorbic acid, erythorbic acid, tartaric acid, citric acid and other carboxylic acids and salts thereof; dextrose, saccharose and other reducing sugars; dimethylaniline, triethanolamine, etc. amines of. These can be used individually by 1 type or in combination of 2 or more types. Among these, L-ascorbic acid and erythorbic acid are preferred. The blending amount of the reducing agent can be appropriately adjusted in consideration of the combination with other additives.
  • the reaction system contains saturated hydrocarbons such as pentane, hexane, heptane, octane, cyclohexane, and cycloheptane; pentene, hexene, heptene, Hydrocarbon compounds such as unsaturated hydrocarbons such as cyclopentene, cyclohexene, cycloheptene, 4-methylcyclohexene and 1-methylcyclohexene; aromatic hydrocarbons such as benzene, toluene and xylene can be blended. These can be used individually by 1 type or in combination of 2 or more types. Among these, it is preferable to use cyclohexene and toluene.
  • saturated hydrocarbons such as pentane, hexane, heptane, octane, cyclohexane, and cycloheptane
  • pentene, hexene, heptene Hydrocarbon compounds
  • the polymerization temperature during emulsion polymerization is preferably in the range of 30 to 85°C, and the polymerization time is preferably in the range of 3 to 20 hours.
  • the fiber bundling composition of the present invention 2 contains an emulsifier, a dispersant, a lubricant, an antifoaming agent, a preservative, an antioxidant, an ultraviolet absorber, a light stabilizer, and a colorant. , an antistatic agent, a plasticizer, etc. can be blended and used within a range that does not impair the effects of the present invention 2.
  • the content of the thermoplastic resin emulsion (in terms of solid content) in the fiber bundling composition of Invention 2 is preferably 80% by weight or more, more preferably 90% by weight or more.
  • the weight-average molecular weight of the thermoplastic resin emulsion in the fiber bundling composition of Invention 2 is preferably in the range of 1.0 ⁇ 10 4 to 8 ⁇ 10 4 . If the weight-average molecular weight is lower than 1.0 ⁇ 10 4 , the strength of the final product, which is the objective of Invention 2, is inferior, and if it exceeds 8 ⁇ 10 4 , impregnation between fibers, which is the feature of Invention 2, is impaired. descend. More preferably 2 ⁇ 10 4 to 7.5 ⁇ 10 4 , still more preferably 2.5 ⁇ 10 4 to 7 ⁇ 10 4 , particularly preferably 3.5 ⁇ 10 4 to 6.8 ⁇ 10 4 , most preferably It is in the range of 4 ⁇ 10 4 to 6.5 ⁇ 10 4 .
  • the weight-average molecular weight of the thermoplastic resin emulsion was measured using a commercially available gel permeation chromatogram (GPC) measurement device equipped with a UV detector and column (Agilent MIXD-B) at a column temperature of 50°C and a solvent It is a polystyrene-equivalent molecular weight measured under the conditions of tetrahydrofuran (THF), a flow rate of 1 ml/min, and a detection wavelength of 254 nm.
  • GPC gel permeation chromatogram
  • the glass transition temperature of the solid content of the thermoplastic resin emulsion in the fiber bundling composition of Invention 2 is preferably in the range of 30 to 200°C from the standpoint of the strength of the final product.
  • the range is more preferably 35 to 190°C, still more preferably 60 to 140°C, and particularly preferably 80 to 120°C.
  • This glass transition temperature can be measured according to JIS K7121-2012.
  • the method for extracting the solid content in the thermoplastic resin emulsion is not particularly limited, but it can be obtained, for example, by drying the thermoplastic resin emulsion in a dryer adjusted to 90° C. for 10 hours.
  • the surface tension of the fiber bundling composition of the present invention 2 is required to be 25 to 45 mN/m, particularly preferably 26 to 42 mN/m, particularly preferably 27 to 40 mN/m. . If the surface tension exceeds 45 mN/m, the uniform adhesion of the thermoplastic resin emulsion to the reinforcing fibers is lowered, and the adhesiveness between the thermoplastic matrix resin and the reinforcing fibers is deteriorated. On the other hand, when the surface tension is less than 25 mN/m, it becomes difficult to control the amount of the sizing agent attached to the reinforcing fibers.
  • the surface tension can be measured, for example, by the method described in Examples.
  • the surface tension can be adjusted by adjusting the content of the ethylenically unsaturated carboxylic acid monomer and the type and amount of the emulsifier added to the thermoplastic resin emulsion.
  • the type of emulsifier added to the thermoplastic resin emulsion is preferably at least one of nonionic surfactants and anionic surfactants, such as acetylene glycol type nonionic surfactants, dodecylbenzene sulfone At least one of sodium sulfate and dialkylsulfosuccinate anionic surfactants is more preferred.
  • the amount of emulsifier to be added is preferably 0.5 to 2.5 parts by weight with respect to 100 parts by weight (solid content) of the thermoplastic resin emulsion.
  • the method for bundling fibers with the fiber bundling composition of the present invention 2 is not particularly limited, and it is possible to select one or a combination of two or more of known methods such as a spray method, a coating method, and an impregnation method. be.
  • Fibers to be bundled by the composition for fiber bundling of the present invention 2 include carbon fiber, glass fiber, boron fiber, silicon carbide fiber, metal fiber such as aluminum fiber, stainless steel fiber, copper fiber, nickel fiber, polyamide fiber, and polyester.
  • Organic fibers such as fibers, polyarylate fibers, polyimide fibers, and (nano)cellulose fibers can be used. Furthermore, these fibers can be used singly or in combination of two or more. Among them, carbon fiber and glass fiber are preferred.
  • carbon fibers include carbon fibers coated with metal such as nickel, and there are no particular restrictions on the form thereof, and may be continuous fibers, chopped fibers, milled shapes, non-woven fabrics, etc. Any form can be selected according to the requirements.
  • the fiber bundling composition is 1 to 20 parts by weight and the fiber is 99 to 80 parts by weight in terms of solid content in terms of the strength of the final product. is preferably impregnated in the range of
  • the method for evaporating the moisture of the fiber bundled with the fiber bundling composition is not particularly limited, and includes a method using a dryer, a method of irradiating with infrared rays, and a method of continuously using a dryer. It is possible to adopt a method such as passing through, depending on the purpose.
  • the drying temperature is preferably adjusted to the glass transition temperature of the thermoplastic resin emulsion plus 60 to 80° C. for handling the fibers after the bundling treatment.
  • the resin-impregnated fiber of Invention 2 can be melt-kneaded with a thermoplastic resin and used as a fiber-reinforced thermoplastic resin composition. Furthermore, it can also be used as a laminate laminated with a thermoplastic resin sheet or film.
  • thermoplastic resin to be combined with the resin-impregnated fiber of the present invention 2 examples include polystyrene (PS), high-impact polystyrene (HIPS), acrylonitrile-butadiene rubber-styrene copolymer (ABS), acrylonitrile-acrylic rubber-styrene copolymer.
  • PS polystyrene
  • HIPS high-impact polystyrene
  • ABS acrylonitrile-butadiene rubber-styrene copolymer
  • ABS acrylonitrile-acrylic rubber-styrene copolymer
  • ASA acrylonitrile-ethylene propylene rubber-styrene copolymer
  • AS acrylonitrile-styrene copolymer
  • PES polyethylene
  • PP polypropylene
  • PC polyethylene terephthalate
  • PBT polybutylene terephthalate
  • polyester resins such as polylactic acid resin (PLA), polymethyl methacrylate resin (PMMA), polyamide resin (PA), thermoplastic polyurethane resin (TPU),
  • PLA polylactic acid resin
  • PMMA polymethyl methacrylate resin
  • PA thermoplastic polyurethane resin
  • TPU thermoplastic polyurethane resin
  • Examples include alloys of polyether sulfone (PES), polyphenylene sulfide (PPS) or styrene resins and one or more resins selected from polyester resins and polyamide resins.
  • styrene resins styrene resins, polyester resins, polyamide resins, and alloys of styrene resins and polyester resins or polyamides are preferred from the viewpoint of the balance between moldability and strength of the final product.
  • the thermoplastic resin to be combined with the resin-impregnated fiber of the present invention 2 includes, for example, a light stabilizer, an antioxidant, a heat stabilizer, an ultraviolet absorber, a lubricant, a flame retardant, a flame retardant aid, a plasticizer, a pigment, and a dye.
  • a light stabilizer for example, an antioxidant, a heat stabilizer, an ultraviolet absorber, a lubricant, a flame retardant, a flame retardant aid, a plasticizer, a pigment, and a dye.
  • a light stabilizer for example, a light stabilizer, an antioxidant, a heat stabilizer, an ultraviolet absorber, a lubricant, a flame retardant, a flame retardant aid, a plasticizer, a pigment, and a dye.
  • Various additives such as can also be included.
  • the fiber-reinforced thermoplastic resin composition obtained by melt-kneading the resin-impregnated fiber and the thermoplastic resin of the present invention 2 can be, for example, injection molding, multilayer extrusion molding, film molding, sheet molding, inflation molding, press molding,
  • a molded article can be obtained by adopting a processing method according to the purpose, such as the SMC molding method and the LFT-D method. In some cases, it is also possible to interpose a step of pre-shaping.
  • a molded product by press molding, SMC molding, or the like using a laminate obtained by laminating a layer comprising the resin-impregnated fiber of the present invention 2 with a thermoplastic resin sheet or film. It is possible. In some cases, it is also possible to interpose a step of pre-shaping.
  • thermoplastic resin used for molding the processing temperature of the molded product, but it is preferable to mold in the range of 180 to 300 ° C. from the viewpoint of the molding cycle. , and more preferably in the range of 200 to 280°C.
  • the fiber bundling composition of Invention 3 contains a thermoplastic resin emulsion and at least one of acetylene glycol-based nonionic surfactants and dialkylsulfosuccinate-based anionic surfactants.
  • thermoplastic resin emulsion contained in the fiber bundling composition of the present invention 3 is not particularly limited as long as it is an aqueous dispersion of a thermoplastic resin.
  • thermoplastic resin examples include polyester resin emulsion, polyurethane resin emulsion, vinyl acetate resin emulsion, Examples include vinylidene chloride resin emulsions, polyamide resin emulsions, aromatic vinyl resin emulsions, acrylic resin emulsions, and olefin resin emulsions.
  • an aromatic vinyl-based resin emulsion is preferable from the viewpoint of adhesiveness between the resin-impregnated fiber and the thermoplastic resin.
  • the aromatic vinyl resin emulsion contains a copolymer of an aromatic vinyl monomer and another monomer copolymerizable with the aromatic vinyl monomer.
  • Other monomers copolymerizable with aromatic vinyl monomers include ethylenically unsaturated carboxylic acid monomers, vinyl cyanide monomers, alkyl ester monomers, and hydroxyalkyl group-containing monomers.
  • unsaturated monomers, unsaturated carboxylic acid amide-based monomers, vinylpyridine-based monomers, conjugated diene-based monomers, etc., and depending on the purpose, each may be used alone or in combination of two or more. It is possible to
  • the aromatic vinyl-based monomers include styrene, ⁇ -methylstyrene, vinyltoluene, divinylbenzene, and the like, and one or more of these can be used. Styrene and ⁇ -methylstyrene are particularly preferred.
  • ethylenically unsaturated carboxylic acid monomers include mono- or dicarboxylic acids (anhydrides) such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, and itaconic acid.
  • vinyl cyanide-based monomers examples include acrylonitrile, methacrylonitrile, ⁇ -chloroacrylonitrile, ⁇ -ethylacrylonitrile and the like.
  • Alkyl ester monomers include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, glycidyl methacrylate, dimethyl fumarate, diethyl fumarate, dimethyl maleate, diethyl malate, dimethyl itaconate, and monomethyl fumarate. , monoethyl fumarate, 2-ethylhexyl acrylate and the like.
  • Unsaturated monomers containing hydroxyalkyl groups include ⁇ -hydroxyethyl acrylate, ⁇ -hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, hydroxybutyl methacrylate, 3-chloro-2-hydroxypropyl Methacrylate, di-(ethylene glycol) maleate, di-(ethylene glycol) itaconate, 2-hydroxyethyl maleate, bis(2-hydroxyethyl) maleate, 2-hydroxyethyl methyl fumarate and the like.
  • unsaturated carboxylic acid amide-based monomers include acrylamide, methacrylamide, N-methylol acrylamide, N-methylol methacrylamide, and N,N-dimethylacrylamide.
  • vinylpyridine-based monomers examples include 2-vinylpyridine, 3-vinylpyridine, 4-vinylpyridine, and 2-methyl-5-vinylpyridine.
  • Conjugated diene-based monomers include 1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 2-chloro-1,3-butadiene, substituted linear Conjugated pentadienes, substituted and side chain conjugated hexadienes, and the like.
  • other monomers copolymerizable with aromatic vinyl monomers include acrylic acid, methacrylic acid, fumaric acid, itaconic acid, acrylonitrile, methacrylonitrile, methyl methacrylate, butyl acrylate, and ⁇ -hydroxyethyl. Preference is given to using acrylates, acrylamides or methacrylamides, 2-vinylpyridine, 1,3-butadiene.
  • the content of the aromatic vinyl monomer in the total amount of monomers (total monomers) used for producing the thermoplastic resin emulsion is preferably 40 to 98.5% by weight, preferably 45 to 95% by weight. % by weight is more preferred, and 47 to 90% by weight is even more preferred. By adjusting it within this range, the adhesion between the resin-impregnated fiber and the thermoplastic resin tends to be excellent.
  • the content of the "other monomer copolymerizable with the aromatic vinyl monomer" in all the monomers is preferably 1.5 to 60% by weight, and 5 to 55% by weight. is more preferable, and 10 to 53% by weight is even more preferable. By adjusting it within this range, the adhesion between the resin-impregnated fiber and the thermoplastic resin tends to be excellent.
  • the preferable composition ratio of each monomer in the aromatic vinyl resin emulsion is 60 to 95% by weight of the aromatic vinyl monomer, 4 to 39% by weight of the vinyl cyanide monomer, and the ethylenically unsaturated carboxylic acid. 1 to 15% by weight of the monomer, and more preferable composition ratios are: 80 to 94% by weight of the aromatic vinyl monomer, 5 to 15% by weight of the vinyl cyanide monomer, and the ethylenically unsaturated carboxylic acid. 1 to 5% by weight of acid monomer may be mentioned.
  • thermoplastic resin emulsion contained in the composition for fiber bundling of the present invention 3 is obtained by emulsion polymerization
  • known emulsion polymerization methods such as batch addition method, divided addition method, continuous addition method, multistage polymerization method, Either a seed polymerization method, a power feed polymerization method, or the like may be employed.
  • the continuous addition method is preferable from the standpoint of stability during polymerization and ease of adjustment of the molecular weight.
  • n-hexylmercaptan, n-octylmercaptan, t-octylmercaptan, n-dodecylmercaptan, t-dodecylmercaptan, n - alkyl mercaptans such as stearyl mercaptan
  • xanthogen compounds such as dimethylxanthogen disulfide and diisopropyl xanthogen disulfide
  • thiuram compounds such as tetramethylthiuram disulfide, tetraethylthiuram disulfide and tetramethylthiuram monosulfide
  • Phenolic compounds such as butyl-4-methylphenol and styrenated phenol, allyl compounds such as allyl alcohol, halogenated hydrocarbon compounds such as dichloromethane, dibrom
  • Surfactants used in emulsion polymerization of the thermoplastic emulsion contained in the fiber bundling composition of the present invention 3 are not particularly limited. acid salts, aliphatic sulfonates, aliphatic carboxylates, nonionic surfactants such as acetylene glycol-based surfactants, acetylene alcohol-based surfactants, polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether , polyoxyethylene dodecyl phenyl ether, polyoxyethylene alkyl allyl ether, polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene alkyl ether, polyoxyalkylene alkyl ether, etc., polyoxyethylene oleic acid, poly Esters such as oxyethylene oleate, polyoxyethylene distearate, sorbitan laurate, sorbitan monostearate, sorbitan monooleate, sorbitan sesqui
  • One or more of these can be used, and it is preferable to use them in the range of 0.05 to 10 parts by weight per 100 parts by weight of the total monomers. If the amount is less than 0.05 parts, the stability of the polymerization liquid is poor, and if the amount exceeds 10 parts by weight, a large amount of gas is generated during molding of the final product, resulting in the problem of damaging the surface of the molded product.
  • the range is preferably 0.1 to 8 parts by weight, more preferably 0.5 to 5 parts by weight.
  • electrolytes can be used during polymerization.
  • polymerization accelerators can be used during polymerization.
  • chelating agents can be used during polymerization.
  • the polymerization temperature during emulsion polymerization is preferably in the range of 40 to 80°C, and the polymerization time is preferably in the range of 3 to 15 hours.
  • the fiber bundling composition of Invention 3 contains at least one of acetylene glycol-based nonionic surfactants and dialkylsulfosuccinate-based anionic surfactants.
  • the acetylene glycol-based nonionic surfactant is a compound represented by the following general formula (1) or (2).
  • R1, R2, R3 and R4 in the above general formula (1) each represent an alkyl group having 1 or more and 5 or less carbon atoms.
  • R1, R2, R3 and R4 preferably have bilaterally symmetrical structures centering on the acetylene group.
  • R5, R6, R7 and R8 in the general formula (2) each represent an alkyl group having 1 to 5 carbon atoms.
  • m and n are each an integer of 1 or more and 25 or less, and m+n is 2 or more and 40 or less.
  • OE is an oxyethylene chain ( --O--CH.sub.2--CH.sub.2--) and OP is an oxypropylene chain ( --O-- CH.sub.2 --CH[ CH.sub.3 ]--).
  • OE and OP may each be single-stranded or mixed-stranded.
  • R5, R6, R7 and R8 preferably have a bilaterally symmetrical structure centering on the acetylene group.
  • Acetylene glycol-based nonionic surfactants are manufactured by Nissin Chemical Industry Co., Ltd. under the name of "Surfynol (registered trademark)” or “Olfine (registered trademark)", and manufactured by Kawaken Fine Chemicals Co., Ltd. under the name of "Acetylenol (registered trademark)”. Trademark)”.
  • Acetylene glycol-based nonionic surfactants include 2,4,7,9-tetramethyl-5-decyne-4,7-diol or 2,4,7,9-tetramethyl-5-decyne-4,7- Ethoxylates of diols are preferred.
  • the dialkyl sulfosuccinate-based anionic surfactant is not particularly limited, but one having an alkyl group with 8 to 16 carbon atoms is preferable.
  • salts include alkali metal salts such as sodium salts and potassium salts, alkaline earth metal salts, ammonium salts, and organic amine salts such as alkanolamines.
  • dialkylsulfosuccinate examples include sodium dioctylsulfosuccinate, magnesium dioctylsulfosuccinate, triethanolamine dioctylsulfosuccinate, sodium didecylsulfosuccinate, sodium didodecylsulfosuccinate (sodium dilaurylsulfosuccinate). salt), didodecylsulfosuccinate magnesium salt, ditetradecylsulfosuccinate lithium salt, dihexadecylsulfosuccinate potassium salt, and the like.
  • these dialkylsulfosuccinates one dialkylsulfosuccinate may be used alone, or two or more dialkylsulfosuccinates may be used in combination.
  • sodium dioctyl sulfosuccinate is preferable from the viewpoint of improving bending strength.
  • the content of at least one of the acetylene glycol nonionic surfactant and the dialkylsulfosuccinate anionic surfactant is preferably 0.5 to 10 parts by weight based on 100 parts by weight of the thermoplastic resin emulsion. , more preferably 0.7 to 3.2 parts by weight. By adjusting it within this range, the adhesion between the resin-impregnated fiber and the thermoplastic resin tends to be excellent.
  • At least one of the acetylene glycol-based nonionic surfactant and the dialkylsulfosuccinate-based anionic surfactant may be added during the production of the thermoplastic resin emulsion, or may be added after the completion of the production of the thermoplastic resin emulsion. good.
  • the fiber bundling composition of the present invention 3 contains a dispersant, a lubricant, an antifoaming agent, a preservative, an antioxidant, an ultraviolet absorber, a light stabilizer, a coloring agent, an antistatic agent, a plasticizer, and the like. It is possible to mix and use within a range that does not impair the effects of Invention 3.
  • the content of the thermoplastic resin emulsion (in terms of solid content) in the fiber bundling composition of Invention 3 is preferably 80% by weight or more, more preferably 90% by weight or more.
  • the weight-average molecular weight of the thermoplastic resin emulsion in the fiber bundling composition of Invention 3 is preferably in the range of 1.0 ⁇ 10 4 to 8 ⁇ 10 4 . If the weight-average molecular weight is lower than 1.0 ⁇ 10 4 , the strength of the final product, which is the object of Invention 3, is inferior, and if it exceeds 8 ⁇ 10 4 , impregnation between carbon fibers, which is the feature of Invention 3, is poor. descend. More preferably 2 ⁇ 10 4 to 7.5 ⁇ 10 4 , still more preferably 2.5 ⁇ 10 4 to 7 ⁇ 10 4 , particularly preferably 3.5 ⁇ 10 4 to 6.8 ⁇ 10 4 , most preferably It is in the range of 4 ⁇ 10 4 to 6.5 ⁇ 10 4 .
  • the weight-average molecular weight of the thermoplastic resin emulsion was measured using a commercially available gel permeation chromatogram (GPC) measurement device equipped with a UV detector and column (Agilent MIXD-B) at a column temperature of 50°C and a solvent It is a polystyrene-equivalent molecular weight measured under the conditions of tetrahydrofuran (THF), a flow rate of 1 ml/min, and a detection wavelength of 254 nm.
  • GPC gel permeation chromatogram
  • the glass transition temperature of the solid content of the thermoplastic resin emulsion in the composition for fiber bundling of Invention 3 is preferably in the range of 30 to 200°C from the standpoint of the strength of the final product.
  • the range is more preferably 35 to 190°C, still more preferably 60 to 140°C, and particularly preferably 80 to 120°C.
  • This glass transition temperature can be measured according to JIS K7121-2012.
  • the method for extracting the solid content in the thermoplastic resin emulsion is not particularly limited, but it can be obtained, for example, by drying the thermoplastic resin emulsion in a dryer adjusted to 90° C. for 10 hours.
  • the fiber bundling composition of the present invention 3 must have a dynamic surface tension of 25 to 55 mN/m, particularly preferably 29 to 40 mN/m. If the dynamic surface tension is more than 55 mN/m, the wettability of the fiber bundling composition to the fibers is lowered, and the adhesion between the thermoplastic resin and the fibers is deteriorated. On the other hand, if the dynamic surface tension is less than 25 mN/m, it may be difficult to control the amount of the fiber bundling composition attached to the fibers.
  • the dynamic surface tension can be measured, for example, by the method described in Examples.
  • the dynamic surface tension can be adjusted, for example, by the type and amount of surfactant added to the fiber bundling composition.
  • the method for bundling the fiber bundling composition of the present invention 3 into fibers is not particularly limited, and it is possible to select one or a combination of two or more from methods such as a spray method, a coating method, and an impregnation method.
  • the fibers to be bundled with the fiber bundling composition of the present invention 3 include carbon fiber, glass fiber, boron fiber, silicon carbide fiber, metal fiber such as aluminum fiber, stainless fiber, copper fiber, nickel fiber, polyamide fiber, and polyester.
  • Organic fibers such as fibers, polyarylate fibers, polyimide fibers, and (nano)cellulose fibers can be used.
  • these fibers can be used singly or in combination of two or more.
  • carbon fiber is most preferred.
  • carbon fibers include carbon fibers coated with metal such as nickel, and there are no particular restrictions on the form thereof, and may be continuous fibers, chopped fibers, milled shapes, non-woven fabrics, etc. Any form can be selected according to the requirements.
  • the fiber bundling composition is 1 to 20 in terms of solid content. It is preferably in the range of 99 to 80 parts by weight of the fiber.
  • the method of evaporating the moisture after the fiber bundling composition is bundled into the fiber is not particularly limited.
  • a method of passing through a dryer or the like can be employed depending on the purpose.
  • the glass transition temperature of the fiber bundling composition + 1 m or more adjusted to 60 ° C. or higher It is preferable to dry while continuously passing through a dryer having tracks at a speed of 0.5 m/min or more.
  • the resin-impregnated fiber of Invention 3 can be melt-kneaded with a thermoplastic resin and used as a fiber-reinforced thermoplastic resin composition. Furthermore, it can also be used as a laminate laminated with a thermoplastic resin sheet or film.
  • thermoplastic resin to be combined with the resin-impregnated fiber of the present invention 3 examples include polystyrene (PS), high-impact polystyrene (HIPS), acrylonitrile-butadiene rubber-styrene copolymer (ABS), acrylonitrile-ethylene propylene rubber-styrene.
  • PS polystyrene
  • HIPS high-impact polystyrene
  • ABS acrylonitrile-butadiene rubber-styrene copolymer
  • ABS acrylonitrile-ethylene propylene rubber-styrene
  • AES acrylonitrile-acrylic rubber-styrene copolymer
  • ASA acrylonitrile-styrene copolymer
  • AS acrylonitrile-styrene copolymer
  • PE polyethylene
  • PC polypropylene
  • PET polyethylene terephthalate
  • PET polyester resins such as polybutylene terephthalate (PBT), polymethyl methacrylate resin (PMMA), polyamide resin (PA), thermoplastic polyurethane resin (TPU), polylactic acid resin (PLA)
  • PES acrylonitrile-acrylic rubber-styrene copolymer
  • PPS polypropylene
  • PET polyethylene terephthalate
  • PET polyester resins such as polybutylene terephthalate (PBT), polymethyl methacrylate resin (PMMA), polyamide resin (PA), thermoplastic polyurethane resin (TPU), polylactic acid resin (PLA)
  • PES polyether sulfone
  • PPS polyphenylene
  • styrene resins polyester resins, polyamide resins, and alloys of styrene resins and polyester resins or polyamides are preferred from the viewpoint of the balance between moldability and strength of the final product.
  • thermoplastic resin to be combined with the resin-impregnated fiber of the present invention 3 includes, for example, a light stabilizer, an antioxidant, a heat stabilizer, an ultraviolet absorber, a lubricant, a flame retardant, a flame retardant aid, a plasticizer, a pigment, and a dye.
  • a light stabilizer for example, an antioxidant, a heat stabilizer, an ultraviolet absorber, a lubricant, a flame retardant, a flame retardant aid, a plasticizer, a pigment, and a dye.
  • a light stabilizer for example, a light stabilizer, an antioxidant, a heat stabilizer, an ultraviolet absorber, a lubricant, a flame retardant, a flame retardant aid, a plasticizer, a pigment, and a dye.
  • Various additives such as can also be included.
  • the fiber-reinforced thermoplastic resin composition obtained by melt-kneading the resin-impregnated fiber and the thermoplastic resin of the present invention 3 can be, for example, injection molding, multilayer extrusion molding, film molding, sheet molding, inflation molding, press molding,
  • a molded article can be obtained by adopting a processing method according to the purpose, such as the SMC molding method and the LFT-D method. In some cases, it is also possible to interpose a step of pre-shaping.
  • a laminate obtained by laminating a layer made of the resin-impregnated fiber of the present invention 3 with a thermoplastic resin sheet or film can be molded by press molding or the like. In some cases, it is also possible to interpose a step of pre-shaping.
  • thermoplastic resin used for molding molded product.
  • the thermoplastic emulsion contained in the fiber bundling composition of the present invention 4 contains a copolymer obtained by polymerizing a plurality of monomers.
  • a plurality of monomers contain an aromatic vinyl-based monomer as an essential component.
  • the aromatic vinyl-based monomer include styrene, ⁇ -methylstyrene, vinyltoluene, divinylbenzene, and the like, and one or more of these can be used. Styrene and ⁇ -methylstyrene are particularly preferred.
  • Other monomers copolymerizable with aromatic vinyl monomers include ethylenically unsaturated carboxylic acid monomers, vinyl cyanide monomers, alkyl ester monomers, and hydroxyalkyl group-containing monomers. unsaturated monomers, unsaturated carboxylic acid amide-based monomers, vinylpyridine-based monomers, and conjugated diene-based monomers. It is possible to
  • ethylenically unsaturated carboxylic acid monomers include mono- or dicarboxylic acids (anhydrides) such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, and itaconic acid.
  • vinyl cyanide-based monomers examples include acrylonitrile, methacrylonitrile, ⁇ -chloroacrylonitrile, ⁇ -ethylacrylonitrile and the like.
  • Alkyl ester monomers include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, glycidyl methacrylate, dimethyl fumarate, diethyl fumarate, dimethyl maleate, diethyl malate, dimethyl itaconate, and monomethyl fumarate. , monoethyl fumarate, 2-ethylhexyl acrylate and the like.
  • Unsaturated monomers containing hydroxyalkyl groups include ⁇ -hydroxyethyl acrylate, ⁇ -hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, hydroxybutyl methacrylate, 3-chloro-2-hydroxypropyl Methacrylate, di-(ethylene glycol) maleate, di-(ethylene glycol) itaconate, 2-hydroxyethyl maleate, bis(2-hydroxyethyl) maleate, 2-hydroxyethyl methyl fumarate and the like.
  • unsaturated carboxylic acid amide-based monomers include acrylamide, methacrylamide, N-methylol acrylamide, N-methylol methacrylamide, and N,N-dimethylacrylamide.
  • vinylpyridine-based monomers examples include 2-vinylpyridine, 3-vinylpyridine, 4-vinylpyridine, and 2-methyl-5-vinylpyridine.
  • Conjugated diene-based monomers include 1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 2-chloro-1,3-butadiene, substituted linear Conjugated pentadienes, substituted and side chain conjugated hexadienes, and the like.
  • other monomers copolymerizable with aromatic vinyl monomers include acrylic acid, methacrylic acid, fumaric acid, itaconic acid, acrylonitrile, methacrylonitrile, methyl methacrylate, butyl acrylate, and ⁇ -hydroxyethyl. Preference is given to using acrylates, acrylamides or methacrylamides, 2-vinylpyridine, 1,3-butadiene.
  • the content of the aromatic vinyl monomer in the total monomer is 40 to 98.5% by weight, preferably 45 to 95% by weight, more preferably 47 to 90% by weight. . By adjusting it within this range, the adhesion between the resin-impregnated fiber and the thermoplastic resin tends to be excellent.
  • the content of "other monomers copolymerizable with the aromatic vinyl monomer” in all monomers is 1.5 to 60% by weight with respect to 100% by weight of the aromatic vinyl resin emulsion. and preferably 5 to 55% by weight, more preferably 10 to 53% by weight. By adjusting it within this range, the adhesion between the resin-impregnated fiber and the thermoplastic resin tends to be excellent.
  • the preferable composition ratio of each monomer in the thermoplastic resin emulsion is 60 to 95% by weight of aromatic vinyl monomer, 4 to 39% by weight of vinyl cyanide monomer, and ethylenically unsaturated carboxylic acid monomer. 1 to 15% by weight of aromatic vinyl monomers, 5 to 15% by weight of vinyl cyanide monomers, and ethylenically unsaturated carboxylic acid monomers. from 1 to 5% by weight.
  • thermoplastic resin emulsion contained in the fiber bundling composition of the present invention 4 is obtained by emulsion polymerization, it is not particularly limited as long as it does not impair the purpose of the present invention 4.
  • Any of an addition method, a divided addition method, a continuous addition method, a multistage polymerization method, a seed polymerization method, a power feed polymerization method, and the like may be employed.
  • the continuous addition method is preferable from the standpoint of stability during polymerization and ease of adjustment of the molecular weight.
  • n-hexylmercaptan, n-octylmercaptan, t-octylmercaptan, n-dodecylmercaptan, t-dodecylmercaptan, n - alkyl mercaptans such as stearyl mercaptan
  • xanthogen compounds such as dimethylxanthogen disulfide and diisopropyl xanthogen disulfide
  • thiuram compounds such as tetramethylthiuram disulfide, tetraethylthiuram disulfide and tetramethylthiuram monosulfide
  • Phenolic compounds such as butyl-4-methylphenol and styrenated phenol, allyl compounds such as allyl alcohol, halogenated hydrocarbon compounds such as dichloromethane, dibrom
  • the emulsifier used in the emulsion polymerization of the thermoplastic resin emulsion contained in the fiber bundling composition of the present invention 4 is not particularly limited. Salts, aliphatic sulfonates, aliphatic carboxylates, anionic surfactants such as sulfuric acid ester salts of nonionic surfactants, or nonions such as alkyl ester types, alkylphenyl ether types, and alkyl ether types of polyethylene glycol One or more of these may be used, and it is preferable to use them in the range of 0.05 to 10 parts by weight per 100 parts by weight of the total monomers.
  • the range is preferably 0.1 to 8 parts by weight, more preferably 0.5 to 5 parts by weight.
  • electrolytes can be used during polymerization.
  • polymerization accelerators can be used during polymerization.
  • chelating agents can be used during polymerization.
  • the glass transition temperature of the thermoplastic resin emulsion contained in the fiber bundling composition of the present invention 4 is preferably 110°C or less from the viewpoint of impregnation between fibers. Particularly preferably, it is 105° C. or less. Incidentally, the glass transition temperature can be measured by a normal DSC method.
  • the above glass transition temperature can be adjusted by adjusting the mixing ratio of the monomers, the types and amounts of additives used during polymerization, the polymerization temperature, additives added after polymerization, and the like.
  • the average particle size of the thermoplastic resin emulsion is 150 nm or less, preferably 130 nm or less, more preferably 127 nm or less, and even more preferably 100 nm or less.
  • thermoplastic resin emulsion When the average particle size of the thermoplastic resin emulsion exceeds 150 nm, it becomes difficult for the fiber bundling composition to permeate the carbon fibers, resulting in a decrease in impregnability. Further, when the average particle size of the thermoplastic resin emulsion is less than 70 nm, the dispersion stability of the thermoplastic resin emulsion is lowered.
  • the average particle size of the thermoplastic resin emulsion can be measured, for example, by the method described in Examples.
  • the particle size of the thermoplastic resin emulsion can be adjusted by changing the amount of emulsifier during emulsion polymerization and the polymerization water used during polymerization.
  • the amount of emulsifier is preferably 1.8 to 2.5 parts by weight with respect to 100 parts by weight of all monomers.
  • the emulsifier is preferably added in two or more stages, preferably 15 to 95% by weight of the total amount added in the first stage, more preferably 30 to 90% by weight.
  • the amount of polymerization water used is preferably 90 to 270 parts by weight, more preferably 140 to 250 parts by weight.
  • the fiber bundling composition of the present invention 4 includes a polyester resin emulsion, a polyurethane resin emulsion, a vinyl acetate resin emulsion, a vinylidene chloride resin emulsion, a polyamide resin emulsion, an aromatic vinyl resin emulsion, and an acrylic resin emulsion.
  • Other thermoplastic resin emulsions such as resin emulsions and olefin resin emulsions, dispersants, leveling agents, lubricants, antifoaming agents, wetting agents, preservatives, antioxidants, UV absorbers, light stabilizers, colorants, An antistatic agent, a plasticizer, etc. can be blended and used within a range that does not impair the effects of the present invention 4.
  • the content of the thermoplastic resin emulsion (in terms of solid content) in the fiber bundling composition of the present invention 4 is preferably 80% by weight or more, more preferably 90% by weight or more.
  • the content of the other resin emulsion in the fiber bundling composition (in terms of solid content) is preferably 20% by weight or less, more preferably 10% by weight or less.
  • the method for bundling the fiber bundling composition of the present invention 4 into fibers is not particularly limited, and it is possible to select one or a combination of two or more from methods such as a spray method, a coating method, and an impregnation method.
  • fibers for bundling the fiber bundling composition of the present invention 4 include carbon fiber, glass fiber, boron fiber, silicon carbide fiber, metal fiber such as aluminum fiber, stainless steel fiber, copper fiber, nickel fiber, polyamide fiber, and polyester.
  • Organic fibers such as fibers, polyarylate fibers, polyimide fibers, and (nano)cellulose fibers can be used.
  • these fibers can be used singly or in combination of two or more.
  • carbon fiber is most preferable.
  • carbon fibers include carbon fibers coated with metal such as nickel, and there are no particular restrictions on the form thereof, and may be continuous fibers, chopped fibers, milled shapes, non-woven fabrics, etc. Any form can be selected according to the requirements.
  • the fiber bundling composition is 1 to 20 in terms of solid content. It is preferable to impregnate in the range of 99 to 80 parts by weight of fibers.
  • the method of evaporating the moisture after the fiber bundling composition is bundled is not particularly limited.
  • a method of passing through a dryer or the like can be employed depending on the purpose.
  • the glass transition temperature of the fiber bundling composition + 1 m or more adjusted to 60 ° C. or higher It is preferable to dry while continuously passing through a dryer having tracks at a speed of 0.5 m/min or more.
  • the resin-impregnated fiber of the present invention 4 can be melt-kneaded with a thermoplastic resin and used as a fiber-reinforced thermoplastic resin composition. Furthermore, it can also be used as a laminate laminated with a thermoplastic resin sheet or film.
  • thermoplastic resin to be combined with the resin-impregnated fiber of the present invention 4 examples include polystyrene (PS), high-impact polystyrene (HIPS), acrylonitrile-butadiene rubber-styrene copolymer (ABS), acrylonitrile-ethylene propylene rubber-styrene.
  • PS polystyrene
  • HIPS high-impact polystyrene
  • ABS acrylonitrile-butadiene rubber-styrene copolymer
  • ABS acrylonitrile-ethylene propylene rubber-styrene
  • AES acrylonitrile-acrylic rubber-styrene copolymer
  • ASA acrylonitrile-styrene copolymer
  • AS acrylonitrile-styrene copolymer
  • PE polyethylene
  • PC polypropylene
  • PET polyethylene terephthalate
  • PET polyester resins such as polybutylene terephthalate (PBT), polymethyl methacrylate resin (PMMA), polyamide resin (PA), thermoplastic polyurethane resin (TPU), polylactic acid resin (PLA)
  • PES acrylonitrile-acrylic rubber-styrene copolymer
  • PPS polypropylene
  • PET polyethylene terephthalate
  • PET polyester resins such as polybutylene terephthalate (PBT), polymethyl methacrylate resin (PMMA), polyamide resin (PA), thermoplastic polyurethane resin (TPU), polylactic acid resin (PLA)
  • PES polyether sulfone
  • PPS polyphenylene
  • styrene resins polyester resins, polyamide resins, and alloys of styrene resins and polyester resins or polyamides are preferred from the viewpoint of the balance between moldability and strength of the final product, and polyester resins or polyamides are more preferred.
  • thermoplastic resin to be combined with the resin-impregnated fiber of the present invention 4 includes, for example, light stabilizers, antioxidants, heat stabilizers, ultraviolet absorbers, lubricants, flame retardants, flame retardant aids, plasticizers, pigments, dyes. Various additives such as can also be included.
  • the fiber-reinforced thermoplastic resin composition obtained by melt-kneading the resin-impregnated fiber of the present invention 4 and a thermoplastic resin can be, for example, injection molding, multilayer extrusion molding, film molding, sheet molding, inflation molding, press molding,
  • a molded article can be obtained by adopting a processing method according to the purpose, such as the SMC molding method and the LFT-D method. In some cases, it is also possible to interpose a step of pre-shaping.
  • a laminate obtained by laminating a layer made of the resin-impregnated fiber of the present invention 4 with a thermoplastic resin sheet or film can be molded by press molding or the like. In some cases, it is also possible to interpose a step of pre-shaping.
  • thermoplastic resin used for molding molded product.
  • the fiber bundling composition of the present invention 5 contains a thermoplastic resin emulsion.
  • thermoplastic resin emulsion contained in the fiber bundling composition of the present invention 5 is not particularly limited as long as it is an aqueous dispersion of a thermoplastic resin.
  • examples include polyester resin emulsion, polyurethane resin emulsion, vinyl acetate resin emulsion, Examples include vinylidene chloride resin emulsions, polyamide resin emulsions, aromatic vinyl resin emulsions, acrylic resin emulsions, and olefin resin emulsions.
  • thermoplastic resin emulsion is preferably a copolymer obtained by polymerizing a plurality of monomers containing an ethylenically unsaturated carboxylic acid monomer, from the viewpoint of ease of handling of bundled fibers and performance of the final product. Contains coalescence.
  • Ethylenically unsaturated carboxylic acid monomers include monocarboxylic acid monomers such as acrylic acid, methacrylic acid and crotonic acid, dicarboxylic acid monomers such as maleic acid, fumaric acid and itaconic acid, and their anhydrides. mentioned. These monomers can be used individually by 1 type or in combination of 2 or more types. The use of acrylic acid, methacrylic acid and itaconic acid is particularly preferred.
  • Other monomers copolymerizable with ethylenically unsaturated carboxylic acid monomers include aromatic vinyl monomers, vinyl cyanide monomers, alkyl ester monomers, and hydroxyalkyl group-containing monomers.
  • unsaturated monomers, unsaturated carboxylic acid amide-based monomers, vinylpyridine-based monomers, oxazoline-based monomers, and conjugated diene-based monomers It is possible to use a mixture of more than one species.
  • the aromatic vinyl-based monomers include styrene, ⁇ -methylstyrene, vinyltoluene, divinylbenzene, and the like, and one or more of these can be used.
  • vinyl cyanide-based monomers examples include acrylonitrile, methacrylonitrile, ⁇ -chloroacrylonitrile, ⁇ -ethylacrylonitrile, and the like, and one or more of these can be used.
  • Alkyl ester monomers include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, glycidyl methacrylate, dimethyl fumarate, diethyl fumarate, dimethyl maleate, diethyl malate, dimethyl itaconate, and monomethyl fumarate. , monoethyl fumarate, 2-ethylhexyl acrylate and the like, and one or more of these can be used.
  • Unsaturated monomers containing hydroxyalkyl groups include ⁇ -hydroxyethyl acrylate, ⁇ -hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, hydroxybutyl methacrylate, 3-chloro-2-hydroxypropyl methacrylate, di-(ethylene glycol) maleate, di-(ethylene glycol) itaconate, 2-hydroxyethyl maleate, bis(2-hydroxyethyl) maleate, 2-hydroxyethyl methyl fumarate and the like, one of which Or 2 or more types can be used.
  • unsaturated carboxylic acid amide-based monomers include acrylamide, methacrylamide, N-methylol acrylamide, N-methylol methacrylamide, N,N-dimethylacrylamide and the like, and one or more of these may be used. can be done.
  • Vinylpyridine-based monomers include 2-vinylpyridine, 3-vinylpyridine, 4-vinylpyridine, 2-methyl-5-vinylpyridine and the like, and one or more of these may be used. .
  • oxazoline-based monomers examples include 2-vinyl-2-oxazoline and 4,4-dimethyl-2-vinyl-2-oxazoline-5-one, and one or more of these may be used. can be done.
  • Conjugated diene monomers include 1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 2-chloro-1,3-butadiene and the like. , these can be used alone or in combination of two or more.
  • other monomers copolymerizable with ethylenically unsaturated carboxylic acid monomers include styrene, ⁇ -methylstyrene, acrylonitrile, methyl methacrylate, butyl acrylate, ⁇ -hydroxyethyl acrylate, acrylamide or methacrylamide, 2 -Vinylpyridine, 1,3-butadiene is preferred.
  • the content of the ethylenically unsaturated carboxylic acid monomer in all monomers is preferably 0.1 to 20% by weight, more preferably 0.5 to 18% by weight, and 0.5 to 16% by weight. % is more preferred. By adjusting it within this range, there tends to be an excellent balance between the bundling property and the dispersibility of the resin-impregnated fibers in the thermoplastic resin.
  • the preferable composition ratio of each monomer in the thermoplastic resin emulsion is 60 to 95% by weight of aromatic vinyl monomer, 4 to 39% by weight of vinyl cyanide monomer, and ethylenically unsaturated carboxylic acid monomer. 1 to 15% by weight of aromatic vinyl monomer, 5 to 15% by weight of vinyl cyanide monomer, and ethylenically unsaturated carboxylic acid monomer. from 1 to 10% by weight.
  • thermoplastic resin emulsion contained in the fiber bundling composition of the present invention 5 is obtained by an emulsion polymerization method
  • a known emulsion polymerization method such as a batch addition method, a divided addition method, a continuous addition method, and a multistage polymerization method is used.
  • a seed polymerization method, a power feed polymerization method, and the like may be employed depending on the intended purpose, but the continuous addition method is preferred from the standpoint of stability during polymerization and ease of molecular weight adjustment.
  • surfactants used in emulsion polymerization of the thermoplastic resin emulsion contained in the fiber bundling composition of the present invention 5 include linear alkylbenzene sulfonates, polyoxyethylene alkyl ether sulfates, and ⁇ -olefins.
  • Anionic surfactants such as sulfonates, alkanesulfonates, polyoxyethylene alkyl ether acetates, fatty acid salts, ⁇ -sulfo fatty acid methyl ester salts, dialkylsulfosuccinates and alkyl sulfates, and nonionic surfactants Active agents such as acetylene glycol-based surfactants, acetylene alcohol-based surfactants, polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene dodecylphenyl ether, polyoxyethylene alkylallyl ether, polyoxyethylene Ethers such as oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene alkyl ether, polyoxyalkylene alkyl ether, polyoxyethylene oleic acid, polyoxyethylene oleate, polyoxyethylene distearate, sorbitan laurate, sorbitan Esters such as
  • the surfactant used during emulsion polymerization is preferably used in the range of 0.05 to 10 parts by weight with respect to 100 parts by weight of all the monomers. If it is less than 0.05 part by weight, the stability of the emulsion is poor and the yield at the time of impregnation treatment is lowered. Product strength tends to decrease.
  • the range is preferably 0.06 to 8 parts by weight, more preferably 0.08 to 5 parts by weight.
  • polymerization initiators used for emulsion polymerization of the thermoplastic resin emulsion contained in the fiber bundling composition of the present invention 5 include water-soluble agents such as lithium persulfate, potassium persulfate, sodium persulfate and ammonium persulfate.
  • Oil-soluble polymerization initiators such as cumene hydroperoxide, benzoyl peroxide, t-butyl hydroperoxide, acetyl peroxide, diisopropylbenzene hydroperoxide, and 1,1,3,3-tetramethylbutyl hydroperoxide initiators. These can be used individually by 1 type or in combination of 2 or more types.
  • potassium persulfate sodium persulfate
  • cumene hydroperoxide or t-butyl hydroperoxide.
  • the amount of the polymerization initiator to be blended is appropriately adjusted in consideration of the monomer composition, the pH of the polymerization reaction system, the combination of other additives, and the like.
  • Examples of chain transfer agents used in emulsion polymerization of the thermoplastic resin emulsion contained in the fiber bundling composition of the present invention 5 include n-hexylmercaptan, n-octylmercaptan, t-octylmercaptan, and n-dodecyl.
  • Alkyl mercaptans such as mercaptan, t-dodecyl mercaptan and n-stearyl mercaptan; xanthogen compounds such as dimethylxanthogen disulfide and diisopropyl xanthogen disulfide; thiuram compounds such as tetramethylthiuram disulfide, tetraethylthiuram disulfide and tetramethylthiuram monosulfide; Phenolic compounds such as 2,6-di-t-butyl-4-methylphenol and styrenated phenol; Allyl compounds such as allyl alcohol; Dichloromethane, dibromomethane, halogenated hydrocarbon compounds such as carbon tetrabromide; Vinyl ethers such as benzyloxystyrene, ⁇ -benzyloxyacrylonitrile, ⁇ -benzyloxyacrylamide; Chain transfer agents such as methylstyrene dim
  • Examples of the reducing agent used in the emulsion polymerization of the thermoplastic resin emulsion contained in the fiber bundling composition of the present invention 5 include sulfite, hydrogen sulfite, pyrosulfite, nitionite, and nitionate. , thiosulfate, formaldehyde sulfonate, benzaldehyde sulfonate; L-ascorbic acid, erythorbic acid, tartaric acid, citric acid and other carboxylic acids and salts thereof; dextrose, saccharose and other reducing sugars; dimethylaniline, triethanolamine, etc. amines of. These can be used individually by 1 type or in combination of 2 or more types. Among these, L-ascorbic acid and erythorbic acid are preferred.
  • the blending amount of the reducing agent can be appropriately adjusted in consideration of the combination with other additives.
  • the reaction system contains saturated hydrocarbons such as pentane, hexane, heptane, octane, cyclohexane, and cycloheptane; pentene, hexene, heptene, Hydrocarbon compounds such as unsaturated hydrocarbons such as cyclopentene, cyclohexene, cycloheptene, 4-methylcyclohexene and 1-methylcyclohexene; aromatic hydrocarbons such as benzene, toluene and xylene can be blended. These can be used individually by 1 type or in combination of 2 or more types. Among these, it is preferable to use cyclohexene and toluene.
  • saturated hydrocarbons such as pentane, hexane, heptane, octane, cyclohexane, and cycloheptane
  • pentene, hexene, heptene Hydrocarbon compounds
  • the polymerization temperature during emulsion polymerization is preferably in the range of 30 to 85°C, and the polymerization time is preferably in the range of 3 to 20 hours.
  • the glass transition temperature of the solid content of the thermoplastic resin emulsion in the fiber bundling composition of the present invention is preferably in the range of 30 to 200°C from the standpoint of the strength of the final product.
  • the range is more preferably 35 to 190°C, still more preferably 60 to 140°C, and particularly preferably 80 to 120°C.
  • This glass transition temperature can be measured according to JIS K7121-2012.
  • the method for extracting the solid content in the thermoplastic resin emulsion is not particularly limited, but it can be obtained, for example, by drying the thermoplastic resin emulsion in a dryer adjusted to 90° C. for 10 hours.
  • the fiber bundling composition of the present invention 5 contains a dispersant, a lubricant, an antifoaming agent, a preservative, an antioxidant, an ultraviolet absorber, a light stabilizer, a coloring agent, and an antistatic agent. , a plasticizer, etc., can be mixed and used within a range that does not impair the effects of the present invention 5.
  • the content of the thermoplastic resin emulsion (in terms of solid content) in the fiber bundling composition of the present invention 5 is preferably 80% by weight or more, more preferably 90% by weight or more.
  • the pH of the fiber bundling composition of the present invention 5 is in the range of 4 to 7, preferably 4 to 6.4, more preferably 4.1 to 5.5. If the pH is less than 4 or more than 7, hydrolysis of the polyester resin, which is the matrix resin, tends to proceed remarkably.
  • the pH of the fiber bundling composition depends on the type and amount of the ethylenically unsaturated carboxylic acid monomer added when polymerizing the thermoplastic resin emulsion, sodium hydroxide, potassium hydroxide, etc. added during polymerization or at the completion of polymerization. It is possible to adjust the addition amount of the alkaline substance and the addition amount of the acidic substance such as acetic acid, sulfuric acid, hydrochloric acid and phosphoric acid.
  • the method for bundling fibers with the fiber bundling composition of the present invention 5 is not particularly limited, and it is possible to select one or a combination of two or more from known methods such as spraying, coating, and impregnation. be.
  • Fibers to be bundled by the composition for fiber bundling of the present invention 5 include carbon fiber, glass fiber, boron fiber, silicon carbide fiber, metal fiber such as aluminum fiber, stainless fiber, copper fiber, nickel fiber, polyamide fiber, and polyester.
  • Organic fibers such as fibers, polyarylate fibers, polyimide fibers, and (nano)cellulose fibers can be used. Furthermore, these fibers can be used singly or in combination of two or more. Among them, carbon fiber and glass fiber are preferred.
  • carbon fibers include carbon fibers coated with metal such as nickel, and there are no particular restrictions on the form thereof, and may be continuous fibers, chopped fibers, milled shapes, non-woven fabrics, etc. Any form can be selected according to the requirements.
  • the composition for fiber bundling is 1 to 20 parts by weight and the fiber is 99 to 80 parts by weight in terms of solid content. is preferably impregnated in the range of
  • the method for evaporating the moisture of the fiber bundled with the fiber bundling composition is not particularly limited, and includes a method using a dryer, a method of irradiating infrared rays, and a method of continuously using a dryer. It is possible to adopt a method such as passing through, depending on the purpose.
  • the drying temperature is preferably adjusted to the glass transition temperature of the thermoplastic resin emulsion plus 60 to 80° C. for handling the fibers after the bundling treatment.
  • the resin-impregnated fiber of the present invention 5 can be melt-kneaded with a thermoplastic resin and used as a fiber-reinforced thermoplastic resin composition. Furthermore, it can also be used as a laminate laminated with a thermoplastic resin sheet or film.
  • thermoplastic resin to be combined with the resin-impregnated fiber of the present invention 5 examples include polyester resins such as polycarbonate (PC), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polylactic acid resin (PLA), and polystyrene (PS).
  • PC polycarbonate
  • PET polyethylene terephthalate
  • PBT polybutylene terephthalate
  • PLA polylactic acid resin
  • PS polystyrene
  • thermoplastic resin containing a polyester resin is preferable in order to obtain the effect of the present invention 5 more remarkably.
  • the thermoplastic resin to be combined with the resin-impregnated fiber of the present invention 5 includes, for example, a light stabilizer, an antioxidant, a heat stabilizer, an ultraviolet absorber, a lubricant, a flame retardant, a flame retardant auxiliary, a plasticizer, a pigment, and a dye.
  • a light stabilizer for example, an antioxidant, a heat stabilizer, an ultraviolet absorber, a lubricant, a flame retardant, a flame retardant auxiliary, a plasticizer, a pigment, and a dye.
  • the fiber-reinforced thermoplastic resin composition obtained by melt-kneading the resin-impregnated fiber and the thermoplastic resin of the present invention 5 can be, for example, injection molding, multilayer extrusion molding, film molding, sheet molding, inflation molding, press molding,
  • a molded article can be obtained by adopting a processing method according to the purpose, such as the SMC molding method and the LFT-D method. In some cases, it is also possible to interpose a step of pre-shaping.
  • a molded product by press molding, SMC molding, or the like using a laminate obtained by laminating a layer made of the resin-impregnated fiber of the present invention 5 with a thermoplastic resin sheet or film. It is possible. In some cases, it is also possible to interpose a step of pre-shaping.
  • thermoplastic resin used for molding the processing temperature of the molded product, but it is preferable to mold in the range of 180 to 300 ° C. from the viewpoint of the molding cycle. , and more preferably in the range of 200 to 280°C.
  • inventions 1 to 5 will be described more specifically using examples and comparative examples corresponding to each invention, but Inventions 1 to 5 are not limited by the following examples.
  • Various physical properties in each example and comparative example are measured by the following methods.
  • Detector UV Column: MIXD-B manufactured by Agilent Column temperature: 50°C Solvent: Tetrahydrofuran (THF) Flow rate: 1 ml/min, Detection wavelength: 254 nm Standard sample: Polystyrene Charpy impact strength (NC) Using the pellets obtained in each example and comparative example, various test pieces were molded according to ISO test method 294, and the notched Charpy impact value was measured according to ISO test method 179 with a thickness of 4 mm. Unit: kJ/ m2 Bending Strength Bending strength was measured according to JIS K7074 using the test pieces obtained in Examples and Comparative Examples.
  • the number average molecular weight was measured by GPC to be 2.5 ⁇ 10 4 , and the tetrahydrofuran-insoluble portion was 0% by weight.
  • Copolymer Emulsion-2 was obtained by the same polymerization method as Copolymer Emulsion-1, except that the amount of t-dodecylmercaptan used was changed to 2 parts.
  • the number average molecular weight was measured by GPC to be 1.0 ⁇ 10 4 , and the tetrahydrofuran-insoluble portion was 0% by weight.
  • Copolymer emulsion-3 was obtained by the same polymerization method as for copolymer emulsion-1, except that the amount of t-dodecylmercaptan used was changed to 0.4 parts.
  • the number average molecular weight was measured by GPC to be 3.9 ⁇ 10 4 , and the tetrahydrofuran-insoluble portion was 0% by weight.
  • Copolymer emulsion-4 was obtained by the same polymerization method as for copolymer emulsion-1, except that the amount of t-dodecylmercaptan used was changed to 0.06 parts.
  • the number average molecular weight was measured by GPC to be 8 ⁇ 10 4 , and the tetrahydrofuran-insoluble portion was 0% by weight.
  • ⁇ Method for producing continuous resin-impregnated fiber-1 100 parts by weight of the carbon fibers were impregnated with the copolymer emulsion-1 (in terms of solid content) using a cloth drawing apparatus so that the adhesion amount was 15 parts by weight. Moisture was completely removed by moving in a drying oven adjusted to 1 m/min for 3 minutes to obtain the final continuous resin-impregnated fiber-1.
  • Continuous resin-impregnated fibers-2 to 4 were obtained in the same manner as the continuous resin-impregnated fiber-1, except that copolymer emulsion-1 was changed to copolymer emulsion-2 to 4.
  • the carbon fiber used for the above chopped strands and continuous resin-impregnated fibers is Tenax (registered trademark)-J STS40 F13 24K 1600tex manufactured by Teijin Limited.
  • Thermoplastic resin-1 Techniace (registered trademark) TA-1500 manufactured by Nippon A&L Co., Ltd. (Alloy of polyamide resin and ABS resin)
  • Thermoplastic resin-2 Techniace (registered trademark) PAX-1439 manufactured by Nippon A&L Co., Ltd. (alloy of polycarbonate resin and ABS resin)
  • Thermoplastic resin-3 Prime Polypro (registered trademark) J106G manufactured by Prime Polymer Co., Ltd.
  • thermoplastic resin ⁇ Method for producing fiber-reinforced thermoplastic resin composition> After mixing the thermoplastic resin and chopped strands at the blending ratio shown in Table 1, using OMega30H manufactured by STEER, which has two feeders, the thermoplastic resin is fed from F1 and the chopped strands from F2, and melted. The pellets of the fiber-reinforced thermoplastic resin composition were obtained by kneading. Using the pellets, test pieces for Charpy impact strength were molded with an injection molding machine.
  • the direction of the carbon fibers was aligned in one direction, and the test piece for the bending test was cut out in the direction in which the direction of the carbon fiber and the direction of the long side of the test piece coincided. .
  • Examples 1 to 8 which are fiber-reinforced thermoplastic resin compositions containing chopped strands produced using the fiber bundling composition of the present invention, were excellent in Charpy impact strength.
  • Comparative Example 1 was inferior in Charpy impact strength because the number average molecular weight of the copolymer emulsion contained in the fiber bundling composition of the present invention did not satisfy the specified range.
  • Comparative Example 2 was inferior in Charpy impact strength because it was a fiber-reinforced thermoplastic resin composition containing chopped strands that did not use a fiber bundling composition.
  • Comparative Example 3 was inferior in bending strength because the number average molecular weight of the copolymer emulsion contained in the fiber bundling composition of the present invention did not satisfy the specified range.
  • thermoplastic resin emulsion was dried at room temperature for a whole day and night, and then dried in an oven at 70°C for 1 hour to obtain a measurement sample. After that, a solution obtained by dissolving 0.02 g of the measurement sample in 10 ml of tetrahydrofuran (THF) was measured using a gel permeation chromatogram (GPC) measurement device under the following conditions.
  • GPC gel permeation chromatogram
  • thermoplastic resin emulsion was dried in an oven at 90°C for 10 hours to prepare a measurement sample. After that, it was measured according to JIS K7121-2012 using a differential scanning calorimeter.
  • Pure water was added to the surface tension fiber bundling composition to adjust the solid content to 30%, and then the surface tension was measured at 30°C using an automatic surface tension meter K11 (manufactured by KRUSS).
  • the solid content in the thermoplastic resin emulsion (1) had a weight average molecular weight of 5.4 ⁇ 10 4 and a glass transition temperature of 102°C.
  • thermoplastic resin emulsion (2) Heating was performed in the same manner as the thermoplastic resin emulsion (1) except that the monomer mixture was changed to 86 parts by weight of styrene, 9 parts by weight of acrylonitrile, 0.8 parts by weight of t-dodecylmercaptan, and 5 parts by weight of methacrylic acid. A plastic resin emulsion (2) was obtained.
  • the solid content in the thermoplastic resin emulsion (2) had a weight average molecular weight of 5.2 ⁇ 10 4 and a glass transition temperature of 103°C.
  • thermoplastic resin emulsion (3) was prepared in the same manner as thermoplastic resin emulsion (1) except that the monomer mixture was changed to 90 parts by weight of styrene, 10 parts by weight of acrylonitrile, and 0.8 parts by weight of t-dodecylmercaptan. Obtained.
  • the solid content in the thermoplastic resin emulsion (3) had a weight average molecular weight of 5.0 ⁇ 10 4 and a glass transition temperature of 100°C.
  • thermoplastic resin emulsion (1) was used as the fiber bundling composition (1).
  • the surface tension measured by the method described above was 40 mN/m.
  • ⁇ Method for producing fiber bundling composition (2)> After adding 1 part by weight of acetylene glycol-type nonionic surfactant (Surfinol (registered trademark) 104E manufactured by Nissin Chemical Industry Co., Ltd.) to 100 parts by weight (solid content) of thermoplastic resin emulsion (1) The mixture was sufficiently stirred to obtain a fiber bundling composition (2).
  • the surface tension measured by the method described above was 27 mN/m.
  • thermoplastic resin emulsion (1) To 100 parts by weight (solid content) of thermoplastic resin emulsion (1), 1 part by weight of a dialkylsulfosuccinate-based anionic surfactant (Sanmorin (registered trademark) OT-70 manufactured by Sanyo Chemical Industries, Ltd.) was added. After that, the mixture was sufficiently stirred to obtain a fiber bundling composition (4).
  • the surface tension measured by the method described above was 27 mN/m.
  • thermoplastic resin emulsion (2) was used as a fiber bundling composition (5).
  • the surface tension measured by the method described above was 36 mN/m.
  • thermoplastic resin emulsion (3) was used as a fiber bundling composition (6).
  • the surface tension measured by the method described above was 55 mN/m.
  • thermoplastic resin emulsion (1) To 100 parts by weight of the thermoplastic resin emulsion (1), 4 parts by weight of a dialkylsulfosuccinate-based anionic surfactant (Sanmorin (registered trademark) OT-70 manufactured by Sanyo Chemical Industries, Ltd.) was added and thoroughly stirred. A fiber bundling composition (7) was obtained. The surface tension measured by the method described above was 24 mN/m.
  • a dialkylsulfosuccinate-based anionic surfactant Sanmorin (registered trademark) OT-70 manufactured by Sanyo Chemical Industries, Ltd.
  • ⁇ Method for producing continuous resin-impregnated fiber (1) Using a cloth binding device, the fiber bundling composition (1) (converted to solid content) was bundled so that the adhesion amount was 10 parts by weight (converted to solid content) with respect to 100 parts by weight of carbon fiber, and then obtained The continuous resin-impregnated fiber was moved in a drying oven adjusted to 180° C. at a speed of 1 m/min for 3 minutes to completely remove moisture, thereby obtaining the final continuous resin-impregnated fiber (1).
  • Continuous resin-impregnated fibers (2) to (7) are produced in the same manner as the continuous resin-impregnated fiber (1) except that the fiber bundling composition (1) is changed to the fiber bundling composition (2) to (7). got
  • the carbon fiber used for the above chopped strands and continuous resin-impregnated fibers is Tenax (registered trademark)-J STS40 F13 24K 1600 tex manufactured by Teijin Limited.
  • Thermoplastic resin (1) Nippon A&L Co., Ltd. Clarastick (registered trademark) GA-501 (ABS resin) Thermoplastic resin (2) Techniace (registered trademark) TA-1500 manufactured by Nippon A&L Co., Ltd. (Alloy of polyamide resin and ABS resin) Thermoplastic resin (3) Techniace (registered trademark) PAX-1439 manufactured by Nippon A&L Co., Ltd.
  • thermoplastic resin composition (alloy of polycarbonate resin and ABS resin) ⁇ Method for producing fiber-reinforced thermoplastic resin composition> After mixing the thermoplastic resin and the chopped strands at the blending ratio shown in Table 3, the thermoplastic resin was chopped from F1 and the chopped strands from F2 using OMega30H manufactured by STEER, which has two feeders set at 260°C. A strand was added and melt-kneaded to obtain pellets of a fiber-reinforced thermoplastic resin composition. Using the pellets, a test piece for Charpy impact strength was molded with an injection molding machine, and a test piece of 5 mm ⁇ 5 mm ⁇ 4 mm was cut from the center of the obtained molded product and used for evaluation of openability.
  • a polyamide resin film Rayfan (registered trademark) NO 1401, thickness 40 ⁇ m, manufactured by Toray Advanced Film Co., Ltd.
  • a carbon fiber content 30% by weight.
  • Examples 1 to 15 were compositions for fiber bundling that satisfied the surface tension specified in the present invention, and therefore had an excellent balance between bundling and opening properties.
  • Comparative Examples 1 to 4 were fiber bundling compositions that did not satisfy the surface tension specified in the present invention, and were inferior in bundling and opening properties.
  • Example and Comparative Example Weight Average Molecular Weight The obtained thermoplastic resin emulsion was dried at room temperature for a whole day and night, and then dried in an oven at 70° C. for 1 hour to obtain a measurement sample. After that, a solution obtained by dissolving 0.02 g of the measurement sample in 10 ml of tetrahydrofuran (THF) was measured using a gel permeation chromatogram (GPC) measurement device under the following conditions.
  • GPC gel permeation chromatogram
  • thermoplastic resin emulsion was dried in an oven at 90°C for 10 hours to prepare a measurement sample. After that, it was measured according to JIS K7121-2012 using a differential scanning calorimeter.
  • a monomer mixture A consisting of 88 parts of styrene, 10 parts of acrylonitrile, and 0.8 parts of t-dodecylmercaptan was prepared, and this was mixed with 5% by weight of monomer mixture A-1 per 100% by weight of monomer mixture A. It was divided into 95% by weight monomer mixture A-2.
  • the solid content of the thermoplastic resin emulsion had a weight average molecular weight of 5.4 ⁇ 10 4 and a glass transition temperature of 102°C.
  • ⁇ Method for producing fiber bundling composition-1 1 part by weight (converted to solid content) of an acetylene glycol-based nonionic surfactant (product name “Surfinol (registered trademark) 104E”) is added to 100 parts by weight (converted to solid content) of a thermoplastic resin emulsion, and the mixture is sufficiently stirred. Then, a fiber bundling composition-1 was obtained.
  • the dynamic surface tension measured by the method described above was 40 mN/m.
  • acetylene glycol-based nonionic surfactant product name “Surfinol (registered trademark) 104E”
  • a dialkyl sulfosuccinate-based anionic surfactant product name “Sanmorin (registered trademark) OT-70”
  • the dynamic surface tension measured by the above method was 44 mN/m.
  • Sanmorin (registered trademark) OT-70 manufactured by Sanyo Chemical Industries, Ltd.
  • the dynamic surface tension measured by the above method was 30 mN/m.
  • thermoplastic resin emulsion was used as a fiber sizing agent composition-5.
  • the dynamic surface tension measured by the method described above was 62 mN/m.
  • Fiber bundling composition-1 (in terms of solid content) is bundled so that the content is 15 parts by weight with respect to 100 parts by weight of carbon fiber, and then the obtained continuous resin-impregnated fiber is 180 parts by weight. C. for 3 minutes at a speed of 1 m/min to completely remove moisture, thereby obtaining a final continuous resin-impregnated fiber-1.
  • Continuous resin-impregnated fibers-2 to 5 were obtained in the same manner as the continuous resin-impregnated fiber-1, except that the fiber bundling composition-1 was changed to fiber sizing agent compositions 2-5.
  • the carbon fiber used for the above-mentioned continuous resin-impregnated fiber is Tenax (registered trademark)-J STS40 F13 24K 1600tex manufactured by Teijin Limited.
  • ⁇ Method for producing a laminated product composed of continuous resin-impregnated fibers and thermoplastic resin> After arranging a plurality of continuous resin-impregnated fibers in parallel to form a 20 cm square sheet, a polyamide resin film (Rayfan (registered trademark) N0 1401, thickness 40 ⁇ m, manufactured by Toray Advanced Film Co., Ltd.) and a carbon fiber content of 30% by weight.
  • test piece having a width of 15 mm and a length of 150 mm was cut out from the obtained laminated product and used as a test piece for a bending test.
  • the direction of the carbon fibers was aligned in one direction, and the test piece for the bending test was cut out in the direction in which the direction of the carbon fiber and the direction of the long side of the test piece coincided. .
  • Comparative Example 1 was inferior in bending strength because the dynamic surface tension of the fiber bundling composition of the present invention did not satisfy the specified range.
  • the reactor was heated to 75° C., 0.7 parts of sodium dodecylbenzenesulfonate (in terms of solid content) and the monomer mixture A-1 were added and sufficiently stirred, and then 0.1 parts of potassium persulfate was added. After charging, polymerization was started at 80°C.
  • the polymerization temperature was maintained at 80°C for 5 hours to complete the polymerization.
  • the pH of the thermoplastic resin emulsion was maintained at 80°C for 5 hours to complete the polymerization.
  • unreacted monomers and other low boiling point compounds are removed by steam distillation, the solid content is adjusted to 45%, and the thermoplastic resin emulsion is (1) was obtained.
  • the average particle size measured by the method described above was 126 nm.
  • ⁇ Thermoplastic resin emulsion (2)> After adding 120 parts of deionized water to a pressure-resistant polymerization reactor, nitrogen substitution was performed. Prepare 100 parts of a monomer mixture A consisting of 88 parts of styrene, 10 parts of acrylonitrile, and 0.8 parts of t-dodecyl mercaptan, and add 5% by weight of monomer mixture A-1 to 100% by weight of monomer mixture A. It was divided into 95% by weight monomer mixture A-2.
  • the polymerization temperature was maintained at 80°C for 5 hours to complete the polymerization.
  • the pH of the thermoplastic resin emulsion was adjusted to about 7 with an aqueous solution of caustic soda, unreacted monomers and other low boiling point compounds are removed by steam distillation, the solid content is adjusted to 45%, and the thermoplastic resin emulsion is (2) was obtained.
  • the average particle size was measured by the method described above, it was 99 nm.
  • the polymerization temperature was maintained at 80°C for 5 hours to complete the polymerization.
  • the average particle size was measured by the method described above, it was 94 nm.
  • ⁇ Thermoplastic resin emulsion (4)> After adding 190 parts of deionized water to a pressure-resistant polymerization reactor, nitrogen substitution was performed. 100 parts of a monomer mixture A consisting of 88 parts of styrene, 10 parts of acrylonitrile, and 0.8 parts of t-dodecylmercaptan was prepared, and this was mixed with 5% by weight of monomer mixture A-1 per 100% by weight of monomer mixture A. It was divided into 95% by weight monomer mixture A-2.
  • the polymerization temperature was maintained at 80°C for 5 hours to complete the polymerization.
  • the pH of the thermoplastic resin emulsion was adjusted to about 7 with an aqueous solution of caustic soda, unreacted monomers and other low boiling point compounds are removed by steam distillation, the solid content is adjusted to 45%, and the thermoplastic resin emulsion is (4) was obtained.
  • the average particle size was measured by the method described above, it was 79 nm.
  • the polymerization temperature was maintained at 80°C for 5 hours to complete the polymerization.
  • the pH of the thermoplastic resin emulsion was adjusted to about 7 with an aqueous solution of caustic soda, unreacted monomers and other low boiling point compounds are removed by steam distillation, the solid content is adjusted to 45%, and the thermoplastic resin emulsion is (5) was obtained.
  • the average particle size was 145 nm.
  • Thermoplastic resin emulsion (6) After adding 45 parts of deionized water to the pressure-resistant polymerization reactor, nitrogen substitution was performed. Prepare 100 parts of a monomer mixture A consisting of 88 parts of styrene, 10 parts of acrylonitrile, and 0.8 parts of t-dodecyl mercaptan, and add 5% by weight of monomer mixture A-1 to 100% by weight of monomer mixture A. It was divided into 95% by weight monomer mixture A-2.
  • the polymerization temperature was maintained at 80°C for 5 hours to complete the polymerization.
  • the polymerization temperature was maintained at 80°C for 5 hours to complete the polymerization.
  • the pH of the thermoplastic resin emulsion was adjusted to about 7 with an aqueous solution of caustic soda, unreacted monomers and other low boiling point compounds are removed by steam distillation, the solid content is adjusted to 45%, and the thermoplastic resin emulsion is (6) was obtained.
  • the average particle size measured by the method described above was 160 nm.
  • thermoplastic resin emulsions (1) to (6) were used as fiber bundling compositions (1) to (6).
  • ⁇ Method for producing continuous resin-impregnated fiber (1) 100 parts by weight of the carbon fiber is impregnated with the fiber bundling composition (1) (in terms of solid content) using a cloth binding apparatus so that the adhesion amount is 15 parts by weight, and then the obtained continuous resin-impregnated fiber is Moisture was completely removed by moving in a drying oven adjusted to 180° C. for 3 minutes at a speed of 1 m/min to obtain a final continuous resin-impregnated fiber (1).
  • Continuous resin-impregnated fibers (2) to (6) are produced in the same manner as the continuous resin-impregnated fiber (1) except that the fiber bundling composition (1) is changed to the fiber bundling composition (2) to (6). Obtained.
  • the carbon fiber used for the above-mentioned continuous resin-impregnated fiber is Tenax (registered trademark)-J STS40 F13 24K 1600tex manufactured by Teijin Limited.
  • ⁇ Method for producing a laminated product composed of continuous resin-impregnated fibers and thermoplastic resin> After arranging a plurality of continuous resin-impregnated fibers in parallel to form a 20 cm square sheet, a polyamide resin film (Rayfan (registered trademark) N0 1401, thickness 40 ⁇ m, manufactured by Toray Advanced Film Co., Ltd.) and a carbon fiber content of 30% by weight.
  • test piece having a width of 15 mm and a length of 150 mm was cut out from the obtained laminated product and used as a test piece for a bending test.
  • the direction of the carbon fibers was aligned in one direction, and the test piece for the bending test was cut out in the direction in which the direction of the carbon fiber and the direction of the long side of the test piece coincided. .
  • Examples 1 to 5 in which continuous resin-impregnated fibers produced using the fiber bundling composition of the present invention were laminated with a polyamide resin film were excellent in impact absorption energy and bending strength.
  • Comparative Example 1 since the average particle size of the thermoplastic resin emulsion contained in the fiber bundling composition of the present invention did not satisfy the specified range, the impact absorption energy and bending strength were inferior.
  • thermoplastic resin emulsion was dried in an oven at 90°C for 10 hours to prepare a measurement sample. After that, it was measured according to JIS K7121-2012 using a differential scanning calorimeter.
  • melt flow rate (MFR-0) was measured according to ISO1133.
  • the melt flow rate (MFR-500) was also measured after being stored in a thermo-hygrostat at 85° C. and a relative humidity of 95% for 500 hours and then dried at 100° C. for 4 hours. Based on the measured values obtained, the rate of increase in melt flow rate was determined using the following formula (1). A larger value indicates that the hydrolysis is progressing.
  • Melt flow rate increase rate (%) MFR-500/MFR-0 x 100 (Formula 1) The measurement of MFR was performed under the following conditions.
  • Fiber-reinforced thermoplastic resin composition using thermoplastic resin (1) 300° C., 1.2 kg Fiber-reinforced thermoplastic resin composition using thermoplastic resin (2): 240° C., 10 kg Fiber-reinforced thermoplastic resin composition using thermoplastic resin (3): 220° C., 10 kg Evaluation of hydrolysis (2)
  • An ISO dumbbell was prepared using the pellets obtained in each example and comparative example, and the bending strength (FS-0) was measured according to ISO178.
  • the flexural strength (FS-500) after storage for 500 hours in a constant temperature and humidity chamber at 85° C. and a relative humidity of 95% was also measured in the same manner as in hydrolyzability evaluation (1).
  • the bending strength retention rate was obtained from the bending strength (FS-0) before moisture absorption and the bending strength (FS-500) after moisture absorption using the following formula (2). A smaller value indicates that the hydrolysis is progressing.
  • Bending strength retention rate (%) FS-500/FS-0 x 100 (Formula 2) Evaluation of hydrolysis (3) A test piece having a width of 15 mm and a length of 150 mm was cut out from the laminate obtained in each example and comparative example, and the bending strength (FS) was measured according to JISK7074. The bending strength retention rate was obtained from the bending strength (FS-0) before moisture absorption and the bending strength (FS-500) after moisture absorption.
  • thermoplastic resin emulsion (1) After adding 45 parts by weight of pure water to the polymerization reactor, the reactor was purged with nitrogen. Thereafter, the temperature was started to rise, and when the temperature reached 75°C, 0.2 parts by weight of potassium persulfate was added. Furthermore, when the reactor reached 80° C., a solution of 2.1 parts by weight of sodium dodecylbenzenesulfonate (in terms of solid content) dissolved in 30 parts by weight of pure water, 88 parts by weight of styrene, 10 parts by weight of acrylonitrile, and acrylic acid were added.
  • thermoplastic resin emulsion (1) A continuous addition of a monomer mixture consisting of 2 parts by weight and 0.8 parts by weight of t-dodecyl mercaptan was initiated over a period of 7.5 hours.
  • the temperature of the reactor was maintained at 80° C. during that time, and after the continuous addition was completed, the temperature was maintained at 80° C. for 5 hours in order to complete the polymerization.
  • pure water was used to adjust the solid content to 45% to obtain a thermoplastic resin emulsion (1).
  • the glass transition temperature of the solid content in the thermoplastic resin emulsion (1) was 102°C.
  • thermoplastic resin emulsion (2) After adding 45 parts by weight of pure water to the polymerization reactor, the reactor was purged with nitrogen. Thereafter, the temperature was started to rise, and when the temperature reached 75°C, 0.4 parts by weight of ammonium persulfate was added. Furthermore, when the reactor reaches 80° C., a solution of 3.0 parts by weight of ammonium dodecylbenzenesulfonate (in terms of solid content) dissolved in 30 parts by weight of pure water, 89 parts by weight of styrene, 10 parts by weight of acrylonitrile, and acrylic acid are added.
  • thermoplastic resin emulsion (2) A continuous addition of a monomer mixture consisting of 1 part by weight and 0.8 parts by weight of t-dodecyl mercaptan was initiated over a period of 7.5 hours.
  • the temperature of the reactor was maintained at 80° C. during that time, and after the continuous addition was completed, the temperature was maintained at 80° C. for 5 hours in order to complete the polymerization.
  • pure water was used to adjust the solid content to 45% to obtain a thermoplastic resin emulsion (2).
  • the glass transition temperature of the solid content in the thermoplastic resin emulsion (2) was 100°C.
  • thermoplastic resin emulsion (3) After adding 45 parts by weight of pure water to the polymerization reactor, the reactor was purged with nitrogen. Thereafter, the temperature was started to rise, and when the temperature reached 75°C, 0.4 parts by weight of potassium persulfate was added.
  • thermoplastic resin emulsion (1) was used as the fiber bundling composition (1).
  • the pH measured by the method described above was 4.8.
  • thermoplastic resin emulsion (2) was used as the fiber bundling composition (2).
  • the pH measured by the method described above was 5.2.
  • thermoplastic resin emulsion (3) was used as a fiber bundling composition (3).
  • the pH measured by the method described above was 4.2.
  • ⁇ Method for producing fiber bundling composition (4)> After adding 1 part by weight of an acetylene glycol-type nonionic surfactant (Nissin Chemical Industry Co., Ltd., Surfynol (registered trademark) 104E) to 100 parts by weight (solid content) of thermoplastic resin emulsion (1), to obtain a fiber bundling composition (4).
  • the pH measured by the method described above was 5.2.
  • thermoplastic resin emulsion Using a cloth binding device, each thermoplastic resin emulsion is bundled so that the adhesion amount is 10 parts by weight (converted to solid content) with respect to 100 parts by weight of continuous carbon fiber, and the continuous resin-impregnated fiber obtained after that is heated at 180 ° C. Moisture was completely removed by moving in a drying oven adjusted to 1 m/min for 3 minutes to obtain the final continuous resin-impregnated fiber (1).
  • Continuous resin-impregnated fibers (2) to (7) are produced in the same manner as the continuous resin-impregnated fiber (1) except that the fiber bundling composition (1) is changed to the fiber bundling composition (2) to (7). got
  • the carbon fiber used for the above chopped strands and continuous resin-impregnated fibers is Tenax (registered trademark)-J STS40 F13 24K 1600 tex manufactured by Teijin Limited.
  • Thermoplastic resin (1) SD POLYCA (registered trademark) 301-10 manufactured by Sumika Polycarbonate Co., Ltd. Thermoplastic resin (2) Techniace (registered trademark) PAX-1439 manufactured by Nippon A&L Co., Ltd. (alloy of polycarbonate resin and ABS resin) Thermoplastic resin (3) Alloy of polylactic acid resin and ABS resin ⁇ Method for producing fiber-reinforced thermoplastic resin composition> After mixing the thermoplastic resin and chopped strands at the blending ratio shown in Table 7, the thermoplastic resin was chopped from F1 and the chopped strands were chopped from F2 using OMega30H manufactured by STEER, which has two feeders set at 260°C. A strand was added and melt-kneaded to obtain pellets of a fiber-reinforced thermoplastic resin composition. An ISO dumbbell was prepared using the obtained pellets and used for hydrolyzability evaluation (2).
  • ⁇ Method for producing molded article composed of continuous resin-impregnated continuous fiber and thermoplastic resin After arranging a plurality of continuous resin-impregnated fibers in parallel to form a sheet of 20 cm square, a polycarbonate resin film (thickness 40 ⁇ m) prepared using a known film molding machine and carbon fibers were combined to form a carbon fiber content of 25% by weight. After preheating for 5 minutes with a pressure of 5 MPa using a compression molding machine NF37 with a set temperature of 280 ° C., hot press treatment for 5 minutes with a pressure of 15 MPa was performed to produce a laminate having a thickness of 2 mm. A test piece having a width of 15 mm and a length of 150 mm was cut out from the obtained laminate and used for hydrolyzability evaluation (3).
  • Examples 1 to 15 are fiber bundling compositions that satisfy the pH specified in the present invention, hydrolysis was suppressed and strength retention was excellent.
  • Comparative Examples 1 and 2 were fiber bundling compositions that did not satisfy the pH specified in the present invention, so hydrolysis proceeded and the strength retention rate was poor.
  • the present inventions 1 to 5 are suitable as molded articles, for example, for automobile parts and electric appliances.

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Abstract

A copolymer emulsion which is contained in a composition for fiber binding for the production of a resin-impregnated fiber by binding a plurality of fibers during the production of a fiber-reinforced thermoplastic resin composite material wherein the resin-impregnated fiber and a thermoplastic resin are complexed with each other. This copolymer emulsion is characterized by containing a copolymer of 40 to 98.5% by weight of an aromatic vinyl monomer and 1.5 to 60% by weight of another monomer that is copolymerizable with the aromatic vinyl monomer, and is also characterized in that the number average molecular weight of the copolymer is 0.5 × 104 to 4 × 104.

Description

共重合体エマルジョン、熱可塑性樹脂エマルジョン、繊維集束用組成物、及びこれを用いた樹脂含浸繊維、熱可塑性樹脂組成物、成形品Copolymer emulsion, thermoplastic resin emulsion, composition for fiber bundling, and resin-impregnated fiber, thermoplastic resin composition, molded article using the same

　本発明は、主に繊維強化熱可塑性樹脂複合材料の製造に用いられる共重合体エマルジョン、熱可塑性樹脂エマルジョン、繊維の集束用組成物、その集束用組成物で集束された樹脂含浸繊維、およびこれを用いた熱可塑性樹脂組成物、成形品に関するものである。 The present invention relates to a copolymer emulsion, a thermoplastic resin emulsion, a composition for bundling fibers, a resin-impregnated fiber bundled with the composition for bundling, and the It relates to a thermoplastic resin composition and a molded product using.

　炭素繊維を代表とする繊維材料は高強度、高弾性、電気伝導性等の優れた特徴をもち、その特徴を活かして熱可塑性樹脂をマトリックスとした繊維含有熱可塑性樹脂複合材料として、家電、輸送機械、スポーツ用品など様々な産業分野で広く利用されている。 Fiber materials, typified by carbon fiber, have excellent characteristics such as high strength, high elasticity, and electrical conductivity. It is widely used in various industrial fields such as machinery and sporting goods.

　これら繊維含有熱可塑性樹脂複合材料の製造に際しては、繊維に対して集束処理を行い繊維ストランドとした後に、混練や被覆などの方法で熱可塑性樹脂と複合化を行なっている。 In the production of these fiber-containing thermoplastic resin composite materials, the fibers are bundled to form fiber strands, which are then compounded with the thermoplastic resin by methods such as kneading and coating.

　集束処理は、数百本～数万本からなる独立した繊維を集束剤により一体化させ、ストランドとするもので、後の熱可塑性樹脂との複合化工程に必要不可欠な処理である。 The bundling process integrates hundreds to tens of thousands of independent fibers with a bundling agent to form a strand, and is an essential process for the subsequent process of combining with thermoplastic resin.

　この集束剤は、ストランドに耐擦性を付与させ、複合化工程における作業性に影響を与えるのみならず、本質的に相溶性のない繊維と熱可塑性樹脂マトリックスとの間に濡れ性や接着性等を付与し、最終的な繊維含有熱可塑性樹脂複合材料の性能や品質に大きく影響を与える重要なものである。 This sizing agent not only imparts abrasion resistance to the strands and affects workability in the composite process, but also wettability and adhesiveness between the essentially incompatible fibers and the thermoplastic resin matrix. etc., and is important because it greatly affects the performance and quality of the final fiber-containing thermoplastic resin composite material.

　従来、繊維束とマトリックス樹脂との親和性を高める目的では、さまざまな集束剤が検討されている。例えば、特許文献１では、共重合ナイロン樹脂を主成分とする水系エマルジョンを繊維束に付着させることで、繊維束とマトリックス樹脂との接着性を向上させて、複合材料の強度を改善する方法が開示されている。あるいは特許文献２では、特定のカルボキシル基量を有するスチレン系エマルジョンで処理する方法が開示されている。 Conventionally, various sizing agents have been investigated for the purpose of increasing the affinity between fiber bundles and matrix resins. For example, Patent Document 1 discloses a method for improving the strength of a composite material by attaching an aqueous emulsion containing a copolymerized nylon resin as a main component to a fiber bundle to improve the adhesiveness between the fiber bundle and the matrix resin. disclosed. Alternatively, Patent Document 2 discloses a method of treating with a styrene emulsion having a specific amount of carboxyl groups.

　また、特許文献３では、炭素繊維等からなる連続強化繊維シートと、熱可塑性樹脂からなる樹脂シートとを交互に積層した状態で、熱プレス処理（加熱加圧処理）を行うことにより、連続強化繊維間の隙間に熱可塑性樹脂を含浸させた繊維強化複合材料が開示されている。 Further, in Patent Document 3, a continuous reinforcing fiber sheet made of carbon fiber or the like and a resin sheet made of a thermoplastic resin are alternately laminated, and a heat press treatment (heating and pressurizing treatment) is performed to continuously strengthen the sheet. A fiber-reinforced composite material is disclosed in which interstices between fibers are impregnated with a thermoplastic resin.

　さらに、特許文献４では、炭素繊維等からなる連続強化繊維間の隙間に熱可塑性樹脂を含浸させたシート状のプリプレグを積層することにより形成された繊維強化複合材料が提案されており、この繊維強化複合材料は、プリプレグの強化繊維を所定の方向に配向させた状態で、予め所定の形状（長さ）に切断された各プリプレグを熱プレスにより付着（溶融接着）させて積層することで、生産性に優れ、高性能を有する繊維強化複合材料を得ることができると開示されている。 Furthermore, Patent Document 4 proposes a fiber-reinforced composite material formed by laminating sheet-like prepregs impregnated with a thermoplastic resin in the gaps between continuous reinforcing fibers made of carbon fibers or the like. Reinforced composite materials are produced by laminating prepregs, which have been cut into predetermined shapes (lengths) in advance, with the reinforcing fibers of the prepregs oriented in a predetermined direction, and are adhered (melted and bonded) by a hot press. It is disclosed that a fiber-reinforced composite material having excellent productivity and high performance can be obtained.

特開昭６１－２５４６２９号公報JP-A-61-254629 特開２００４－１７６２２７号公報JP 2004-176227 A 特開２０１３－１８９６３４号公報JP 2013-189634 A 国際公開ＷＯ２０１６／０６７７１１号公報International publication WO2016/067711

　しかし、これらの方法では、繊維とマトリックス樹脂との界面接着強度こそ向上するものの、最終的に得られる複合材料の曲げ強度や耐衝撃性等の機械的物性は、未だ満足できるものではない（第１の課題）。 However, although these methods improve the interfacial adhesive strength between the fiber and the matrix resin, the mechanical properties such as bending strength and impact resistance of the finally obtained composite material are still unsatisfactory. 1 issue).

　また、これらの方法では、繊維と熱可塑性樹脂との界面接着強度こそ向上するものの、取り扱い時の摩擦により繊維自体が毛羽だってしまいその取扱い性が著しく損なわれる集束性の不足、あるいは取り扱い性を改善しようとすると逆に繊維の集束性が強すぎて熱可塑性樹脂中に均一に分散することが困難になる、等の問題が発生し、取り扱い性と分散性のバランスは、未だ満足できるものが得られていないのが現状である（第２の課題）。 In these methods, although the interfacial adhesive strength between the fiber and the thermoplastic resin is improved, the fiber itself becomes fuzzy due to friction during handling, and the handleability is significantly impaired. On the contrary, problems such as difficulty in uniformly dispersing the fibers in the thermoplastic resin due to excessive fiber bundles occur, and the balance between handling and dispersibility is still satisfactory. It is the current situation that it is not done (the second problem).

　また、これらの方法では、繊維と熱可塑性樹脂との界面接着強度こそ向上するものの、熱可塑性樹脂にポリエステル樹脂を用いた場合、ポリエステル樹脂の加水分解を引き起こすという不具合があり、最終製品における長期安定性の面で未だ満足できるものが得られていないのが現状である（第３の課題）。 In addition, although these methods improve the interfacial adhesive strength between the fiber and the thermoplastic resin, there is a problem that the polyester resin is hydrolyzed when the polyester resin is used as the thermoplastic resin, resulting in long-term stability in the final product. The current situation is that no satisfactory product has been obtained yet in terms of sexuality (the third problem).

　本発明１は、上記第１の課題を解決するものであり、以下の［１］、［２］を含む。
［１］樹脂含浸繊維と熱可塑性樹脂とが複合化した繊維強化熱可塑性樹脂複合材料の製造において、複数の繊維を集束して前記樹脂含浸繊維を製造するための繊維集束用組成物に配合される共重合体エマルジョンであり、芳香族ビニル系単量体４０～９８．５重量％と、前記芳香族ビニル系単量体と共重合可能な他の単量体１．５～６０重量％との共重合体を含有し、前記共重合体の数平均分子量が０．５×１０４～４×１０４であることを特徴とする共重合体エマルジョン。
［２］［１］の共重合体エマルジョンを含有することを特徴とする繊維集束用組成物。 The present invention 1 solves the above first problem and includes the following [1] and [2].
[1] In the production of a fiber-reinforced thermoplastic resin composite material in which a resin-impregnated fiber and a thermoplastic resin are combined, it is blended in a fiber bundling composition for bundling a plurality of fibers to produce the resin-impregnated fiber. A copolymer emulsion comprising 40 to 98.5% by weight of an aromatic vinyl monomer and 1.5 to 60% by weight of another monomer copolymerizable with the aromatic vinyl monomer. and wherein the copolymer has a number average molecular weight of 0.5×10 4 to 4×10 4 .
[2] A fiber bundling composition comprising the copolymer emulsion of [1].

　本発明２は、上記第２の課題を解決するものであり、以下の［３］～［５］を含む。
［３]熱可塑性樹脂エマルジョンを含み、かつ固形分濃度を３０％とした際の、３０℃でのリング法により測定された表面張力が２５～４５ｍＮ／ｍである繊維集束用組成物。
［４］前記熱可塑性樹脂エマルジョンが、エチレン系不飽和カルボン酸単量体０．１～２０重量％と、前記エチレン系不飽和カルボン酸単量体と共重合可能な他の単量体８０～９９．９重量％との共重合物を含有することを特徴とする[３]の繊維集束用組成物。
［５］非イオン系界面活性剤または陰イオン系界面活性剤の少なくとも１種を含むことを特徴とする[３]または[４]の繊維集束用組成物。 The present invention 2 solves the above second problem, and includes the following [3] to [5].
[3] A fiber bundling composition containing a thermoplastic resin emulsion and having a surface tension of 25 to 45 mN/m as measured by the ring method at 30° C. when the solid content is 30%.
[4] The thermoplastic resin emulsion contains 0.1 to 20% by weight of an ethylenically unsaturated carboxylic acid monomer and 80 to 80% of another monomer copolymerizable with the ethylenically unsaturated carboxylic acid monomer. The composition for fiber bundling according to [3], characterized by containing a copolymer with 99.9% by weight.
[5] The fiber bundling composition of [3] or [4], which contains at least one of a nonionic surfactant and an anionic surfactant.

　本発明３は、上記第１の課題を解決するものであり、以下の［６］および［７］を含む。
［６］熱可塑性樹脂エマルジョンと、アセチレングリコール系非イオン界面活性剤またはジアルキルスルホコハク酸塩系陰イオン界面活性剤の少なくとも１種を含む繊維集束用組成物であって、動的表面張力が２５～５５ｍＮ／ｍであることを特徴とする繊維集束用組成物。
［７］前記熱可塑性樹脂エマルジョンが、芳香族ビニル系単量体４０～９８．５重量％と、前記芳香族ビニル系単量体と共重合可能な他の単量体１．５～６０重量％との共重合体を含有することを特徴とする[６]の繊維集束用組成物。 Invention 3 solves the first problem described above and includes the following [6] and [7].
[6] A fiber bundling composition containing a thermoplastic resin emulsion and at least one of an acetylene glycol-based nonionic surfactant and a dialkylsulfosuccinate-based anionic surfactant, and having a dynamic surface tension of 25 to A composition for fiber bundling, characterized in that it is 55 mN/m.
[7] The thermoplastic resin emulsion contains 40 to 98.5% by weight of an aromatic vinyl monomer and 1.5 to 60% by weight of another monomer copolymerizable with the aromatic vinyl monomer. % of the fiber bundling composition of [6].

　本発明４は、上記第１の課題を解決するものであり、以下の［８］および［９］を含む。
［８］樹脂含浸繊維と熱可塑性樹脂とが複合化した繊維強化熱可塑性樹脂複合材料の製造において、複数の繊維を集束して前記樹脂含浸繊維を製造するための繊維集束用組成物に配合される熱可塑性樹脂エマルジョンであり、芳香族ビニル系単量体４０～９８．５重量％と、前記芳香族ビニル系単量体と共重合可能な他の単量体１．５～６０重量％との共重合体を含有し、前記共重合体の平均粒子径が、７０ｎｍ以上１５０ｎｍ以下であることを特徴とする熱可塑性樹脂エマルジョン。
［９］ ［８］の熱可塑性樹脂エマルジョンを含有することを特徴とする繊維集束用組成物。 The present invention 4 solves the above first problem and includes the following [8] and [9].
[8] In the production of a fiber-reinforced thermoplastic resin composite material in which a resin-impregnated fiber and a thermoplastic resin are combined, it is blended in a fiber bundling composition for bundling a plurality of fibers to produce the resin-impregnated fiber. A thermoplastic resin emulsion comprising 40 to 98.5% by weight of an aromatic vinyl monomer and 1.5 to 60% by weight of another monomer copolymerizable with the aromatic vinyl monomer. A thermoplastic resin emulsion comprising a copolymer of (1) and having an average particle size of 70 nm or more and 150 nm or less.
[9] A fiber bundling composition comprising the thermoplastic resin emulsion of [8].

　本発明５は、上記第３の課題を解決するものであり、以下の［１０］～［１３］を含む。
［１０］熱可塑性樹脂エマルジョンを含み、ｐＨが４～７である繊維集束用組成物。
［１１］前記熱可塑性樹脂エマルジョンが、エチレン系不飽和カルボン酸単量体０．１～２０重量％と、前記エチレン系不飽和カルボン酸単量体と共重合可能な他の単量体８０～９９．９重量％との共重合物を含有することを特徴とする[１０]の繊維集束用組成物。
［１２］直鎖アルキルベンゼンスルホン酸塩、ポリオキシエチレンアルキルエーテル硫酸塩、α－オレフィンスルホン酸塩、アルカンスルホン酸塩、ジアルキルスルホコハク酸塩及びアルキル硫酸塩から選ばれた少なくとも１種を含む[１０]または［１１］の繊維集束用組成物。
［１３］非イオン系界面活性剤を含むことを特徴とする[１０]～[１２]のいずれか１つに記載の繊維集束用組成物。 The present invention 5 is to solve the above third problem, and includes the following [10] to [13].
[10] A fiber bundling composition containing a thermoplastic resin emulsion and having a pH of 4 to 7.
[11] The thermoplastic resin emulsion contains 0.1 to 20% by weight of an ethylenically unsaturated carboxylic acid monomer and 80 to 80% of another monomer copolymerizable with the ethylenically unsaturated carboxylic acid monomer. The composition for fiber bundling according to [10], characterized by containing a copolymer with 99.9% by weight.
[12] Contains at least one selected from linear alkylbenzenesulfonates, polyoxyethylene alkyl ether sulfates, α-olefinsulfonates, alkanesulfonates, dialkylsulfosuccinates and alkyl sulfates [10] Or the fiber bundling composition of [11].
[13] The fiber bundling composition according to any one of [10] to [12], which contains a nonionic surfactant.

　また、本発明１～５のそれぞれは、以下の［１４］～［１７］を含む。
［１４］［２］～［７］、［９］～［１３］のいずれか１つの繊繊維集束用組成物で集束された樹脂含浸繊維。
［１５］[１４]の樹脂含浸繊維と熱可塑性樹脂とを含む繊維強化熱可塑性樹脂組成物。
［１６］[１５]の繊維強化熱可塑性樹脂組成物を成形してなる成形品。
［１７］[１４]の樹脂含浸繊維からなる層と熱可塑性樹脂層を含む積層体を成形してなる成形品。 Moreover, each of the present inventions 1 to 5 includes the following [14] to [17].
[14] A resin-impregnated fiber bundled with the fiber bundling composition according to any one of [2] to [7] and [9] to [13].
[15] A fiber-reinforced thermoplastic resin composition comprising the resin-impregnated fibers of [14] and a thermoplastic resin.
[16] A molded article obtained by molding the fiber-reinforced thermoplastic resin composition of [15].
[17] A molded article obtained by molding a laminate comprising a layer made of the resin-impregnated fiber of [14] and a thermoplastic resin layer.

　本発明１によれば、成形品の曲げ強度および耐衝撃物性を向上させることのできる共重合体エマルジョン、繊維集束用組成物、及びこれを用いた樹脂含浸繊維、熱可塑性樹脂組成物、成形品を提供することにある。 According to the present invention 1, a copolymer emulsion, a composition for fiber bundling, and a resin-impregnated fiber, a thermoplastic resin composition, and a molded product using the same can improve the flexural strength and impact resistance properties of a molded product. is to provide

　本発明２によれば、取り扱い性と分散性に優れる繊維集束用組成物、及びこれを用いた樹脂含浸繊維、熱可塑性樹脂組成物、成形品を提供することが可能である。 According to the second aspect of the invention, it is possible to provide a fiber bundling composition that is excellent in handleability and dispersibility, and a resin-impregnated fiber, a thermoplastic resin composition, and a molded product using the composition.

　本発明３、４によれば、成形品の曲げ強度を向上させることのできる熱可塑性樹脂エマルジョン、繊維集束用組成物、及びこれを用いた樹脂含浸繊維、成形品を提供することにある。 According to the present inventions 3 and 4, there are provided a thermoplastic resin emulsion and a fiber bundling composition that can improve the bending strength of molded articles, and resin-impregnated fibers and molded articles using the same.

　本発明５によれば、ポリエステル樹脂の加水分解を抑制する熱可塑性樹脂エマルジョンを含む繊維集束用組成物、及びこれを用いた樹脂含浸繊維、熱可塑性樹脂組成物、成形品を提供することが可能である。 According to the fifth aspect of the present invention, it is possible to provide a fiber bundling composition containing a thermoplastic resin emulsion that suppresses hydrolysis of a polyester resin, and a resin-impregnated fiber, a thermoplastic resin composition, and a molded product using the same. is.

　＜本発明１＞
　以下、本発明１につき詳細に説明する。 <Invention 1>
The present invention 1 will be described in detail below.

　本発明１の繊維集束用組成物に含まれる共重合体エマルジョンは、複数の単量体が重合した共重合体を含有する。複数の単量体は、芳香族ビニル系単量体を必須成分として含有する。芳香族ビニル系単量体としては、スチレン、α－メチルスチレン、ビニルトルエンおよびジビニルベンゼン等が挙げられ、これらを１種または２種以上使用することができる。特にスチレン、α－メチルスチレンの使用が好ましい。 The copolymer emulsion contained in the fiber bundling composition of the present invention 1 contains a copolymer obtained by polymerizing a plurality of monomers. A plurality of monomers contain an aromatic vinyl-based monomer as an essential component. Examples of the aromatic vinyl-based monomer include styrene, α-methylstyrene, vinyltoluene, divinylbenzene, and the like, and one or more of these can be used. Styrene and α-methylstyrene are particularly preferred.

　全単量体中の芳香族ビニル系単量体の含有量は、４０～９８．５重量％であることが必要であり、芳香族ビニル系単量体の含有量が４０重量％未満では、得られる樹脂含浸繊維の熱可塑性樹脂への分散性が低下し、９８．５重量％を超えると樹脂含浸繊維と熱可塑性樹脂との接着性に劣るため好ましくない。好ましくは４５～９５重量％、より好ましくは４７～９０重量％の範囲である。 The content of the aromatic vinyl-based monomer in the total monomers must be 40 to 98.5% by weight, and if the content of the aromatic vinyl-based monomer is less than 40% by weight, The dispersibility of the obtained resin-impregnated fibers in the thermoplastic resin is lowered, and if it exceeds 98.5% by weight, the adhesiveness between the resin-impregnated fibers and the thermoplastic resin is deteriorated, which is not preferable. The range is preferably 45-95% by weight, more preferably 47-90% by weight.

　本発明１の繊維集束用組成物に含まれる共重合体エマルジョンは、芳香族ビニル系単量体と共重合可能な他の単量体を含み、芳香族系ビニル単量体と共重合可能な他の単量体としては、エチレン系不飽和カルボン酸単量体、シアン化ビニル系単量体、アルキルエステル系単量体、ヒドロキシアルキル基を含有する不飽和単量体、不飽和カルボン酸アミド系単量体、ビニルピリジン系単量体、共役ジエン系単量体等が挙げられ、目的に応じて各々１種または２種以上混合して使用することが可能である。 The copolymer emulsion contained in the fiber bundling composition of the present invention 1 contains another monomer copolymerizable with the aromatic vinyl monomer, and is copolymerizable with the aromatic vinyl monomer. Other monomers include ethylenically unsaturated carboxylic acid monomers, vinyl cyanide monomers, alkyl ester monomers, unsaturated monomers containing hydroxyalkyl groups, and unsaturated carboxylic acid amides. monomers, vinylpyridine-based monomers, conjugated diene-based monomers, etc., and each may be used alone or in combination of two or more depending on the purpose.

　エチレン系不飽和カルボン酸単量体としては、アクリル酸、メタクリル酸、クロトン酸、マレイン酸、フマル酸、イタコン酸などのモノまたはジカルボン酸（無水物）等が挙げられる。 Examples of ethylenically unsaturated carboxylic acid monomers include mono- or dicarboxylic acids (anhydrides) such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, and itaconic acid.

　シアン化ビニル系単量体としては、アクリロニトリル、メタクリロニトリル、α－クロルアクリロニトリル、α－エチルアクリロニトリル等が挙げられる。 Examples of vinyl cyanide-based monomers include acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, α-ethylacrylonitrile and the like.

　アルキルエステル系単量体としては、メチルアクリレート、メチルメタクリレート、エチルアクリレート、エチルメタクリレート、ブチルアクリレート、グリシジルメタクリレート、ジメチルフマレート、ジエチルフマレート、ジメチルマレエート、ジエチルマルエート、ジメチルイタコネート、モノメチルフマレート、モノエチルフマレート、２－エチルヘキシルアクリレート等が挙げられる。 Alkyl ester monomers include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, glycidyl methacrylate, dimethyl fumarate, diethyl fumarate, dimethyl maleate, diethyl malate, dimethyl itaconate, and monomethyl fumarate. , monoethyl fumarate, 2-ethylhexyl acrylate and the like.

　ヒドロキシアルキル基を含有する不飽和単量体としては、β－ヒドロキシエチルアクリレート、β－ヒドロキシエチルメタクリレート、ヒドロキシプロピルアクリレート、ヒドロキシプロピルメタクリレート、ヒドロキシブチルアクリレート、ヒドロキシブチルメタクリレート、３－クロロ－２－ヒドロキシプロピルメタクリレート、ジ－（エチレングリコール）マレエート、ジ－（エチレングリコール）イタコネート、２－ヒドロキシエチルマレエート、ビス（２－ヒドロキシエチル）マレエート、２－ヒドロキシエチルメチルフマレート等が挙げられる。 Unsaturated monomers containing hydroxyalkyl groups include β-hydroxyethyl acrylate, β-hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, hydroxybutyl methacrylate, 3-chloro-2-hydroxypropyl Methacrylate, di-(ethylene glycol) maleate, di-(ethylene glycol) itaconate, 2-hydroxyethyl maleate, bis(2-hydroxyethyl) maleate, 2-hydroxyethyl methyl fumarate and the like.

　不飽和カルボン酸アミド系単量体としては、アクリルアミド、メタクリルアミド、Ｎ－メチロールアクリルアミド、Ｎ－メチロールメタクリルアミド、Ｎ，Ｎ－ジメチルアクリルアミド等が挙げられる。 Examples of unsaturated carboxylic acid amide-based monomers include acrylamide, methacrylamide, N-methylol acrylamide, N-methylol methacrylamide, and N,N-dimethylacrylamide.

　ビニルピリジン系単量体としては、２－ビニルピリジン、３－ビニルピリジン、４－ビニルピリジン、２－メチル－５－ビニルピリジン等が挙げられる。 Examples of vinylpyridine-based monomers include 2-vinylpyridine, 3-vinylpyridine, 4-vinylpyridine, and 2-methyl-5-vinylpyridine.

　共役ジエン系単量体としては、１，３－ブタジエン、２－メチル－１，３－ブタジエン、２，３－ジメチル－１，３－ブタジエン、２－クロル－１，３－ブタジエン、置換直鎖共役ペンタジエン類、置換および側鎖共役ヘキサジエン類等が挙げられる。 Conjugated diene-based monomers include 1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 2-chloro-1,3-butadiene, substituted linear Conjugated pentadienes, substituted and side chain conjugated hexadienes, and the like.

　中でも、芳香族系ビニル単量体と共重合可能な他の単量体としては、アクリル酸、メタクリル酸、フマル酸、イタコン酸、アクリロニトリル、メタクリロニトリル、メチルメタクリレート、ブチルアクリレート、β－ヒドロキシエチルアクリレート、アクリルアミドまたはメタクリルアミド、２－ビニルピリジン、１，３－ブタジエンの使用が好ましい。 Among others, other monomers copolymerizable with aromatic vinyl monomers include acrylic acid, methacrylic acid, fumaric acid, itaconic acid, acrylonitrile, methacrylonitrile, methyl methacrylate, butyl acrylate, and β-hydroxyethyl. Preference is given to using acrylates, acrylamides or methacrylamides, 2-vinylpyridine, 1,3-butadiene.

　全単量体中の「芳香族系ビニル単量体と共重合可能な他の単量体」の含有量は、１．５重量％以上であることが必要であり、１．５重量％未満では樹脂含浸繊維と熱可塑性樹脂との接着性に劣り、６０重量％を超えると樹脂含浸繊維の熱可塑性樹脂への分散性が劣るため好ましくない。好ましくは５～５５重量％、より好ましくは１０～５３重量％の範囲である。 The content of "other monomers copolymerizable with the aromatic vinyl monomer" in all monomers must be 1.5% by weight or more, and less than 1.5% by weight. If it exceeds 60% by weight, the dispersibility of the resin-impregnated fiber in the thermoplastic resin is poor, which is not preferable. It is preferably in the range of 5 to 55% by weight, more preferably 10 to 53% by weight.

　各単量体の好ましい組成比率としては、芳香族系ビニル単量体６０～９５重量％、シアン化ビニル系単量体４～３９重量％、エチレン系不飽和カルボン酸単量体１～１５重量％が挙げられ、さらに好ましい組成比率としては、芳香族系ビニル単量体８０～９４重量％、シアン化ビニル系単量体５～１５重量％、エチレン系不飽和カルボン酸単量体１～５重量％が挙げられる。 A preferable composition ratio of each monomer is 60 to 95% by weight of aromatic vinyl monomer, 4 to 39% by weight of vinyl cyanide monomer, and 1 to 15% by weight of ethylenically unsaturated carboxylic acid monomer. %, and more preferred composition ratios are 80 to 94% by weight of aromatic vinyl monomer, 5 to 15% by weight of vinyl cyanide monomer, and 1 to 5% of ethylenically unsaturated carboxylic acid monomer. % by weight.

　本発明１の繊維集束用組成物に含まれる共重合体エマルジョンは、乳化重合により得られるものであり、本発明１の目的を損なわない範囲であれば特に制限はなく公知の乳化重合法、例えば、一括添加方法、分割添加方法、連続添加方法、多段階重合法、シード重合法、パワーフィード重合法等の何れを採用してもよい。中でも重合時の安定性や分子量の調整の容易さから連続添加方法が好ましい。 The copolymer emulsion contained in the fiber bundling composition of the present invention 1 is obtained by emulsion polymerization, and is not particularly limited as long as the object of the present invention 1 is not impaired. , a batch addition method, a divided addition method, a continuous addition method, a multistage polymerization method, a seed polymerization method, a power feed polymerization method, and the like may be employed. Among them, the continuous addition method is preferable from the standpoint of stability during polymerization and ease of adjustment of the molecular weight.

　本発明１の繊維集束用組成物に含まれる共重合体エマルジョンの乳化重合の際には、ｎ－ヘキシルメルカプタン、ｎ－オクチルメルカプタン、ｔ－オクチルメルカプタン、ｎ－ドデシルメルカプタン、ｔ－ドデシルメルカプタン、ｎ－ステアリルメルカプタン等のアルキルメルカプタン、ジメチルキサントゲンジサルファイド、ジイソプロピルキサントゲンジサルファイド等のキサントゲン化合物、テトラメチルチウラムジスルフィド、テトラエチルチウラムジスルフィド、テトラメチルチウラムモノスルフィド等のチウラム系化合物、２，６－ジ－ｔ－ブチル－４－メチルフェノール、スチレン化フェノール等のフェノール系化合物、アリルアルコール等のアリル化合物、ジクロルメタン、ジブロモメタン、四臭化炭素等のハロゲン化炭化水素化合物、α－ベンジルオキシスチレン、α－ベンジルオキシアクリロニトリル、α－ベンジルオキシアクリルアミド等のビニルエーテル、トリフェニルエタン、ペンタフェニルエタン、アクロレイン、メタアクロレイン、チオグリコール酸、チオリンゴ酸、２－エチルヘキシルチオグリコレート、α－メチルスチレンダイマー、ターピノレン等の連鎖移動剤や過硫酸カリウム、過硫酸ナトリウム、過硫酸アンモニウム等の水溶性重合開始剤、クメンハイドロパーオキサイド、過酸化ベンゾイル、t－ブチルハイドロパーオキサイド、アセチルパーオキサイド、ジイソプロピルベンゼンハイドロパーオキサイド、１，１，３，３－テトラメチルブチルハイドロパーオキサイド等の油溶性重合開始剤、還元剤である硫酸第一鉄、亜硫酸塩、亜硫酸水素塩、ピロ亜硫酸塩、亜ニチオン酸塩、ニチオン酸塩、チオ硫酸塩、また、ホルムアルデヒドスルホン酸塩、ベンズアルデヒドスルホン酸塩などの還元性スルホン酸塩、更にはＬ－アスコルビン酸、酒石酸、クエン酸などのカルボン酸類、更にはデキストロース、サッカロースなどの還元糖類、更にはジメチルアニリン、トリエタノールアミンなどのアミン類の各々１種または２種以上の添加剤を使用することも可能であり、更にはこれらの添加量を調整することにより、目的とする分子量のものを得ることが可能である。これらの添加剤の使用量に特に制限は無いが、製品コストや最終製品の外観への影響を考えると、全単量体１００重量部に対して、各々０．０１～５重量部の範囲で使用することが好ましい。 During the emulsion polymerization of the copolymer emulsion contained in the fiber bundling composition of the present invention 1, n-hexylmercaptan, n-octylmercaptan, t-octylmercaptan, n-dodecylmercaptan, t-dodecylmercaptan, n - alkyl mercaptans such as stearyl mercaptan; xanthogen compounds such as dimethylxanthogen disulfide and diisopropyl xanthogen disulfide; thiuram compounds such as tetramethylthiuram disulfide, tetraethylthiuram disulfide and tetramethylthiuram monosulfide; Phenolic compounds such as butyl-4-methylphenol and styrenated phenol, allyl compounds such as allyl alcohol, halogenated hydrocarbon compounds such as dichloromethane, dibromomethane, and carbon tetrabromide, α-benzyloxystyrene, α-benzyloxy Acrylonitrile, vinyl ethers such as α-benzyloxyacrylamide, chain transfer agents such as triphenylethane, pentaphenylethane, acrolein, methacrolein, thioglycolic acid, thiomalic acid, 2-ethylhexylthioglycolate, α-methylstyrene dimer, and terpinolene and water-soluble polymerization initiators such as potassium persulfate, sodium persulfate and ammonium persulfate, cumene hydroperoxide, benzoyl peroxide, t-butyl hydroperoxide, acetyl peroxide, diisopropylbenzene hydroperoxide, 1,1,3 , an oil-soluble polymerization initiator such as 3-tetramethylbutyl hydroperoxide, a reducing agent ferrous sulfate, sulfite, hydrogen sulfite, pyrosulfite, nitionite, nitionate, thiosulfate, In addition, reducing sulfonates such as formaldehyde sulfonate and benzaldehyde sulfonate, further carboxylic acids such as L-ascorbic acid, tartaric acid and citric acid, further reducing sugars such as dextrose and saccharose, further dimethylaniline, It is also possible to use one or two or more additives for each of amines such as triethanolamine, and furthermore, by adjusting the amount of these additives, it is possible to obtain the desired molecular weight. is. There is no particular limit to the amount of these additives used, but considering the effect on the product cost and the appearance of the final product, each in the range of 0.01 to 5 parts by weight per 100 parts by weight of the total monomers. It is preferred to use

　本発明１の繊維集束用組成物に含まれる共重合体エマルジョンを乳化重合する際に使用される乳化剤に特に制限はなく、例えば、高級アルコールの硫酸エステル塩、アルキルベンゼンスルホン酸塩、アルキルジフェニルエーテルスルホン酸塩、脂肪族スルホン酸塩、脂肪族カルボン酸塩、非イオン性界面活性剤の硫酸エステル塩等のアニオン性界面活性剤あるいはポリエチレングリコールのアルキルエステル型、アルキルフェニルエーテル型、アルキルエーテル型等のノニオン性界面活性剤が挙げられ、これらを１種又は２種以上使用することができ、全単量体１００重量部に対して、０．０５～１０重量部の範囲で使用するのが好ましい。０．０５重量部未満では重合液の安定性に劣り、１０重量部を越えると最終製品での成型の際にガスが多量に発生し、成形品表面を損なう不具合が発生する。好ましくは０．１～８重量部、より好ましくは０．５～５重量部の範囲である。 The emulsifier used for emulsion polymerization of the copolymer emulsion contained in the fiber bundling composition of the present invention 1 is not particularly limited. Salts, aliphatic sulfonates, aliphatic carboxylates, anionic surfactants such as sulfuric acid ester salts of nonionic surfactants, or nonions such as alkyl ester types, alkylphenyl ether types, and alkyl ether types of polyethylene glycol One or more of these may be used, and it is preferable to use them in the range of 0.05 to 10 parts by weight per 100 parts by weight of the total monomers. If it is less than 0.05 parts by weight, the stability of the polymerization liquid is poor, and if it exceeds 10 parts by weight, a large amount of gas is generated during the molding of the final product, resulting in damage to the surface of the molded product. The range is preferably 0.1 to 8 parts by weight, more preferably 0.5 to 5 parts by weight.

　更に、重合時には、公知の電解質、重合促進剤、キレート剤等を使用することができる。 Furthermore, known electrolytes, polymerization accelerators, chelating agents, etc. can be used during polymerization.

　また、本発明１の繊維集束用組成物に含まれる共重合体エマルジョンの分子量は、その乳化重合時に用いる連鎖移動剤や重合開始剤の使用量、また、重合時間や重合温度を変えることによって調整することも可能である。連鎖移動剤は、全単量体１００重量部に対して、０．３～２．１重量部の範囲で使用することが好ましい。重合開始剤は、全単量体１００重量部に対して、０．１～０．３重量部の範囲で使用することが好ましい。重合時間や重合温度に特に制限はなく、重合温度に関しては、一定温度での重合や重合途中で重合温度に傾斜をかける方法等、本発明１の目的を損なわない範囲で調整することが可能である。生産性の点から、重合時間については３～１５時間の範囲であることが好ましく、重合温度については４０～９０℃の範囲で行うことが好ましく、７０～８５℃の範囲で行うことがより好ましい。 Further, the molecular weight of the copolymer emulsion contained in the fiber bundling composition of the present invention 1 is adjusted by changing the amount of the chain transfer agent and polymerization initiator used in the emulsion polymerization, and the polymerization time and polymerization temperature. It is also possible to The chain transfer agent is preferably used in an amount of 0.3 to 2.1 parts by weight per 100 parts by weight of all monomers. It is preferable to use the polymerization initiator in the range of 0.1 to 0.3 parts by weight with respect to 100 parts by weight of all the monomers. The polymerization time and polymerization temperature are not particularly limited, and the polymerization temperature can be adjusted within a range that does not impair the object of the present invention 1, such as polymerization at a constant temperature or a method of ramping the polymerization temperature during polymerization. be. From the viewpoint of productivity, the polymerization time is preferably in the range of 3 to 15 hours, and the polymerization temperature is preferably in the range of 40 to 90°C, more preferably in the range of 70 to 85°C. .

　本発明１の繊維集束用組成物に含まれる共重合体エマルジョンのガラス転移温度は１１０℃以下であることが、繊維間への含浸の点から好ましい。特に好ましくは１０５℃以下である。尚、ガラス転移温度は通常のＤＳＣ法により測定することが可能である。 The glass transition temperature of the copolymer emulsion contained in the fiber bundling composition of the present invention 1 is preferably 110°C or less from the viewpoint of impregnation between fibers. Particularly preferably, it is 105° C. or less. Incidentally, the glass transition temperature can be measured by a normal DSC method.

　本発明１の繊維集束用組成物に含まれる共重合体エマルジョンの数平均分子量は、０．５×１０４～４×１０４の範囲にあることが必要である。数平均分子量が、０．５×１０４より低いと本発明１の目的である最終製品での強度が劣り、４×１０４を超えると本発明１の特徴である繊維間への含浸性が低下する。好ましくは０．６×１０４～３．５×１０４、より好ましくは０．８×１０４～３×１０４の範囲である。 The number-average molecular weight of the copolymer emulsion contained in the fiber bundling composition of the present invention 1 must be in the range of 0.5×10 4 to 4×10 4 . If the number average molecular weight is lower than 0.5×10 4 , the strength of the final product, which is the object of the present invention 1, is inferior, and if it exceeds 4×10 4 , the impregnation between fibers, which is the feature of the present invention 1, is poor. descend. The range is preferably 0.6×10 4 to 3.5×10 4 , more preferably 0.8×10 4 to 3×10 4 .

　尚、この数平均分子量は、ＵＶ検出装置、カラム（Ａｇｉｌｅｎｔ社製　ＭＩＸＤ－Ｂ　５０℃）を備えた市販のゲルパーミエーションクロマトグラム（ＧＰＣ）測定装置を用いて、溶媒テトラヒドロフラン（ＴＨＦ）、流量１ｍｌ／ｍｉｎ、検出波長２５４ｎｍの条件で測定したポリスチレン換算分子量である。 The number average molecular weight was measured using a commercially available gel permeation chromatogram (GPC) measurement device equipped with a UV detector and a column (Agilent MIXD-B 50°C) using tetrahydrofuran (THF) as the solvent and a flow rate of 1 ml. /min, the polystyrene-equivalent molecular weight measured under the conditions of a detection wavelength of 254 nm.

　本発明１の繊維集束用組成物に含まれる共重合体エマルジョンのテトラヒドロフラン不溶部は、共重合体エマルジョンの固形分中に、１０重量％未満であることが、繊維間への含浸の点から好ましい。更に好ましくは５重量％未満である。 The tetrahydrofuran-insoluble portion of the copolymer emulsion contained in the fiber bundling composition of the present invention 1 is preferably less than 10% by weight in the solid content of the copolymer emulsion from the viewpoint of impregnation between fibers. . More preferably less than 5% by weight.

　上記テトラヒドロフラン不溶部は、下記により求めることができる。 The tetrahydrofuran-insoluble portion can be obtained as follows.

　水酸化ナトリウムを用いてｐＨ８に調整した共重合体エマルジョンを２３℃で１２時間燥後、２３℃で２４時間減圧乾燥することでフィルムを作製した。得られたフィルムを５ｍｍ角に裁断し、約１ｇ秤量しＸｇとする。これをテトラヒドロフラン１００ｍｌに２４時間浸漬した後、３００メッシュの金網を用いてろ過し、その後テトラヒドロフランを蒸発乾燥させた重量から金網重量を減じて、試料の乾燥後重量を秤量しＹｇとする。 A film was produced by drying the copolymer emulsion adjusted to pH 8 using sodium hydroxide at 23°C for 12 hours and then drying it under reduced pressure at 23°C for 24 hours. The obtained film is cut into 5 mm squares, and weighed about 1 g to be X g. After immersing this in 100 ml of tetrahydrofuran for 24 hours, it is filtered using a 300-mesh wire mesh, and then the weight of the dried tetrahydrofuran is subtracted from the weight of the wire mesh.

　テトラヒドロフランに対する不溶部（重量％）＝Ｙ／Ｘ×１００
　上記、ガラス転移温度やテトラヒドロフラン不溶部量の調整は、単量体の混合比率、重合時に用いる添加剤の種類や量、重合温度、重合後に添加する添加剤等により調整することが可能である。 Insoluble portion in tetrahydrofuran (% by weight) = Y/X x 100
The glass transition temperature and the amount of the tetrahydrofuran-insoluble portion can be adjusted by adjusting the mixing ratio of the monomers, the type and amount of additives used during polymerization, the polymerization temperature, additives added after polymerization, and the like.

　また、本発明１の繊維集束用組成物には、他の樹脂エマルジョン、分散剤、レベリング剤、滑剤、消泡剤、濡れ剤、防腐剤、酸化防止剤、紫外線吸収剤、光安定化剤、着色剤、帯電防止剤、可塑剤等を本発明１の効果を損なわない範囲に配合して使用することが可能である。 In addition, the composition for fiber bundling of the present invention 1 contains other resin emulsions, dispersants, leveling agents, lubricants, antifoaming agents, wetting agents, preservatives, antioxidants, ultraviolet absorbers, light stabilizers, A coloring agent, an antistatic agent, a plasticizer, etc. can be mixed and used within a range that does not impair the effects of the first invention.

　他の樹脂エマルジョンとしては、例えば、ウレタン系エマルジョン、アクリル系エマルジョン、酢酸ビニル系エマルジョン、塩化ビニリデン系エマルジョン、オレフィン系樹脂エマルジョン等の熱可塑性樹脂エマルジョンから選ばれたものが本発明１における繊維集束用組成物の特性の点から好ましい。 As other resin emulsions, for example, those selected from thermoplastic resin emulsions such as urethane emulsions, acrylic emulsions, vinyl acetate emulsions, vinylidene chloride emulsions, and olefin resin emulsions are used for fiber bundling in Invention 1. It is preferable from the viewpoint of the properties of the composition.

　本発明１の繊維集束用組成物中の共重合体エマルジョンの含有割合（固形分換算）は、８０重量％以上であることが好ましく、９０重量％以上であることがより好ましい。また、繊維集束用組成物中の他の樹脂エマルジョンの含有割合（固形分換算）は、２０重量％以下であることが好ましく、１０重量％以下であることがより好ましい。 The content of the copolymer emulsion in the fiber bundling composition of the first invention (in terms of solid content) is preferably 80% by weight or more, more preferably 90% by weight or more. The content of the other resin emulsion in the fiber bundling composition (in terms of solid content) is preferably 20% by weight or less, more preferably 10% by weight or less.

　本発明１の繊維集束用組成物を繊維に含浸させる方法には特に制限はなく、スプレー法や塗布法または含浸法等の方法から１種または２種以上組み合わせて選択することが可能である。 The method for impregnating fibers with the fiber bundling composition of the present invention 1 is not particularly limited, and it is possible to select one or a combination of two or more from methods such as a spray method, a coating method, and an impregnation method.

　本発明１の繊維集束用組成物を含浸させる繊維としては、炭素繊維、ガラス繊維、硼素繊維、炭化ケイ素繊維、あるいはアルミウム繊維、ステンレス繊維、銅繊維、ニッケル繊維などの金属繊維、ポリアミド繊維、ポリエステル繊維、ポリアリレート繊維、ポリイミド繊維、（ナノ）セルロース繊維などの有機繊維等を用いることが出来る。さらにこれらの繊維は１種または２種以上を組み合わせて用いることも可能である。中でも、炭素繊維が最も好ましい。炭素繊維には、通常の炭素繊維に加えて、ニッケルなどの金属で被覆処理した炭素繊維なども含まれ、かつその形態に特に制限はなく、連続繊維、チョップド繊維、ミルド形状や不織布等、目的に応じて任意の形態のものを選ぶことが可能である。 Examples of fibers to be impregnated with the fiber bundling composition of the present invention 1 include carbon fiber, glass fiber, boron fiber, silicon carbide fiber, metal fiber such as aluminum fiber, stainless fiber, copper fiber, nickel fiber, polyamide fiber, and polyester. Organic fibers such as fibers, polyarylate fibers, polyimide fibers, and (nano)cellulose fibers can be used. Furthermore, these fibers can be used singly or in combination of two or more. Among them, carbon fiber is most preferred. In addition to ordinary carbon fibers, carbon fibers include carbon fibers coated with metal such as nickel, and there are no particular restrictions on the form thereof, and may be continuous fibers, chopped fibers, milled shapes, non-woven fabrics, etc. Any form can be selected according to the requirements.

　本発明１における繊維集束用組成物と繊維の含浸比率には特に制限は無いが、熱可塑性樹脂との接着性や最終製品の強度面から、固形分換算で、繊維集束用組成物１～２０重量部、繊維９９～８０重量部の範囲で含浸させることが好ましい。 Although there is no particular limitation on the impregnation ratio of the fiber bundling composition and the fibers in Invention 1, from the standpoint of adhesiveness to the thermoplastic resin and strength of the final product, the fiber bundling composition is 1 to 20 in terms of solid content. It is preferable to impregnate in the range of 99 to 80 parts by weight of fibers.

　本発明１の樹脂含浸繊維における、繊維に繊維集束用組成物を含浸させた後の水分の蒸発方法については特に制限はなく、例えば乾燥機を使用する方法、赤外線を照射する方法、連続的に乾燥機を通過させる方法等を目的に応じて採用することが可能である。中でも、水分の蒸発だけではなく、含浸した繊維集束用組成物を溶融させ、繊維表面を更に均一に被覆させるために、繊維集束用組成物のガラス転移温度＋６０℃以上に調整された１ｍ以上の行路を持つ乾燥機内を０．５ｍ/分以上の速度で連続的に通過させながら乾燥することが好ましい。 In the resin-impregnated fiber of the present invention 1, the method of evaporating water after impregnating the fiber with the fiber bundling composition is not particularly limited, and for example, a method using a dryer, a method of irradiating infrared rays, and a continuous method. A method of passing through a dryer or the like can be employed depending on the purpose. Above all, in order not only to evaporate water but also to melt the impregnated fiber bundling composition and more uniformly coat the fiber surface, the glass transition temperature of the fiber bundling composition + 1 m or more adjusted to 60 ° C. or higher It is preferable to dry while continuously passing through a dryer having tracks at a speed of 0.5 m/min or more.

　本発明１の樹脂含浸繊維は、熱可塑性樹脂と溶融混練し、繊維強化熱可塑性樹脂組成物として用いることができる。さらに、熱可塑性樹脂シートまたはフィルムと積層させた積層品として用いることもできる。 The resin-impregnated fiber of the present invention 1 can be melt-kneaded with a thermoplastic resin and used as a fiber-reinforced thermoplastic resin composition. Furthermore, it can also be used as a laminate laminated with a thermoplastic resin sheet or film.

　本発明１の樹脂含浸繊維と組み合わせる熱可塑性樹脂としては、例えば、ポリスチレン（ＰＳ）、耐衝撃性ポリスチレン（ＨＩＰＳ）、アクリロニトリル－ブタジエンゴム－スチレン共重合体（ＡＢＳ）、アクリロニトリル－エチレンプロピレンゴム－スチレン共重合体（ＡＥＳ）、アクリロニトリル－アクリルゴム－スチレン共重合体（ＡＳＡ）、アクリロニトリル－スチレン共重合体（ＡＳ）等のスチレン系樹脂、ポリエチレン（ＰＥ）、ポリプロピレン（ＰＰ）等のポリオレフィン樹脂、ポリカーボネート（ＰＣ）、ポリエチレンテレフタレート（ＰＥＴ）、ポリブチレンテレフタレート（ＰＢＴ）等のポリエステル樹脂、ポリメチルメタクリレート（ＰＭＭＡ）、ポリアミド（ＰＡ）、熱可塑性ポリウレタン樹脂（ＴＰＵ）、ポリ乳酸樹脂（ＰＬＡ）、ポリエーテルサルフォン（ＰＥＳ）、ポリフェニレンサルファイド（ＰＰＳ）あるいはスチレン系樹脂と、ポリカーボネート（ＰＣ）、ポリアミド樹脂（ＰＡ）、及びポリ乳酸樹脂（ＰＬＡ）から選ばれる１種以上の樹脂とのアロイが例示され、最終製品の要求性能に合わせて１種又は２種以上組み合わせて用いることが可能である。中でもスチレン系樹脂およびスチレン系樹脂とのアロイが最終製品の成形性と強度のバランスの点で好ましい。 Examples of the thermoplastic resin to be combined with the resin-impregnated fiber of the present invention 1 include polystyrene (PS), high-impact polystyrene (HIPS), acrylonitrile-butadiene rubber-styrene copolymer (ABS), acrylonitrile-ethylene propylene rubber-styrene. Copolymer (AES), acrylonitrile-acrylic rubber-styrene copolymer (ASA), acrylonitrile-styrene copolymer (AS) and other styrene resins, polyethylene (PE), polypropylene (PP) and other polyolefin resins, polycarbonate (PC), polyester resins such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polymethyl methacrylate (PMMA), polyamide (PA), thermoplastic polyurethane resin (TPU), polylactic acid resin (PLA), polyether Examples include alloys of sulfone (PES), polyphenylene sulfide (PPS) or styrenic resin and one or more resins selected from polycarbonate (PC), polyamide resin (PA), and polylactic acid resin (PLA), It is possible to use one or a combination of two or more according to the required performance of the final product. Among them, styrene-based resins and alloys with styrene-based resins are preferable from the viewpoint of the balance between moldability and strength of the final product.

　本発明１の樹脂含浸繊維と組み合せる熱可塑性樹脂には、例えば、光安定剤、酸化防止剤、熱安定剤、紫外線吸収剤、滑剤、難燃剤、難燃助剤、可塑剤、顔料、染料等の各種添加剤を含むこともできる。 The thermoplastic resin to be combined with the resin-impregnated fiber of the present invention 1 includes, for example, a light stabilizer, an antioxidant, a heat stabilizer, an ultraviolet absorber, a lubricant, a flame retardant, a flame retardant aid, a plasticizer, a pigment, and a dye. Various additives such as can also be included.

　本発明１の樹脂含浸繊維と熱可塑性樹脂とを溶融混練して得られた繊維強化熱可塑性樹脂組成物は、例えば、射出成形、多層押し出し成形、フィルム成形、シート成形、インフレーション成形、プレス成形、ＳＭＣ成形法、ＬＦＴ－Ｄ法等、目的に応じた加工法を採用することで成形品を得ることが可能である。また、場合によっては予備賦形を行う工程を挟むことも可能である。 The fiber-reinforced thermoplastic resin composition obtained by melt-kneading the resin-impregnated fiber of the present invention 1 and a thermoplastic resin can be, for example, injection molding, multilayer extrusion molding, film molding, sheet molding, inflation molding, press molding, A molded article can be obtained by adopting a processing method according to the purpose, such as the SMC molding method and the LFT-D method. In some cases, it is also possible to interpose a step of pre-shaping.

　本発明１の樹脂含浸繊維からなる層を熱可塑性樹脂シートまたはフィルムと積層させた積層体は、プレス成型等により成形品を得ることができる。また、場合によっては予備賦形を行う工程を挟むことも可能である。 A laminate obtained by laminating a layer made of the resin-impregnated fiber of the present invention 1 with a thermoplastic resin sheet or film can be molded by press molding or the like. In some cases, it is also possible to interpose a step of pre-shaping.

　成形品の加工温度に特に制限はなく、使用される熱可塑性樹脂の特性により任意の温度を選択することが可能であるが、成形サイクルの点から１８０～２７０℃の範囲で成形することが好ましく、更に好ましくは１８０～２５０℃の範囲である。 There is no particular limitation on the processing temperature of the molded product, and it is possible to select any temperature according to the properties of the thermoplastic resin used, but it is preferable to mold in the range of 180 to 270 ° C. , and more preferably in the range of 180 to 250°C.

　＜本発明２＞
　以下、本発明２につき詳細に説明する。 <Invention 2>
The present invention 2 will be described in detail below.

　本発明２の繊維集束用組成物は、熱可塑性樹脂エマルジョンを含むものである。 The fiber bundling composition of the present invention 2 contains a thermoplastic resin emulsion.

　本発明２の繊維集束用組成物に含まれる熱可塑性樹脂エマルジョンは、熱可塑性樹脂の水分散体であれば特に制限なく、例えば、ポリエステル系樹脂エマルジョン、ポリウレタン系樹脂エマルジョン、酢酸ビニル系樹脂エマルジョン、塩化ビニリデン系樹脂エマルジョン、ポリアミド系樹脂エマルジョン、芳香族ビニル系樹脂エマルジョン、アクリル系樹脂エマルジョン、オレフィン系樹脂エマルジョンなどが挙げられる。 The thermoplastic resin emulsion contained in the fiber bundling composition of the present invention 2 is not particularly limited as long as it is an aqueous dispersion of a thermoplastic resin. Examples include polyester resin emulsion, polyurethane resin emulsion, vinyl acetate resin emulsion, Examples include vinylidene chloride resin emulsions, polyamide resin emulsions, aromatic vinyl resin emulsions, acrylic resin emulsions, and olefin resin emulsions.

　中でも、集束された繊維の取り扱いの容易さや最終製品の性能の点から、熱可塑性樹脂エマルジョンは、好ましくは、エチレン系不飽和カルボン酸単量体を含有する複数の単量体が重合した共重合体を含有する。 Among them, the thermoplastic resin emulsion is preferably a copolymer obtained by polymerizing a plurality of monomers containing an ethylenically unsaturated carboxylic acid monomer, from the viewpoint of ease of handling of bundled fibers and performance of the final product. Contains coalescence.

　エチレン系不飽和カルボン酸単量体としては、アクリル酸、メタクリル酸及びクロトン酸などのモノカルボン酸単量体、マレイン酸、フマル酸及びイタコン酸などのジカルボン酸単量体並びにこれらの無水物が挙げられる。これらの単量体は１種を単独でまたは２種以上を組み合わせて使用することができる。特にアクリル酸、メタクリル酸、イタコン酸の使用が好ましい。 Ethylenically unsaturated carboxylic acid monomers include monocarboxylic acid monomers such as acrylic acid, methacrylic acid and crotonic acid, dicarboxylic acid monomers such as maleic acid, fumaric acid and itaconic acid, and their anhydrides. mentioned. These monomers can be used individually by 1 type or in combination of 2 or more types. The use of acrylic acid, methacrylic acid and itaconic acid is particularly preferred.

　エチレン系不飽和カルボン酸単量体と共重合可能な他の単量体としては、芳香族ビニル系単量体、シアン化ビニル系単量体、アルキルエステル系単量体、ヒドロキシアルキル基を含有する不飽和単量体、不飽和カルボン酸アミド系単量体、ビニルピリジン系単量体、オキサゾリン系単量体、共役ジエン系単量体等が挙げられ、目的に応じて各々１種または２種以上混合して使用することが可能である。 Other monomers copolymerizable with ethylenically unsaturated carboxylic acid monomers include aromatic vinyl monomers, vinyl cyanide monomers, alkyl ester monomers, and hydroxyalkyl group-containing monomers. unsaturated monomers, unsaturated carboxylic acid amide-based monomers, vinylpyridine-based monomers, oxazoline-based monomers, and conjugated diene-based monomers. It is possible to use a mixture of more than one species.

　芳香族ビニル系単量体としては、スチレン、α－メチルスチレン、ビニルトルエンおよびジビニルベンゼン等が挙げられ、これらを１種または２種以上使用することができる。 The aromatic vinyl-based monomers include styrene, α-methylstyrene, vinyltoluene, divinylbenzene, and the like, and one or more of these can be used.

　シアン化ビニル系単量体としては、アクリロニトリル、メタクリロニトリル、α－クロルアクリロニトリル、α－エチルアクリロニトリル等が挙げられ、これらを１種または２種以上使用することができる。 Examples of vinyl cyanide-based monomers include acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, α-ethylacrylonitrile, and the like, and one or more of these can be used.

　アルキルエステル系単量体としては、メチルアクリレート、メチルメタクリレート、エチルアクリレート、エチルメタクリレート、ブチルアクリレート、グリシジルメタクリレート、ジメチルフマレート、ジエチルフマレート、ジメチルマレエート、ジエチルマルエート、ジメチルイタコネート、モノメチルフマレート、モノエチルフマレート、２－エチルヘキシルアクリレート等が挙げられ、これらを１種または２種以上使用することができる。 Alkyl ester monomers include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, glycidyl methacrylate, dimethyl fumarate, diethyl fumarate, dimethyl maleate, diethyl malate, dimethyl itaconate, and monomethyl fumarate. , monoethyl fumarate, 2-ethylhexyl acrylate and the like, and one or more of these can be used.

　ヒドロキシアルキル基を含有する不飽和単量体としては、β－ヒドロキシエチルアクリレート、β－ヒドロキシエチルメタクリレート、ヒドロキシプロピルアクリレート、ヒドロキシプロピルメタクリレート、ヒドロキシブチルアクリレート、ヒドロキシブチルメタクリレート、３－クロロ－２－ヒドロキシプロピルメタクリレート、ジ－（エチレングリコール）マレエート、ジ－（エチレングリコール）イタコネート、２－ヒドロキシエチルマレエート、ビス（２－ヒドロキシエチル）マレエート、２－ヒドロキシエチルメチルフマレート等が挙げられ、これらを１種または２種以上使用することができる。 Unsaturated monomers containing hydroxyalkyl groups include β-hydroxyethyl acrylate, β-hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, hydroxybutyl methacrylate, 3-chloro-2-hydroxypropyl methacrylate, di-(ethylene glycol) maleate, di-(ethylene glycol) itaconate, 2-hydroxyethyl maleate, bis(2-hydroxyethyl) maleate, 2-hydroxyethyl methyl fumarate and the like, one of which Or 2 or more types can be used.

　不飽和カルボン酸アミド系単量体としては、アクリルアミド、メタクリルアミド、Ｎ－メチロールアクリルアミド、Ｎ－メチロールメタクリルアミド、Ｎ，Ｎ－ジメチルアクリルアミド等が挙げられ、これらを１種または２種以上使用することができる。 Examples of unsaturated carboxylic acid amide-based monomers include acrylamide, methacrylamide, N-methylol acrylamide, N-methylol methacrylamide, N,N-dimethylacrylamide and the like, and one or more of these may be used. can be done.

　ビニルピリジン系単量体としては、２－ビニルピリジン、３－ビニルピリジン、４－ビニルピリジン、２－メチル－５－ビニルピリジン等が挙げられ、これらを１種または２種以上使用することができる。 Vinylpyridine-based monomers include 2-vinylpyridine, 3-vinylpyridine, 4-vinylpyridine, 2-methyl-5-vinylpyridine and the like, and one or more of these may be used. .

　オキサゾリン系単量体としては、例えば２－ビニル－２－オキサゾリンや４，４－ジメチル－２－ビニル－２－オキサゾリン－５－オン等が挙げられ、これらを１種または２種以上使用することができる。 Examples of oxazoline-based monomers include 2-vinyl-2-oxazoline and 4,4-dimethyl-2-vinyl-2-oxazoline-5-one, and one or more of these may be used. can be done.

　共役ジエン系単量体としては、１，３－ブタジエン、２－メチル－１，３－ブタジエン、２，３－ジメチル－１，３－ブタジエン、２－クロル－１，３－ブタジエン等が挙げられ、これらを１種または２種以上使用することができる。 Conjugated diene monomers include 1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 2-chloro-1,3-butadiene and the like. , these can be used alone or in combination of two or more.

　中でも、エチレン系不飽和カルボン酸単量体と共重合可能な他の単量体として、スチレン、α－メチルスチレン、アクリロニトリル、メチルメタクリレート、ブチルアクリレート、β－ヒドロキシエチルアクリレート、アクリルアミドまたはメタクリルアミド、２－ビニルピリジン、１，３－ブタジエンの使用が好ましい。 Among others, other monomers copolymerizable with ethylenically unsaturated carboxylic acid monomers include styrene, α-methylstyrene, acrylonitrile, methyl methacrylate, butyl acrylate, β-hydroxyethyl acrylate, acrylamide or methacrylamide, 2 -Vinylpyridine, 1,3-butadiene is preferred.

　全単量体中のエチレン系不飽和カルボン酸単量体の含有量は、０．１～２０重量％であることが好ましく、０．５～１８重量％がより好ましく、１～１６重量％がさらに好ましい。この範囲に調整することで集束性と最終製品中での繊維の分散性のバランスに優れる傾向にある。 The content of the ethylenically unsaturated carboxylic acid monomer in all monomers is preferably 0.1 to 20% by weight, more preferably 0.5 to 18% by weight, and 1 to 16% by weight. More preferred. Adjustment within this range tends to provide an excellent balance between bundling properties and fiber dispersibility in the final product.

　熱可塑性樹脂エマルジョンの各単量体の好ましい組成比率としては、芳香族ビニル系単量体６０～９５重量％、シアン化ビニル系単量体４～３９重量％、エチレン系不飽和カルボン酸単量体１～１５重量％が挙げられ、さらに好ましい組成比率としては、芳香族ビニル系単量体８０～９４重量％、シアン化ビニル系単量体５～１５重量％、エチレン系不飽和カルボン酸単量体１～５重量％が挙げられる。 The preferable composition ratio of each monomer in the thermoplastic resin emulsion is 60 to 95% by weight of aromatic vinyl monomer, 4 to 39% by weight of vinyl cyanide monomer, and ethylenically unsaturated carboxylic acid monomer. 1 to 15% by weight of aromatic vinyl monomers, 5 to 15% by weight of vinyl cyanide monomers, and ethylenically unsaturated carboxylic acid monomers. from 1 to 5% by weight.

　本発明２の繊維集束用組成物に含まれる熱可塑性樹脂エマルジョンが、乳化重合により得られる場合、公知の乳化重合法、例えば、一括添加方法、分割添加方法、連続添加方法、多段階重合法、シード重合法、パワーフィード重合法等の何れを採用してもよい。中でも重合時の安定性や分子量の調整の容易さから連続添加方法が好ましい。 When the thermoplastic resin emulsion contained in the fiber bundling composition of the present invention 2 is obtained by emulsion polymerization, known emulsion polymerization methods such as batch addition method, divided addition method, continuous addition method, multistage polymerization method, Either a seed polymerization method, a power feed polymerization method, or the like may be employed. Among them, the continuous addition method is preferable from the standpoint of stability during polymerization and ease of adjustment of the molecular weight.

　本発明２の繊維集束用組成物に含まれる熱可塑性樹脂エマルジョンを乳化重合する際に用いられる乳化剤としては、例えば、高級アルコールの硫酸エステル塩、アルキルベンゼンスルホン酸塩、アルキルジフェニルエーテルジスルホン酸塩、脂肪族スルホン酸塩、脂肪族カルボン酸塩、デヒドロアビエチン酸塩、ナフタレンスルホン酸のホルマリン縮合物、非イオン性界面活性剤の硫酸エステル塩等のアニオン性界面活性剤、ポリエチレングリコールのアルキルエステル型、アルキルフェニルエーテル型、及びアルキルエーテル型等のノニオン性界面活性剤などが挙げられる。これらは１種を単独でまたは２種以上を組み合わせて使用することができる。乳化剤の配合量は、他の添加剤などの組み合わせを考慮して適宜調整することができる。中でも、アルキルベンゼンスルホン酸塩、アルキルジフェニルエーテルジスルホン酸塩、脂肪族スルホン酸塩、ノニオン系界面活性剤がエマルジョンの安定性の面から好ましい。 Examples of the emulsifier used in the emulsion polymerization of the thermoplastic resin emulsion contained in the fiber bundling composition of the present invention 2 include sulfuric acid ester salts of higher alcohols, alkylbenzenesulfonates, alkyldiphenylether disulfonates, and aliphatic Anionic surfactants such as sulfonates, aliphatic carboxylates, dehydroabietic acid salts, formalin condensates of naphthalenesulfonic acid, sulfate ester salts of nonionic surfactants, alkyl esters of polyethylene glycol, alkylphenyls nonionic surfactants such as ether type and alkyl ether type; These can be used individually by 1 type or in combination of 2 or more types. The amount of the emulsifier to be blended can be appropriately adjusted in consideration of the combination with other additives. Among them, alkylbenzenesulfonates, alkyldiphenylether disulfonates, aliphatic sulfonates, and nonionic surfactants are preferred from the viewpoint of emulsion stability.

　乳化重合の際に使用される乳化剤は、全単量体１００重量部に対して、０．０５～１０重量部の範囲で使用するのが好ましい。０．０５部未満ではエマルジョンの安定性に劣るため含浸処理の際の歩留まりが低下し、１０重量部を越えると最終製品の成型の際にガスが多量に発生し成形品表面を損なう不具合や最終製品の強度低下が発生する傾向がある。好ましくは０．０６～８重量部、より好ましくは０．０８～５重量部の範囲である。 The emulsifier used during emulsion polymerization is preferably used in the range of 0.05 to 10 parts by weight with respect to 100 parts by weight of all the monomers. If it is less than 0.05 part by weight, the stability of the emulsion is poor and the yield at the time of impregnation treatment is lowered. Product strength tends to decrease. The range is preferably 0.06 to 8 parts by weight, more preferably 0.08 to 5 parts by weight.

　本発明２の繊維集束用組成物に含まれる熱可塑性樹脂エマルジョンを乳化重合する際に用いられる重合開始剤としては、例えば、過硫酸リチウム、過硫酸カリウム、過硫酸ナトリウム、過硫酸アンモニウム等の水溶性重合開始剤、クメンハイドロパーオキサイド、過酸化ベンゾイル、ｔ－ブチルハイドロパーオキサイド、アセチルパーオキサイド、ジイソプロピルベンゼンハイドロパーオキサイド、及び１，１，３，３－テトラメチルブチルハイドロパーオキサイド等の油溶性重合開始剤が挙げられる。これらは１種を単独でまたは２種以上を組み合わせて使用することができる。これらのうち、過硫酸カリウム、過硫酸ナトリウム、クメンハイドロパーオキサイド、又はｔ－ブチルハイドロパーオキサイドを用いることが好ましい。重合開始剤の配合量は、単量体組成、重合反応系のｐＨ、他の添加剤などの組み合わせを考慮して適宜調整される。 Examples of polymerization initiators used in emulsion polymerization of the thermoplastic resin emulsion contained in the fiber bundling composition of the present invention 2 include water-soluble agents such as lithium persulfate, potassium persulfate, sodium persulfate and ammonium persulfate. Oil-soluble polymerization initiators such as cumene hydroperoxide, benzoyl peroxide, t-butyl hydroperoxide, acetyl peroxide, diisopropylbenzene hydroperoxide, and 1,1,3,3-tetramethylbutyl hydroperoxide initiators. These can be used individually by 1 type or in combination of 2 or more types. Among these, it is preferable to use potassium persulfate, sodium persulfate, cumene hydroperoxide, or t-butyl hydroperoxide. The amount of the polymerization initiator to be blended is appropriately adjusted in consideration of the monomer composition, the pH of the polymerization reaction system, the combination of other additives, and the like.

　本発明２の繊維集束用組成物に含まれる熱可塑性樹脂エマルジョンを乳化重合する際に用いられる連鎖移動剤としては、例えば、ｎ－ヘキシルメルカプタン、ｎ－オクチルメルカプタン、ｔ－オクチルメルカプタン、ｎ－ドデシルメルカプタン、ｔ－ドデシルメルカプタン、ｎ－ステアリルメルカプタン等のアルキルメルカプタン；ジメチルキサントゲンジサルファイド、ジイソプロピルキサントゲンジサルファイド等のキサントゲン化合物；テトラメチルチウラムジスルフィド、テトラエチルチウラムジスルフィド、テトラメチルチウラムモノスルフィド等のチウラム系化合物；２，６－ジ－ｔ－ブチル－４－メチルフェノール、スチレン化フェノール等のフェノール系化合物；アリルアルコール等のアリル化合物；ジクロルメタン、ジブロモメタン、四臭化炭素等のハロゲン化炭化水素化合物；α－ベンジルオキシスチレン、α－ベンジルオキシアクリロニトリル、α－ベンジルオキシアクリルアミド等のビニルエーテル；トリフェニルエタン、ペンタフェニルエタン、アクロレイン、メタアクロレイン、チオグリコール酸、チオリンゴ酸、２－エチルヘキシルチオグリコレート、ターピノレン、α－メチルスチレンダイマーなどの連鎖移動剤が挙げられる。これらは１種を単独でまたは２種以上を組み合わせて使用することができる。連鎖移動剤の配合量は、他の添加剤などの組み合わせを考慮して適宜調整することができる。 Examples of the chain transfer agent used in emulsion polymerization of the thermoplastic resin emulsion contained in the fiber bundling composition of the present invention 2 include n-hexylmercaptan, n-octylmercaptan, t-octylmercaptan, and n-dodecyl. Alkyl mercaptans such as mercaptan, t-dodecyl mercaptan and n-stearyl mercaptan; xanthogen compounds such as dimethylxanthogen disulfide and diisopropyl xanthogen disulfide; thiuram compounds such as tetramethylthiuram disulfide, tetraethylthiuram disulfide and tetramethylthiuram monosulfide; Phenolic compounds such as 2,6-di-t-butyl-4-methylphenol and styrenated phenol; Allyl compounds such as allyl alcohol; Dichloromethane, dibromomethane, halogenated hydrocarbon compounds such as carbon tetrabromide; Vinyl ethers such as benzyloxystyrene, α-benzyloxyacrylonitrile, α-benzyloxyacrylamide; Chain transfer agents such as methylstyrene dimer are included. These can be used individually by 1 type or in combination of 2 or more types. The blending amount of the chain transfer agent can be appropriately adjusted in consideration of the combination with other additives.

　本発明２の繊維集束用組成物に含まれる熱可塑性樹脂エマルジョンを乳化重合する際に用いられる還元剤としては、例えば、亜硫酸塩、亜硫酸水素塩、ピロ亜硫酸塩、亜ニチオン酸塩、ニチオン酸塩、チオ硫酸塩、ホルムアルデヒドスルホン酸塩、ベンズアルデヒドスルホン酸塩；Ｌ－アスコルビン酸、エリソルビン酸、酒石酸、クエン酸などのカルボン酸類およびその塩；デキストロース、サッカロースなどの還元糖類；ジメチルアニリン、トリエタノールアミンなどのアミン類が挙げられる。これらは１種を単独でまたは２種以上を組み合わせて使用することができる。これらのうち、Ｌ－アスコルビン酸、エリソルビン酸が好ましい。還元剤の配合量は、他の添加剤などの組み合わせを考慮して適宜調整することができる。 Examples of the reducing agent used in the emulsion polymerization of the thermoplastic resin emulsion contained in the fiber bundling composition of the present invention 2 include sulfite, hydrogen sulfite, pyrosulfite, nitionite, and nitionate. , thiosulfate, formaldehyde sulfonate, benzaldehyde sulfonate; L-ascorbic acid, erythorbic acid, tartaric acid, citric acid and other carboxylic acids and salts thereof; dextrose, saccharose and other reducing sugars; dimethylaniline, triethanolamine, etc. amines of. These can be used individually by 1 type or in combination of 2 or more types. Among these, L-ascorbic acid and erythorbic acid are preferred. The blending amount of the reducing agent can be appropriately adjusted in consideration of the combination with other additives.

　また、本実施形態に係る反応系には、共重合体の分子量及び架橋構造を制御する目的で、ペンタン、ヘキサン、ヘプタン、オクタン、シクロヘキサン、シクロヘプタン等の飽和炭化水素；ペンテン、ヘキセン、ヘプテン、シクロペンテン、シクロヘキセン、シクロヘプテン、４－メチルシクロヘキセン、１－メチルシクロヘキセン等の不飽和炭化水素；ベンゼン、トルエン、キシレン等の芳香族炭化水素などの炭化水素化合物を配合することができる。これらは１種を単独でまたは２種以上を組み合わせて使用することができる。これらのうち、シクロヘキセン、トルエンを用いることが好ましい。 For the purpose of controlling the molecular weight and crosslinked structure of the copolymer, the reaction system according to the present embodiment contains saturated hydrocarbons such as pentane, hexane, heptane, octane, cyclohexane, and cycloheptane; pentene, hexene, heptene, Hydrocarbon compounds such as unsaturated hydrocarbons such as cyclopentene, cyclohexene, cycloheptene, 4-methylcyclohexene and 1-methylcyclohexene; aromatic hydrocarbons such as benzene, toluene and xylene can be blended. These can be used individually by 1 type or in combination of 2 or more types. Among these, it is preferable to use cyclohexene and toluene.

　また、乳化重合する際の重合温度は、３０～８５℃の範囲で行うことが好ましく、重合時間は、３～２０時間の範囲であることが好ましい。 The polymerization temperature during emulsion polymerization is preferably in the range of 30 to 85°C, and the polymerization time is preferably in the range of 3 to 20 hours.

　また、本発明２の繊維集束用組成物には、熱可塑性樹脂エマルジョン以外に、乳化剤、分散剤、滑剤、消泡剤、防腐剤、酸化防止剤、紫外線吸収剤、光安定化剤、着色剤、帯電防止剤、可塑剤等を、本発明２の効果を損なわない範囲に配合して使用することが可能である。 In addition to the thermoplastic resin emulsion, the fiber bundling composition of the present invention 2 contains an emulsifier, a dispersant, a lubricant, an antifoaming agent, a preservative, an antioxidant, an ultraviolet absorber, a light stabilizer, and a colorant. , an antistatic agent, a plasticizer, etc. can be blended and used within a range that does not impair the effects of the present invention 2.

　本発明２の繊維集束用組成物中の熱可塑性樹脂エマルジョンの含有割合（固形分換算）は、８０重量％以上であることが好ましく、９０重量％以上であることがより好ましい。 The content of the thermoplastic resin emulsion (in terms of solid content) in the fiber bundling composition of Invention 2 is preferably 80% by weight or more, more preferably 90% by weight or more.

　本発明２の繊維集束用組成物中の熱可塑性樹脂エマルジョンの重量平均分子量は、１．０×１０４～８×１０４の範囲にあることが好ましい。重量平均分子量が、１．０×１０４より低いと本発明２の目的である最終製品での強度が劣り、８×１０４を超えると本発明２の特徴である繊維間への含浸性が低下する。より好ましくは２×１０４～７．５×１０４、さらに好ましくは２．５×１０４～７×１０４、特に好ましくは３．５×１０４～６．８×１０４、最も好ましくは４×１０４～６．５×１０４の範囲である。 The weight-average molecular weight of the thermoplastic resin emulsion in the fiber bundling composition of Invention 2 is preferably in the range of 1.0×10 4 to 8×10 4 . If the weight-average molecular weight is lower than 1.0×10 4 , the strength of the final product, which is the objective of Invention 2, is inferior, and if it exceeds 8×10 4 , impregnation between fibers, which is the feature of Invention 2, is impaired. descend. More preferably 2×10 4 to 7.5×10 4 , still more preferably 2.5×10 4 to 7×10 4 , particularly preferably 3.5×10 4 to 6.8×10 4 , most preferably It is in the range of 4×10 4 to 6.5×10 4 .

　なお、熱可塑性樹脂エマルジョンの重量平均分子量は、ＵＶ検出器、カラム（Ａｇｉｌｅｎｔ社製　ＭＩＸＤ－Ｂ）を備えた市販のゲルパーミエーションクロマトグラム（ＧＰＣ）測定装置を用いて、カラム温度５０℃、溶媒テトラヒドロフラン（ＴＨＦ）、流量１ｍｌ／ｍｉｎ、検出波長２５４ｎｍの条件で測定したポリスチレン換算分子量である。 The weight-average molecular weight of the thermoplastic resin emulsion was measured using a commercially available gel permeation chromatogram (GPC) measurement device equipped with a UV detector and column (Agilent MIXD-B) at a column temperature of 50°C and a solvent It is a polystyrene-equivalent molecular weight measured under the conditions of tetrahydrofuran (THF), a flow rate of 1 ml/min, and a detection wavelength of 254 nm.

　本発明２の繊維集束用組成物中の熱可塑性樹脂エマルジョンの固形分のガラス転移温度に特に制限はないが、３０～２００℃の範囲であることが最終製品の強度の点から好ましい。より好ましくは３５～１９０℃、さらに好ましくは６０～１４０℃、特に好ましくは８０～１２０℃の範囲である。このガラス転移温度はＪＩＳ　Ｋ７１２１―２０１２に準拠して測定することができる。なお、この熱可塑性樹脂エマルジョン中の固形分の抽出方法に特に制限はないが、例えば熱可塑性樹脂エマルジョンを９０℃に調整された乾燥機中で１０時間乾燥することにより得ることができる。 Although there is no particular limitation on the glass transition temperature of the solid content of the thermoplastic resin emulsion in the fiber bundling composition of Invention 2, it is preferably in the range of 30 to 200°C from the standpoint of the strength of the final product. The range is more preferably 35 to 190°C, still more preferably 60 to 140°C, and particularly preferably 80 to 120°C. This glass transition temperature can be measured according to JIS K7121-2012. The method for extracting the solid content in the thermoplastic resin emulsion is not particularly limited, but it can be obtained, for example, by drying the thermoplastic resin emulsion in a dryer adjusted to 90° C. for 10 hours.

　本発明２の繊維集束用組成物の表面張力は、２５～４５ｍＮ/ｍであることが必要であり、２６～４２ｍＮ／ｍであることが特に好ましく、２７～４０ｍＮ/ｍであることが特に好ましい。該表面張力が４５ｍＮ／ｍ超の場合、熱可塑性樹脂エマルジョンの強化繊維に対する均一付着性が下がり、熱可塑性マトリックス樹脂と強化繊維との接着性が悪化する。一方、該表面張力が２５ｍＮ／ｍ未満の場合、強化繊維に対する集束剤の付着量を制御することが困難となる。 The surface tension of the fiber bundling composition of the present invention 2 is required to be 25 to 45 mN/m, particularly preferably 26 to 42 mN/m, particularly preferably 27 to 40 mN/m. . If the surface tension exceeds 45 mN/m, the uniform adhesion of the thermoplastic resin emulsion to the reinforcing fibers is lowered, and the adhesiveness between the thermoplastic matrix resin and the reinforcing fibers is deteriorated. On the other hand, when the surface tension is less than 25 mN/m, it becomes difficult to control the amount of the sizing agent attached to the reinforcing fibers.

　表面張力は、例えば、実施例に記載されている方法で測定することができる。 The surface tension can be measured, for example, by the method described in Examples.

　尚、この表面張力はエチレン系不飽和カルボン酸単量体の含有量や熱可塑性樹脂エマルジョンに添加される乳化剤の種類や量によって調整することが可能である。熱可塑性樹脂エマルジョンに添加される乳化剤の種類としては、非イオン系界面活性剤または陰イオン系界面活性剤の少なくとも１種であることが好ましく、アセチレングリコール型非イオン性界面活性剤、ドデシルベンゼンスルホン酸ナトリウム及びジアルキルスルホコハク酸塩系陰イオン界面活性剤の少なくとも１種であることがより好ましい。また、乳化剤の添加量としては、熱可塑性樹脂エマルジョン１００重量部(固形分)に対して、０．５～２．５重量部であることが好ましい。 The surface tension can be adjusted by adjusting the content of the ethylenically unsaturated carboxylic acid monomer and the type and amount of the emulsifier added to the thermoplastic resin emulsion. The type of emulsifier added to the thermoplastic resin emulsion is preferably at least one of nonionic surfactants and anionic surfactants, such as acetylene glycol type nonionic surfactants, dodecylbenzene sulfone At least one of sodium sulfate and dialkylsulfosuccinate anionic surfactants is more preferred. The amount of emulsifier to be added is preferably 0.5 to 2.5 parts by weight with respect to 100 parts by weight (solid content) of the thermoplastic resin emulsion.

　本発明２の繊維集束用組成物により繊維を集束させる方法には特に制限はなく、スプレー法や塗布法または含浸法等の公知の方法から１種または２種以上組み合わせて選択することが可能である。 The method for bundling fibers with the fiber bundling composition of the present invention 2 is not particularly limited, and it is possible to select one or a combination of two or more of known methods such as a spray method, a coating method, and an impregnation method. be.

　本発明２の繊維集束用組成物により集束させる繊維としては、炭素繊維、ガラス繊維、硼素繊維、炭化ケイ素繊維、あるいはアルミウム繊維、ステンレス繊維、銅繊維、ニッケル繊維などの金属繊維、ポリアミド繊維、ポリエステル繊維、ポリアリレート繊維、ポリイミド繊維、（ナノ）セルロース繊維などの有機繊維等を用いることが出来る。さらにこれらの繊維は１種または２種以上を組み合わせて用いることも可能である。中でも、炭素繊維、ガラス繊維が好ましい。炭素繊維には、通常の炭素繊維に加えて、ニッケルなどの金属で被覆処理した炭素繊維なども含まれ、かつその形態に特に制限はなく、連続繊維、チョップド繊維、ミルド形状や不織布等、目的に応じて任意の形態のものを選ぶことが可能である。 Fibers to be bundled by the composition for fiber bundling of the present invention 2 include carbon fiber, glass fiber, boron fiber, silicon carbide fiber, metal fiber such as aluminum fiber, stainless steel fiber, copper fiber, nickel fiber, polyamide fiber, and polyester. Organic fibers such as fibers, polyarylate fibers, polyimide fibers, and (nano)cellulose fibers can be used. Furthermore, these fibers can be used singly or in combination of two or more. Among them, carbon fiber and glass fiber are preferred. In addition to ordinary carbon fibers, carbon fibers include carbon fibers coated with metal such as nickel, and there are no particular restrictions on the form thereof, and may be continuous fibers, chopped fibers, milled shapes, non-woven fabrics, etc. Any form can be selected according to the requirements.

　本発明２における繊維集束用組成物と繊維の含浸比率に特に制限は無いが、最終製品の強度面から、固形分換算で、繊維集束用組成物１～２０重量部、繊維９９～８０重量部の範囲で含浸させることが好ましい。 Although there is no particular limitation on the impregnation ratio of the fiber bundling composition and the fibers in Invention 2, the fiber bundling composition is 1 to 20 parts by weight and the fiber is 99 to 80 parts by weight in terms of solid content in terms of the strength of the final product. is preferably impregnated in the range of

　本発明２の樹脂含浸繊維における、繊維集束用組成物により集束させた繊維の水分の蒸発方法については特に制限はなく、乾燥機を使用する方法、赤外線を照射する方法、連続的に乾燥機を通過させる方法等、目的に応じて採用することが可能である。尚、乾燥温度については、熱可塑性樹脂エマルジョンのガラス転移温度＋６０～８０℃に調整されることが、集束処理後の繊維を取り扱う上で好ましい。 In the resin-impregnated fiber of the present invention 2, the method for evaporating the moisture of the fiber bundled with the fiber bundling composition is not particularly limited, and includes a method using a dryer, a method of irradiating with infrared rays, and a method of continuously using a dryer. It is possible to adopt a method such as passing through, depending on the purpose. The drying temperature is preferably adjusted to the glass transition temperature of the thermoplastic resin emulsion plus 60 to 80° C. for handling the fibers after the bundling treatment.

　本発明２の樹脂含浸繊維は、熱可塑性樹脂と溶融混練し、繊維強化熱可塑性樹脂組成物として用いることができる。さらに、熱可塑性樹脂シートまたはフィルムと積層させた積層品としても用いることもできる。 The resin-impregnated fiber of Invention 2 can be melt-kneaded with a thermoplastic resin and used as a fiber-reinforced thermoplastic resin composition. Furthermore, it can also be used as a laminate laminated with a thermoplastic resin sheet or film.

　本発明２の樹脂含浸繊維と組み合わせる熱可塑性樹脂としては、例えば、ポリスチレン（ＰＳ）、耐衝撃性ポリスチレン（ＨＩＰＳ）、アクリロニトリル－ブタジエンゴム－スチレン共重合体（ＡＢＳ）、アクリロニトリルーアクリルゴム－スチレン共重合体（ＡＳＡ）、アクリロニトリル－エチレンプロピレンゴム－スチレン共重合体（ＡＥＳ）、アクリロニトリル－スチレン共重合体（ＡＳ）等のスチレン系樹脂、ポリエチレン（ＰＥ）、ポリプロピレン（ＰＰ）等のポリオレフィン樹脂、ポリカーボネート（ＰＣ）、ポリエチレンテレフタレート（ＰＥＴ）、ポリブチレンテレフタレート（ＰＢＴ）、ポリ乳酸樹脂（ＰＬＡ）等のポリエステル樹脂、ポリメチルメタクリレート樹脂（ＰＭＭＡ）、ポリアミド樹脂（ＰＡ）、熱可塑性ポリウレタン樹脂（ＴＰＵ）、ポリエーテルサルフォン（ＰＥＳ）、ポリフェニレンサルファイド（ＰＰＳ）あるいはスチレン系樹脂と、ポリエステル樹脂、ポリアミド樹脂から選ばれる１種以上の樹脂とのアロイが例示され、最終製品の要求性能に合わせて１種又は２種以上組み合わせて用いることが可能である。中でもスチレン系樹脂、ポリエステル樹脂、ポリアミド樹脂、およびスチレン系樹脂とポリエステル樹脂またはポリアミドとのアロイが、最終製品の成形性と強度のバランスの点で好ましい。 Examples of the thermoplastic resin to be combined with the resin-impregnated fiber of the present invention 2 include polystyrene (PS), high-impact polystyrene (HIPS), acrylonitrile-butadiene rubber-styrene copolymer (ABS), acrylonitrile-acrylic rubber-styrene copolymer. Polymer (ASA), acrylonitrile-ethylene propylene rubber-styrene copolymer (AES), acrylonitrile-styrene copolymer (AS) and other styrene resins, polyethylene (PE), polypropylene (PP) and other polyolefin resins, polycarbonate (PC), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyester resins such as polylactic acid resin (PLA), polymethyl methacrylate resin (PMMA), polyamide resin (PA), thermoplastic polyurethane resin (TPU), Examples include alloys of polyether sulfone (PES), polyphenylene sulfide (PPS) or styrene resins and one or more resins selected from polyester resins and polyamide resins. It is possible to use it in combination of 2 or more types. Among them, styrene resins, polyester resins, polyamide resins, and alloys of styrene resins and polyester resins or polyamides are preferred from the viewpoint of the balance between moldability and strength of the final product.

　本発明２の樹脂含浸繊維と組み合せる熱可塑性樹脂には、例えば、光安定剤、酸化防止剤、熱安定剤、紫外線吸収剤、滑剤、難燃剤、難燃助剤、可塑剤、顔料、染料等の各種添加剤を含むこともできる。 The thermoplastic resin to be combined with the resin-impregnated fiber of the present invention 2 includes, for example, a light stabilizer, an antioxidant, a heat stabilizer, an ultraviolet absorber, a lubricant, a flame retardant, a flame retardant aid, a plasticizer, a pigment, and a dye. Various additives such as can also be included.

　本発明２の樹脂含浸繊維と熱可塑性樹脂とを溶融混練して得られた繊維強化熱可塑性樹脂組成物は、例えば、射出成形、多層押し出し成形、フィルム成形、シート成形、インフレーション成形、プレス成形、ＳＭＣ成形法、ＬＦＴ－Ｄ法等、目的に応じた加工法を採用することで成形品を得ることが可能である。また、場合によっては予備賦形を行う工程を挟むことも可能である。 The fiber-reinforced thermoplastic resin composition obtained by melt-kneading the resin-impregnated fiber and the thermoplastic resin of the present invention 2 can be, for example, injection molding, multilayer extrusion molding, film molding, sheet molding, inflation molding, press molding, A molded article can be obtained by adopting a processing method according to the purpose, such as the SMC molding method and the LFT-D method. In some cases, it is also possible to interpose a step of pre-shaping.

　また、上記の加工法以外に、本発明２の樹脂含浸繊維からなる層を熱可塑性樹脂シートまたはフィルムと積層させた積層体を用いて、プレス成型、ＳＭＣ成形法等により成形品を得ることが可能である。また、場合によっては予備賦形を行う工程を挟むことも可能である。 In addition to the above-mentioned processing methods, it is also possible to obtain a molded product by press molding, SMC molding, or the like using a laminate obtained by laminating a layer comprising the resin-impregnated fiber of the present invention 2 with a thermoplastic resin sheet or film. It is possible. In some cases, it is also possible to interpose a step of pre-shaping.

　成形品の加工温度に特に制限はなく、使用される熱可塑性樹脂の特性により任意の温度を選択することが可能であるが、成形サイクルの点から１８０～３００℃の範囲で成形することが好ましく、更に好ましくは２００～２８０℃の範囲である。 There is no particular limitation on the processing temperature of the molded product, and it is possible to select any temperature according to the properties of the thermoplastic resin used, but it is preferable to mold in the range of 180 to 300 ° C. from the viewpoint of the molding cycle. , and more preferably in the range of 200 to 280°C.

　＜本発明３＞
　以下、本発明３について詳細に説明する。 <Invention 3>
The present invention 3 will be described in detail below.

　本発明３の繊維集束用組成物は、熱可塑性樹脂エマルジョンと、アセチレングリコール系非イオン界面活性剤またはジアルキルスルホコハク酸塩系陰イオン界面活性剤の少なくとも1種を含むものである。 The fiber bundling composition of Invention 3 contains a thermoplastic resin emulsion and at least one of acetylene glycol-based nonionic surfactants and dialkylsulfosuccinate-based anionic surfactants.

　本発明３の繊維集束用組成物に含まれる熱可塑性樹脂エマルジョンは、熱可塑性樹脂の水分散体であれば特に制限なく、例えば、ポリエステル系樹脂エマルジョン、ポリウレタン系樹脂エマルジョン、酢酸ビニル系樹脂エマルジョン、塩化ビニリデン系樹脂エマルジョン、ポリアミド系樹脂エマルジョン、芳香族ビニル系樹脂エマルジョン、アクリル系樹脂エマルジョン、オレフィン系樹脂エマルジョンなどが挙げられる。中でも芳香族ビニル系樹脂エマルジョンが樹脂含浸繊維と熱可塑性樹脂との接着性の点で好ましい。 The thermoplastic resin emulsion contained in the fiber bundling composition of the present invention 3 is not particularly limited as long as it is an aqueous dispersion of a thermoplastic resin. Examples include polyester resin emulsion, polyurethane resin emulsion, vinyl acetate resin emulsion, Examples include vinylidene chloride resin emulsions, polyamide resin emulsions, aromatic vinyl resin emulsions, acrylic resin emulsions, and olefin resin emulsions. Among them, an aromatic vinyl-based resin emulsion is preferable from the viewpoint of adhesiveness between the resin-impregnated fiber and the thermoplastic resin.

　芳香族ビニル系樹脂エマルジョンは、芳香族ビニル系単量体と、芳香族ビニル系単量体と共重合可能な他の単量体との共重合体を含有する。芳香族ビニル系単量体と共重合可能な他の単量体としては、エチレン系不飽和カルボン酸単量体、シアン化ビニル系単量体、アルキルエステル系単量体、ヒドロキシアルキル基を含有する不飽和単量体、不飽和カルボン酸アミド系単量体、ビニルピリジン系単量体、共役ジエン系単量体等が挙げられ、目的に応じて各々１種または２種以上混合して使用することが可能である。 The aromatic vinyl resin emulsion contains a copolymer of an aromatic vinyl monomer and another monomer copolymerizable with the aromatic vinyl monomer. Other monomers copolymerizable with aromatic vinyl monomers include ethylenically unsaturated carboxylic acid monomers, vinyl cyanide monomers, alkyl ester monomers, and hydroxyalkyl group-containing monomers. unsaturated monomers, unsaturated carboxylic acid amide-based monomers, vinylpyridine-based monomers, conjugated diene-based monomers, etc., and depending on the purpose, each may be used alone or in combination of two or more. It is possible to

　芳香族ビニル系単量体としては、スチレン、α－メチルスチレン、ビニルトルエンおよびジビニルベンゼン等が挙げられ、これらを１種または２種以上使用することができる。特にスチレン、α－メチルスチレンの使用が好ましい。 The aromatic vinyl-based monomers include styrene, α-methylstyrene, vinyltoluene, divinylbenzene, and the like, and one or more of these can be used. Styrene and α-methylstyrene are particularly preferred.

　エチレン系不飽和カルボン酸単量体としては、アクリル酸、メタクリル酸、クロトン酸、マレイン酸、フマル酸、イタコン酸などのモノまたはジカルボン酸（無水物）等が挙げられる。 Examples of ethylenically unsaturated carboxylic acid monomers include mono- or dicarboxylic acids (anhydrides) such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, and itaconic acid.

　シアン化ビニル系単量体としては、アクリロニトリル、メタクリロニトリル、α－クロルアクリロニトリル、α－エチルアクリロニトリル等が挙げられる。 Examples of vinyl cyanide-based monomers include acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, α-ethylacrylonitrile and the like.

　アルキルエステル系単量体としては、メチルアクリレート、メチルメタクリレート、エチルアクリレート、エチルメタクリレート、ブチルアクリレート、グリシジルメタクリレート、ジメチルフマレート、ジエチルフマレート、ジメチルマレエート、ジエチルマルエート、ジメチルイタコネート、モノメチルフマレート、モノエチルフマレート、２－エチルヘキシルアクリレート等が挙げられる。 Alkyl ester monomers include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, glycidyl methacrylate, dimethyl fumarate, diethyl fumarate, dimethyl maleate, diethyl malate, dimethyl itaconate, and monomethyl fumarate. , monoethyl fumarate, 2-ethylhexyl acrylate and the like.

　ヒドロキシアルキル基を含有する不飽和単量体としては、β－ヒドロキシエチルアクリレート、β－ヒドロキシエチルメタクリレート、ヒドロキシプロピルアクリレート、ヒドロキシプロピルメタクリレート、ヒドロキシブチルアクリレート、ヒドロキシブチルメタクリレート、３－クロロ－２－ヒドロキシプロピルメタクリレート、ジ－（エチレングリコール）マレエート、ジ－（エチレングリコール）イタコネート、２－ヒドロキシエチルマレエート、ビス（２－ヒドロキシエチル）マレエート、２－ヒドロキシエチルメチルフマレート等が挙げられる。 Unsaturated monomers containing hydroxyalkyl groups include β-hydroxyethyl acrylate, β-hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, hydroxybutyl methacrylate, 3-chloro-2-hydroxypropyl Methacrylate, di-(ethylene glycol) maleate, di-(ethylene glycol) itaconate, 2-hydroxyethyl maleate, bis(2-hydroxyethyl) maleate, 2-hydroxyethyl methyl fumarate and the like.

　不飽和カルボン酸アミド系単量体としては、アクリルアミド、メタクリルアミド、Ｎ－メチロールアクリルアミド、Ｎ－メチロールメタクリルアミド、Ｎ，Ｎ－ジメチルアクリルアミド等が挙げられる。 Examples of unsaturated carboxylic acid amide-based monomers include acrylamide, methacrylamide, N-methylol acrylamide, N-methylol methacrylamide, and N,N-dimethylacrylamide.

　ビニルピリジン系単量体としては、２－ビニルピリジン、３－ビニルピリジン、４－ビニルピリジン、２－メチル－５－ビニルピリジン等が挙げられる。 Examples of vinylpyridine-based monomers include 2-vinylpyridine, 3-vinylpyridine, 4-vinylpyridine, and 2-methyl-5-vinylpyridine.

　共役ジエン系単量体としては、１，３－ブタジエン、２－メチル－１，３－ブタジエン、２，３－ジメチル－１，３－ブタジエン、２－クロル－１，３－ブタジエン、置換直鎖共役ペンタジエン類、置換および側鎖共役ヘキサジエン類等が挙げられる。 Conjugated diene-based monomers include 1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 2-chloro-1,3-butadiene, substituted linear Conjugated pentadienes, substituted and side chain conjugated hexadienes, and the like.

　中でも、芳香族ビニル系単量体と共重合可能な他の単量体としては、アクリル酸、メタクリル酸、フマル酸、イタコン酸、アクリロニトリル、メタクリロニトリル、メチルメタクリレート、ブチルアクリレート、β－ヒドロキシエチルアクリレート、アクリルアミドまたはメタクリルアミド、２－ビニルピリジン、１，３－ブタジエンの使用が好ましい。 Among others, other monomers copolymerizable with aromatic vinyl monomers include acrylic acid, methacrylic acid, fumaric acid, itaconic acid, acrylonitrile, methacrylonitrile, methyl methacrylate, butyl acrylate, and β-hydroxyethyl. Preference is given to using acrylates, acrylamides or methacrylamides, 2-vinylpyridine, 1,3-butadiene.

　熱可塑性樹脂エマルジョンの製造に用いられる単量体の全量（全単量体）中の芳香族ビニル系単量体の含有量は、４０～９８．５重量％であることが好ましく、４５～９５重量％であることがより好ましく、４７～９０重量％であることがさらに好ましい。この範囲に調整することで樹脂含浸繊維と熱可塑性樹脂との接着性に優れる傾向にある。 The content of the aromatic vinyl monomer in the total amount of monomers (total monomers) used for producing the thermoplastic resin emulsion is preferably 40 to 98.5% by weight, preferably 45 to 95% by weight. % by weight is more preferred, and 47 to 90% by weight is even more preferred. By adjusting it within this range, the adhesion between the resin-impregnated fiber and the thermoplastic resin tends to be excellent.

　全単量体中の「芳香族ビニル系単量体と共重合可能な他の単量体」の含有量は、１．５～６０重量％であることが好ましく、５～５５重量％であることがより好ましく、１０～５３重量％であることがさらに好ましい。この範囲に調整することで樹脂含浸繊維と熱可塑性樹脂との接着性に優れる傾向にある。 The content of the "other monomer copolymerizable with the aromatic vinyl monomer" in all the monomers is preferably 1.5 to 60% by weight, and 5 to 55% by weight. is more preferable, and 10 to 53% by weight is even more preferable. By adjusting it within this range, the adhesion between the resin-impregnated fiber and the thermoplastic resin tends to be excellent.

　芳香族ビニル系樹脂エマルジョンの各単量体の好ましい組成比率としては、芳香族ビニル系単量体６０～９５重量％、シアン化ビニル系単量体４～３９重量％、エチレン系不飽和カルボン酸単量体１～１５重量％が挙げられ、さらに好ましい組成比率としては、芳香族ビニル系単量体８０～９４重量％、シアン化ビニル系単量体５～１５重量％、エチレン系不飽和カルボン酸単量体１～５重量％が挙げられる。 The preferable composition ratio of each monomer in the aromatic vinyl resin emulsion is 60 to 95% by weight of the aromatic vinyl monomer, 4 to 39% by weight of the vinyl cyanide monomer, and the ethylenically unsaturated carboxylic acid. 1 to 15% by weight of the monomer, and more preferable composition ratios are: 80 to 94% by weight of the aromatic vinyl monomer, 5 to 15% by weight of the vinyl cyanide monomer, and the ethylenically unsaturated carboxylic acid. 1 to 5% by weight of acid monomer may be mentioned.

　本発明３の繊維集束用組成物に含まれる熱可塑性樹脂エマルジョンが、乳化重合により得られる場合、公知の乳化重合法、例えば、一括添加方法、分割添加方法、連続添加方法、多段階重合法、シード重合法、パワーフィード重合法等の何れを採用してもよい。中でも重合時の安定性や分子量の調整の容易さから連続添加方法が好ましい。 When the thermoplastic resin emulsion contained in the composition for fiber bundling of the present invention 3 is obtained by emulsion polymerization, known emulsion polymerization methods such as batch addition method, divided addition method, continuous addition method, multistage polymerization method, Either a seed polymerization method, a power feed polymerization method, or the like may be employed. Among them, the continuous addition method is preferable from the standpoint of stability during polymerization and ease of adjustment of the molecular weight.

　本発明３の繊維集束用組成物に含まれる熱可塑性樹脂エマルジョンを乳化重合の際には、ｎ－ヘキシルメルカプタン、ｎ－オクチルメルカプタン、ｔ－オクチルメルカプタン、ｎ－ドデシルメルカプタン、ｔ－ドデシルメルカプタン、ｎ－ステアリルメルカプタン等のアルキルメルカプタン、ジメチルキサントゲンジサルファイド、ジイソプロピルキサントゲンジサルファイド等のキサントゲン化合物、テトラメチルチウラムジスルフィド、テトラエチルチウラムジスルフィド、テトラメチルチウラムモノスルフィド等のチウラム系化合物、２，６－ジ－ｔ－ブチル－４－メチルフェノール、スチレン化フェノール等のフェノール系化合物、アリルアルコール等のアリル化合物、ジクロルメタン、ジブロモメタン、四臭化炭素等のハロゲン化炭化水素化合物、α－ベンジルオキシスチレン、α－ベンジルオキシアクリロニトリル、α－ベンジルオキシアクリルアミド等のビニルエーテル、トリフェニルエタン、ペンタフェニルエタン、アクロレイン、メタアクロレイン、チオグリコール酸、チオリンゴ酸、２－エチルヘキシルチオグリコレート、α－メチルスチレンダイマー、ターピノレン等の連鎖移動剤や過硫酸カリウム、過硫酸ナトリウム、過硫酸アンモニウム等の水溶性重合開始剤、クメンハイドロパーオキサイド、過酸化ベンゾイル、t－ブチルハイドロパーオキサイド、アセチルパーオキサイド、ジイソプロピルベンゼンハイドロパーオキサイド、１，１，３，３－テトラメチルブチルハイドロパーオキサイド等の油溶性重合開始剤、還元剤である硫酸第一鉄、亜硫酸塩、亜硫酸水素塩、ピロ亜硫酸塩、亜ニチオン酸塩、ニチオン酸塩、チオ硫酸塩、また、ホルムアルデヒドスルホン酸塩、ベンズアルデヒドスルホン酸塩などの還元性スルホン酸塩、更にはＬ－アスコルビン酸、酒石酸、クエン酸などのカルボン酸類、更にはデキストロース、サッカロースなどの還元糖類、更にはジメチルアニリン、トリエタノールアミンなどのアミン類の各々１種または２種以上の添加剤を使用することも可能である。これらの添加剤の使用量に特に制限は無いが、製品コストや最終製品の外観への影響を考えると、全単量体１００重量部に対して、各々０．０１～５重量部の範囲で使用することが好ましい。 When emulsifying the thermoplastic resin emulsion contained in the fiber bundling composition of the present invention 3, n-hexylmercaptan, n-octylmercaptan, t-octylmercaptan, n-dodecylmercaptan, t-dodecylmercaptan, n - alkyl mercaptans such as stearyl mercaptan; xanthogen compounds such as dimethylxanthogen disulfide and diisopropyl xanthogen disulfide; thiuram compounds such as tetramethylthiuram disulfide, tetraethylthiuram disulfide and tetramethylthiuram monosulfide; Phenolic compounds such as butyl-4-methylphenol and styrenated phenol, allyl compounds such as allyl alcohol, halogenated hydrocarbon compounds such as dichloromethane, dibromomethane, and carbon tetrabromide, α-benzyloxystyrene, α-benzyloxy Acrylonitrile, vinyl ethers such as α-benzyloxyacrylamide, chain transfer agents such as triphenylethane, pentaphenylethane, acrolein, methacrolein, thioglycolic acid, thiomalic acid, 2-ethylhexylthioglycolate, α-methylstyrene dimer, and terpinolene and water-soluble polymerization initiators such as potassium persulfate, sodium persulfate and ammonium persulfate, cumene hydroperoxide, benzoyl peroxide, t-butyl hydroperoxide, acetyl peroxide, diisopropylbenzene hydroperoxide, 1,1,3 , an oil-soluble polymerization initiator such as 3-tetramethylbutyl hydroperoxide, a reducing agent ferrous sulfate, sulfite, hydrogen sulfite, pyrosulfite, nitionite, nitionate, thiosulfate, In addition, reducing sulfonates such as formaldehyde sulfonate and benzaldehyde sulfonate, further carboxylic acids such as L-ascorbic acid, tartaric acid and citric acid, further reducing sugars such as dextrose and saccharose, further dimethylaniline, It is also possible to use one or more additives each of amines such as triethanolamine. There is no particular limit to the amount of these additives used, but considering the effect on the product cost and the appearance of the final product, each in the range of 0.01 to 5 parts by weight per 100 parts by weight of the total monomers. It is preferred to use

　本発明３の繊維集束用組成物に含まれる熱可塑性エマルジョンを乳化重合する際に使用される界面活性剤に特に制限はなく、例えば、高級アルコールの硫酸エステル塩、アルキルベンゼンスルホン酸塩、アルキルジフェニルエーテルスルホン酸塩、脂肪族スルホン酸塩、脂肪族カルボン酸塩、非イオン界面活性剤、例えば、アセチレングリコール系界面活性剤、アセチレンアルコール系界面活性剤、ポリオキシエチレンノニルフェニルエーテル、ポリオキシエチレンオクチルフェニルエーテル、ポリオキシエチレンドデシルフェニルエーテル、ポリオキシエチレンアルキルアリルエーテル、ポリオキシエチレンオレイルエーテル、ポリオキシエチレンラウリルエーテル、ポリオキシエチレンアルキルエーテル、ポリオキシアルキレンアルキルエーテルなどのエーテル系、ポリオキシエチレンオレイン酸、ポリオキシエチレンオレイン酸エステル、ポリオキシエチレンジステアリン酸エステル、ソルビタンラウレート、ソルビタンモノステアレート、ソルビタンモノオレエート、ソルビタンセスキオレート、ポリオキシエチレンモノオレエート、ポリオキシエチレンステアレート等のエステル系、ジメチルポリシロキサン等のシリコン系界面活性剤、その他フッ素アルキルエステル、パーフルオロアルキルカルボン酸塩等の含フッ素系界面活性剤等が挙げられる。 Surfactants used in emulsion polymerization of the thermoplastic emulsion contained in the fiber bundling composition of the present invention 3 are not particularly limited. acid salts, aliphatic sulfonates, aliphatic carboxylates, nonionic surfactants such as acetylene glycol-based surfactants, acetylene alcohol-based surfactants, polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether , polyoxyethylene dodecyl phenyl ether, polyoxyethylene alkyl allyl ether, polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene alkyl ether, polyoxyalkylene alkyl ether, etc., polyoxyethylene oleic acid, poly Esters such as oxyethylene oleate, polyoxyethylene distearate, sorbitan laurate, sorbitan monostearate, sorbitan monooleate, sorbitan sesquioleate, polyoxyethylene monooleate, polyoxyethylene stearate, dimethyl poly Silicone surfactants such as siloxane, and fluorine-containing surfactants such as fluorine alkyl esters and perfluoroalkyl carboxylates are included.

　これらを１種又は２種以上使用することができ、全単量体１００重量部に対して、０．０５～１０重量部の範囲で使用するのが好ましい。０．０５部未満では重合液の安定性に劣り、１０重量部を越えると最終製品での成型の際にガスが多量に発生し、成形品表面を損なう不具合が発生する。好ましくは０．１～８重量部、より好ましくは０．５～５重量部の範囲である。 One or more of these can be used, and it is preferable to use them in the range of 0.05 to 10 parts by weight per 100 parts by weight of the total monomers. If the amount is less than 0.05 parts, the stability of the polymerization liquid is poor, and if the amount exceeds 10 parts by weight, a large amount of gas is generated during molding of the final product, resulting in the problem of damaging the surface of the molded product. The range is preferably 0.1 to 8 parts by weight, more preferably 0.5 to 5 parts by weight.

　更に、重合時には、公知の電解質、重合促進剤、キレート剤等を使用することができる。 Furthermore, known electrolytes, polymerization accelerators, chelating agents, etc. can be used during polymerization.

　また、乳化重合する際の重合温度は、４０～８０℃の範囲で行うことが好ましく、重合時間は、３～１５時間の範囲であることが好ましい。 The polymerization temperature during emulsion polymerization is preferably in the range of 40 to 80°C, and the polymerization time is preferably in the range of 3 to 15 hours.

　本発明３の繊維集束用組成物は、アセチレングリコール系非イオン界面活性剤またはジアルキルスルホコハク酸塩系陰イオン界面活性剤の少なくとも1種を含むものである。 The fiber bundling composition of Invention 3 contains at least one of acetylene glycol-based nonionic surfactants and dialkylsulfosuccinate-based anionic surfactants.

　アセチレングリコール系非イオン界面活性剤は、下記一般式（１）又は（２）で示される化合物である。 The acetylene glycol-based nonionic surfactant is a compound represented by the following general formula (1) or (2).

Figure JPOXMLDOC01-appb-C000001
Figure JPOXMLDOC01-appb-C000001

　上記一般式（１）中のＲ１、Ｒ２、Ｒ３及びＲ４は、それぞれ炭素数１以上５以下のアルキル基を示す。Ｒ１、Ｒ２、Ｒ３及びＲ４は、アセチレン基を中心に左右対称構造であることが好ましい。 R1, R2, R3 and R4 in the above general formula (1) each represent an alkyl group having 1 or more and 5 or less carbon atoms. R1, R2, R3 and R4 preferably have bilaterally symmetrical structures centering on the acetylene group.

Figure JPOXMLDOC01-appb-C000002
Figure JPOXMLDOC01-appb-C000002

　上記一般式（２）中のＲ５、Ｒ６、Ｒ７及びＲ８は、それぞれ炭素数１以上５以下のアルキル基を示す。ｍ及びｎは、それぞれ１以上２５以下の整数であり、ｍ＋ｎは２以上４０以下である。ＯＥはオキシエチレン鎖（－Ｏ－ＣＨ２－ＣＨ２－）、ＯＰはオキシプロピレン鎖（－Ｏ－ＣＨ２－ＣＨ［ＣＨ３］－）である。ＯＥ及びＯＰはそれぞれ単独鎖であっても混合鎖であってもよい。Ｒ５、Ｒ６、Ｒ７及びＲ８は、アセチレン基を中心に左右対称構造であることが好ましい。 R5, R6, R7 and R8 in the general formula (2) each represent an alkyl group having 1 to 5 carbon atoms. m and n are each an integer of 1 or more and 25 or less, and m+n is 2 or more and 40 or less. OE is an oxyethylene chain ( --O--CH.sub.2--CH.sub.2--) and OP is an oxypropylene chain ( --O-- CH.sub.2 --CH[ CH.sub.3 ]--). OE and OP may each be single-stranded or mixed-stranded. R5, R6, R7 and R8 preferably have a bilaterally symmetrical structure centering on the acetylene group.

　アセチレングリコール系非イオン界面活性剤は、日信化学工業（株）製から「Ｓｕｒｆｙｎｏｌ（登録商標）」又は「Ｏｌｆｉｎｅ（登録商標）」の名称で、川研ファインケミカル（株）製から「Ａｃｅｔｙｌｅｎｏｌ（登録商標）」の名称で市販されている。 Acetylene glycol-based nonionic surfactants are manufactured by Nissin Chemical Industry Co., Ltd. under the name of "Surfynol (registered trademark)" or "Olfine (registered trademark)", and manufactured by Kawaken Fine Chemicals Co., Ltd. under the name of "Acetylenol (registered trademark)". Trademark)”.

　アセチレングリコール系非イオン界面活性剤は、２，４，７，９－テトラメチル－５－デシン－４，７－ジオール又は２，４，７，９－テトラメチル－５－デシン－４，７－ジオールのエトキシレートが好ましい。 Acetylene glycol-based nonionic surfactants include 2,4,7,9-tetramethyl-5-decyne-4,7-diol or 2,4,7,9-tetramethyl-5-decyne-4,7- Ethoxylates of diols are preferred.

　ジアルキルスルホコハク酸塩系陰イオン界面活性剤としては、特に限定されないが、アルキル基の炭素数が８～１６のものが好ましい。塩としては、例えばナトリウム塩、カリウム塩等のアルカリ金属塩、アルカリ土類金属塩、アンモニウム塩、アルカノールアミン等の有機アミン塩等が挙げられる。ジアルキルスルホコハク酸塩の具体例としては、例えばジオクチルスルホコハク酸ナトリウム塩、ジオクチルスルホコハク酸マグネシウム塩、ジオクチルスルホコハク酸トリエタノールアミン塩、ジデシルスルホコハク酸ナトリウム塩、ジドデシルスルホコハク酸ナトリウム塩（ジラウリルスルホコハク酸ナトリウム塩）、ジドデシルスルホコハク酸マグネシウム塩、ジテトラデシルスルホコハク酸リチウム塩、ジヘキサデシルスルホコハク酸カリウム塩等が挙げられる。これらのジアルキルスルホコハク酸塩は、一種類のジアルキルスルホコハク酸塩を単独で使用してもよいし、又は二種以上のジアルキルスルホコハク酸塩を適宜組み合わせて使用してもよい。 The dialkyl sulfosuccinate-based anionic surfactant is not particularly limited, but one having an alkyl group with 8 to 16 carbon atoms is preferable. Examples of salts include alkali metal salts such as sodium salts and potassium salts, alkaline earth metal salts, ammonium salts, and organic amine salts such as alkanolamines. Specific examples of the dialkylsulfosuccinate include sodium dioctylsulfosuccinate, magnesium dioctylsulfosuccinate, triethanolamine dioctylsulfosuccinate, sodium didecylsulfosuccinate, sodium didodecylsulfosuccinate (sodium dilaurylsulfosuccinate). salt), didodecylsulfosuccinate magnesium salt, ditetradecylsulfosuccinate lithium salt, dihexadecylsulfosuccinate potassium salt, and the like. As for these dialkylsulfosuccinates, one dialkylsulfosuccinate may be used alone, or two or more dialkylsulfosuccinates may be used in combination.

　中でも、ジオクチルスルホコハク酸ナトリウムであることが曲げ強度向上の観点から好ましい。 Among them, sodium dioctyl sulfosuccinate is preferable from the viewpoint of improving bending strength.

　アセチレングリコール系非イオン界面活性剤またはジアルキルスルホコハク酸塩系陰イオン界面活性剤の少なくとも１種の含有量は、熱可塑性樹脂エマルジョン１００重量部に対して０．５～１０重量部であることが好ましく、０．７～３．２重量部であることがより好ましい。この範囲に調整することで樹脂含浸繊維と熱可塑性樹脂との接着性に優れる傾向にある。 The content of at least one of the acetylene glycol nonionic surfactant and the dialkylsulfosuccinate anionic surfactant is preferably 0.5 to 10 parts by weight based on 100 parts by weight of the thermoplastic resin emulsion. , more preferably 0.7 to 3.2 parts by weight. By adjusting it within this range, the adhesion between the resin-impregnated fiber and the thermoplastic resin tends to be excellent.

　アセチレングリコール系非イオン界面活性剤またはジアルキルスルホコハク酸塩系陰イオン界面活性剤の少なくとも１種は、熱可塑性樹脂エマルジョンの製造時に添加しても良く、熱可塑性樹脂エマルジョンの製造完了後に添加しても良い。 At least one of the acetylene glycol-based nonionic surfactant and the dialkylsulfosuccinate-based anionic surfactant may be added during the production of the thermoplastic resin emulsion, or may be added after the completion of the production of the thermoplastic resin emulsion. good.

　また、本発明３の繊維集束用組成物には、分散剤、滑剤、消泡剤、防腐剤、酸化防止剤、紫外線吸収剤、光安定化剤、着色剤、帯電防止剤、可塑剤等を本発明３の効果を損なわない範囲に配合して使用することが可能である。 In addition, the fiber bundling composition of the present invention 3 contains a dispersant, a lubricant, an antifoaming agent, a preservative, an antioxidant, an ultraviolet absorber, a light stabilizer, a coloring agent, an antistatic agent, a plasticizer, and the like. It is possible to mix and use within a range that does not impair the effects of Invention 3.

　本発明３の繊維集束用組成物中の熱可塑性樹脂エマルジョンの含有割合（固形分換算）は、８０重量％以上であることが好ましく、９０重量％以上であることがより好ましい。 The content of the thermoplastic resin emulsion (in terms of solid content) in the fiber bundling composition of Invention 3 is preferably 80% by weight or more, more preferably 90% by weight or more.

　本発明３の繊維集束用組成物中の熱可塑性樹脂エマルジョンの重量平均分子量は、１．０×１０４～８×１０４の範囲にあることが好ましい。重量平均分子量が、１．０×１０４より低いと本発明３の目的である最終製品での強度が劣り、８×１０４を超えると本発明３の特徴である炭素繊維間への含浸性が低下する。より好ましくは２×１０４～７．５×１０４、さらに好ましくは２．５×１０４～７×１０４、特に好ましくは３．５×１０４～６．８×１０４、最も好ましくは４×１０４～６．５×１０４の範囲である。 The weight-average molecular weight of the thermoplastic resin emulsion in the fiber bundling composition of Invention 3 is preferably in the range of 1.0×10 4 to 8×10 4 . If the weight-average molecular weight is lower than 1.0×10 4 , the strength of the final product, which is the object of Invention 3, is inferior, and if it exceeds 8×10 4 , impregnation between carbon fibers, which is the feature of Invention 3, is poor. descend. More preferably 2×10 4 to 7.5×10 4 , still more preferably 2.5×10 4 to 7×10 4 , particularly preferably 3.5×10 4 to 6.8×10 4 , most preferably It is in the range of 4×10 4 to 6.5×10 4 .

　なお、熱可塑性樹脂エマルジョンの重量平均分子量は、ＵＶ検出器、カラム（Ａｇｉｌｅｎｔ社製　ＭＩＸＤ－Ｂ）を備えた市販のゲルパーミエーションクロマトグラム（ＧＰＣ）測定装置を用いて、カラム温度５０℃、溶媒テトラヒドロフラン（ＴＨＦ）、流量１ｍｌ／ｍｉｎ、検出波長２５４ｎｍの条件で測定したポリスチレン換算分子量である。 The weight-average molecular weight of the thermoplastic resin emulsion was measured using a commercially available gel permeation chromatogram (GPC) measurement device equipped with a UV detector and column (Agilent MIXD-B) at a column temperature of 50°C and a solvent It is a polystyrene-equivalent molecular weight measured under the conditions of tetrahydrofuran (THF), a flow rate of 1 ml/min, and a detection wavelength of 254 nm.

　本発明３の繊維集束用組成物中の熱可塑性樹脂エマルジョンの固形分のガラス転移温度に特に制限はないが、３０～２００℃の範囲であることが最終製品の強度の点から好ましい。より好ましくは３５～１９０℃、さらに好ましくは６０～１４０℃、特に好ましくは８０～１２０℃の範囲である。このガラス転移温度はＪＩＳ　Ｋ７１２１―２０１２に準拠して測定することができる。なお、この熱可塑性樹脂エマルジョン中の固形分の抽出方法に特に制限はないが、例えば熱可塑性樹脂エマルジョンを９０℃に調整された乾燥機中で１０時間乾燥することにより得ることができる。 Although there is no particular limitation on the glass transition temperature of the solid content of the thermoplastic resin emulsion in the composition for fiber bundling of Invention 3, it is preferably in the range of 30 to 200°C from the standpoint of the strength of the final product. The range is more preferably 35 to 190°C, still more preferably 60 to 140°C, and particularly preferably 80 to 120°C. This glass transition temperature can be measured according to JIS K7121-2012. The method for extracting the solid content in the thermoplastic resin emulsion is not particularly limited, but it can be obtained, for example, by drying the thermoplastic resin emulsion in a dryer adjusted to 90° C. for 10 hours.

　本発明３の繊維集束用組成物は、動的表面張力が、２５～５５ｍＮ／ｍであることが必要であり、２９～４０ｍＮ／ｍが特に好ましい。動的表面張力が５５ｍＮ／ｍ超の場合、繊維集束用組成物の繊維に対する濡れ性が低下し、熱可塑性樹脂と繊維との接着性が悪化する。一方、動的表面張力が２５ｍＮ／ｍ未満の場合、繊維に対する繊維集束用組成物の付着量を制御することが困難となることがある。 The fiber bundling composition of the present invention 3 must have a dynamic surface tension of 25 to 55 mN/m, particularly preferably 29 to 40 mN/m. If the dynamic surface tension is more than 55 mN/m, the wettability of the fiber bundling composition to the fibers is lowered, and the adhesion between the thermoplastic resin and the fibers is deteriorated. On the other hand, if the dynamic surface tension is less than 25 mN/m, it may be difficult to control the amount of the fiber bundling composition attached to the fibers.

　動的表面張力は、例えば、実施例に記載されている方法で測定することができる。 The dynamic surface tension can be measured, for example, by the method described in Examples.

　尚、動的表面張力は、例えば、繊維集束用組成物に添加される界面活性剤の種類や量によって調整することが可能である。 The dynamic surface tension can be adjusted, for example, by the type and amount of surfactant added to the fiber bundling composition.

　本発明３の繊維集束用組成物を繊維に集束させる方法には特に制限はなく、スプレー法や塗布法または含浸法等の方法から１種または２種以上組み合わせて選択することが可能である。 The method for bundling the fiber bundling composition of the present invention 3 into fibers is not particularly limited, and it is possible to select one or a combination of two or more from methods such as a spray method, a coating method, and an impregnation method.

　本発明３の繊維集束用組成物で集束させる繊維としては、炭素繊維、ガラス繊維、硼素繊維、炭化ケイ素繊維、あるいはアルミウム繊維、ステンレス繊維、銅繊維、ニッケル繊維などの金属繊維、ポリアミド繊維、ポリエステル繊維、ポリアリレート繊維、ポリイミド繊維、（ナノ）セルロース繊維などの有機繊維等を用いることが出来る。さらにこれらの繊維は１種または２種以上を組み合わせて用いることも可能である。中でも、炭素繊維が最も好ましい。炭素繊維には、通常の炭素繊維に加えて、ニッケルなどの金属で被覆処理した炭素繊維なども含まれ、かつその形態に特に制限はなく、連続繊維、チョップド繊維、ミルド形状や不織布等、目的に応じて任意の形態のものを選ぶことが可能である。 The fibers to be bundled with the fiber bundling composition of the present invention 3 include carbon fiber, glass fiber, boron fiber, silicon carbide fiber, metal fiber such as aluminum fiber, stainless fiber, copper fiber, nickel fiber, polyamide fiber, and polyester. Organic fibers such as fibers, polyarylate fibers, polyimide fibers, and (nano)cellulose fibers can be used. Furthermore, these fibers can be used singly or in combination of two or more. Among them, carbon fiber is most preferred. In addition to ordinary carbon fibers, carbon fibers include carbon fibers coated with metal such as nickel, and there are no particular restrictions on the form thereof, and may be continuous fibers, chopped fibers, milled shapes, non-woven fabrics, etc. Any form can be selected according to the requirements.

　本発明３における繊維集束用組成物と繊維の含有比率には特に制限は無いが、熱可塑性樹脂との接着性や最終製品の強度面から、固形分換算で、繊維集束用組成物１～２０重量部、繊維９９～８０重量部の範囲であることが好ましい。 Although there is no particular limitation on the content ratio of the fiber bundling composition and the fiber in Invention 3, from the standpoint of adhesiveness to the thermoplastic resin and strength of the final product, the fiber bundling composition is 1 to 20 in terms of solid content. It is preferably in the range of 99 to 80 parts by weight of the fiber.

　本発明３の樹脂含浸繊維における、繊維に繊維集束用組成物を集束させた後の水分の蒸発方法については特に制限はなく、例えば乾燥機を使用する方法、赤外線を照射する方法、連続的に乾燥機を通過させる方法等を目的に応じて採用することが可能である。中でも、水分の蒸発だけではなく、集束した繊維集束用組成物を溶融させ、繊維表面を更に均一に被覆させるために、繊維集束用組成物のガラス転移温度＋６０℃以上に調整された１ｍ以上の行路を持つ乾燥機内を０．５ｍ/分以上の速度で連続的に通過させながら乾燥することが好ましい。 In the resin-impregnated fiber of the present invention 3, the method of evaporating the moisture after the fiber bundling composition is bundled into the fiber is not particularly limited. A method of passing through a dryer or the like can be employed depending on the purpose. Above all, in order not only to evaporate the moisture but also to melt the bundled fiber bundling composition and more uniformly coat the fiber surface, the glass transition temperature of the fiber bundling composition + 1 m or more adjusted to 60 ° C. or higher It is preferable to dry while continuously passing through a dryer having tracks at a speed of 0.5 m/min or more.

　本発明３の樹脂含浸繊維は、熱可塑性樹脂と溶融混練し、繊維強化熱可塑性樹脂組成物として用いることができる。さらに、熱可塑性樹脂シートまたはフィルムと積層させた積層品として用いることもできる。 The resin-impregnated fiber of Invention 3 can be melt-kneaded with a thermoplastic resin and used as a fiber-reinforced thermoplastic resin composition. Furthermore, it can also be used as a laminate laminated with a thermoplastic resin sheet or film.

　本発明３の樹脂含浸繊維と組み合わせる熱可塑性樹脂としては、例えば、ポリスチレン（ＰＳ）、耐衝撃性ポリスチレン（ＨＩＰＳ）、アクリロニトリル－ブタジエンゴム－スチレン共重合体（ＡＢＳ）、アクリロニトリル－エチレンプロピレンゴム－スチレン共重合体（ＡＥＳ）、アクリロニトリル－アクリルゴム－スチレン共重合体（ＡＳＡ）、アクリロニトリル－スチレン共重合体（ＡＳ）等のスチレン系樹脂、ポリエチレン（ＰＥ）、ポリプロピレン（ＰＰ）等のポリオレフィン樹脂、ポリカーボネート（ＰＣ）、ポリエチレンテレフタレート（ＰＥＴ）、ポリブチレンテレフタレート（ＰＢＴ）等のポリエステル樹脂、ポリメチルメタクリレート樹脂（ＰＭＭＡ）、ポリアミド樹脂（ＰＡ）、熱可塑性ポリウレタン樹脂（ＴＰＵ）、ポリ乳酸樹脂（ＰＬＡ）、ポリエーテルサルフォン（ＰＥＳ）、ポリフェニレンサルファイド（ＰＰＳ）あるいはスチレン系樹脂と、ポリカーボネート（ＰＣ）、ポリアミド樹脂（ＰＡ）、及びポリ乳酸樹脂（ＰＬＡ）から選ばれる１種以上の樹脂とのアロイが例示され、最終製品の要求性能に合わせて１種又は２種以上組み合わせて用いることが可能である。中でもスチレン系樹脂、ポリエステル樹脂、ポリアミド樹脂、およびスチレン系樹脂とポリエステル樹脂またはポリアミドとのアロイが、最終製品の成形性と強度のバランスの点で好ましい。 Examples of the thermoplastic resin to be combined with the resin-impregnated fiber of the present invention 3 include polystyrene (PS), high-impact polystyrene (HIPS), acrylonitrile-butadiene rubber-styrene copolymer (ABS), acrylonitrile-ethylene propylene rubber-styrene. Copolymer (AES), acrylonitrile-acrylic rubber-styrene copolymer (ASA), acrylonitrile-styrene copolymer (AS) and other styrene resins, polyethylene (PE), polypropylene (PP) and other polyolefin resins, polycarbonate (PC), polyethylene terephthalate (PET), polyester resins such as polybutylene terephthalate (PBT), polymethyl methacrylate resin (PMMA), polyamide resin (PA), thermoplastic polyurethane resin (TPU), polylactic acid resin (PLA), Examples include alloys of polyether sulfone (PES), polyphenylene sulfide (PPS) or styrenic resin and one or more resins selected from polycarbonate (PC), polyamide resin (PA) and polylactic acid resin (PLA). It is possible to use one type or a combination of two or more types according to the required performance of the final product. Among them, styrene resins, polyester resins, polyamide resins, and alloys of styrene resins and polyester resins or polyamides are preferred from the viewpoint of the balance between moldability and strength of the final product.

　本発明３の樹脂含浸繊維と組み合せる熱可塑性樹脂には、例えば、光安定剤、酸化防止剤、熱安定剤、紫外線吸収剤、滑剤、難燃剤、難燃助剤、可塑剤、顔料、染料等の各種添加剤を含むこともできる。 The thermoplastic resin to be combined with the resin-impregnated fiber of the present invention 3 includes, for example, a light stabilizer, an antioxidant, a heat stabilizer, an ultraviolet absorber, a lubricant, a flame retardant, a flame retardant aid, a plasticizer, a pigment, and a dye. Various additives such as can also be included.

　本発明３の樹脂含浸繊維と熱可塑性樹脂とを溶融混練して得られた繊維強化熱可塑性樹脂組成物は、例えば、射出成形、多層押し出し成形、フィルム成形、シート成形、インフレーション成形、プレス成形、ＳＭＣ成形法、ＬＦＴ－Ｄ法等、目的に応じた加工法を採用することで成形品を得ることが可能である。また、場合によっては予備賦形を行う工程を挟むことも可能である。 The fiber-reinforced thermoplastic resin composition obtained by melt-kneading the resin-impregnated fiber and the thermoplastic resin of the present invention 3 can be, for example, injection molding, multilayer extrusion molding, film molding, sheet molding, inflation molding, press molding, A molded article can be obtained by adopting a processing method according to the purpose, such as the SMC molding method and the LFT-D method. In some cases, it is also possible to interpose a step of pre-shaping.

　本発明３の樹脂含浸繊維からなる層を熱可塑性樹脂シートまたはフィルムと積層させた積層体は、プレス成型等により成形品を得ることができる。また、場合によっては予備賦形を行う工程を挟むことも可能である。 A laminate obtained by laminating a layer made of the resin-impregnated fiber of the present invention 3 with a thermoplastic resin sheet or film can be molded by press molding or the like. In some cases, it is also possible to interpose a step of pre-shaping.

　成形品の加工温度に特に制限はなく、使用される熱可塑性樹脂の特性により任意の温度を選択することが可能であるが、成形サイクルの点から１８０～２７０℃の範囲で成形することが好ましく、更に好ましくは１８０～２５０℃の範囲である。 There is no particular limitation on the processing temperature of the molded product, and it is possible to select any temperature according to the properties of the thermoplastic resin used, but it is preferable to mold in the range of 180 to 270 ° C. , and more preferably in the range of 180 to 250°C.

　＜本発明４＞
　以下、本発明４につき詳細に説明する。 <Invention 4>
Hereinafter, the present invention 4 will be described in detail.

　本発明４の繊維集束用組成物に含まれる熱可塑性エマルジョンは、複数の単量体が重合した共重合体を含有する。複数の単量体は、芳香族ビニル系単量体を必須成分として含有する。芳香族ビニル系単量体としては、スチレン、α－メチルスチレン、ビニルトルエンおよびジビニルベンゼン等が挙げられ、これらを１種または２種以上使用することができる。特にスチレン、α－メチルスチレンの使用が好ましい。 The thermoplastic emulsion contained in the fiber bundling composition of the present invention 4 contains a copolymer obtained by polymerizing a plurality of monomers. A plurality of monomers contain an aromatic vinyl-based monomer as an essential component. Examples of the aromatic vinyl-based monomer include styrene, α-methylstyrene, vinyltoluene, divinylbenzene, and the like, and one or more of these can be used. Styrene and α-methylstyrene are particularly preferred.

　芳香族ビニル系単量体と共重合可能な他の単量体としては、エチレン系不飽和カルボン酸単量体、シアン化ビニル系単量体、アルキルエステル系単量体、ヒドロキシアルキル基を含有する不飽和単量体、不飽和カルボン酸アミド系単量体、ビニルピリジン系単量体、共役ジエン系単量体等が挙げられ、目的に応じて各々1種または2種以上混合して使用することが可能である。 Other monomers copolymerizable with aromatic vinyl monomers include ethylenically unsaturated carboxylic acid monomers, vinyl cyanide monomers, alkyl ester monomers, and hydroxyalkyl group-containing monomers. unsaturated monomers, unsaturated carboxylic acid amide-based monomers, vinylpyridine-based monomers, and conjugated diene-based monomers. It is possible to

　エチレン系不飽和カルボン酸単量体としては、アクリル酸、メタクリル酸、クロトン酸、マレイン酸、フマル酸、イタコン酸などのモノまたはジカルボン酸（無水物）等が挙げられる。 Examples of ethylenically unsaturated carboxylic acid monomers include mono- or dicarboxylic acids (anhydrides) such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, and itaconic acid.

　シアン化ビニル系単量体としては、アクリロニトリル、メタクリロニトリル、α－クロルアクリロニトリル、α－エチルアクリロニトリル等が挙げられる。 Examples of vinyl cyanide-based monomers include acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, α-ethylacrylonitrile and the like.

　アルキルエステル系単量体としては、メチルアクリレート、メチルメタクリレート、エチルアクリレート、エチルメタクリレート、ブチルアクリレート、グリシジルメタクリレート、ジメチルフマレート、ジエチルフマレート、ジメチルマレエート、ジエチルマルエート、ジメチルイタコネート、モノメチルフマレート、モノエチルフマレート、２－エチルヘキシルアクリレート等が挙げられる。 Alkyl ester monomers include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, glycidyl methacrylate, dimethyl fumarate, diethyl fumarate, dimethyl maleate, diethyl malate, dimethyl itaconate, and monomethyl fumarate. , monoethyl fumarate, 2-ethylhexyl acrylate and the like.

　ヒドロキシアルキル基を含有する不飽和単量体としては、β－ヒドロキシエチルアクリレート、β－ヒドロキシエチルメタクリレート、ヒドロキシプロピルアクリレート、ヒドロキシプロピルメタクリレート、ヒドロキシブチルアクリレート、ヒドロキシブチルメタクリレート、３－クロロ－２－ヒドロキシプロピルメタクリレート、ジ－（エチレングリコール）マレエート、ジ－（エチレングリコール）イタコネート、２－ヒドロキシエチルマレエート、ビス（２－ヒドロキシエチル）マレエート、２－ヒドロキシエチルメチルフマレート等が挙げられる。 Unsaturated monomers containing hydroxyalkyl groups include β-hydroxyethyl acrylate, β-hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, hydroxybutyl methacrylate, 3-chloro-2-hydroxypropyl Methacrylate, di-(ethylene glycol) maleate, di-(ethylene glycol) itaconate, 2-hydroxyethyl maleate, bis(2-hydroxyethyl) maleate, 2-hydroxyethyl methyl fumarate and the like.

　不飽和カルボン酸アミド系単量体としては、アクリルアミド、メタクリルアミド、Ｎ－メチロールアクリルアミド、Ｎ－メチロールメタクリルアミド、Ｎ，Ｎ－ジメチルアクリルアミド等が挙げられる。 Examples of unsaturated carboxylic acid amide-based monomers include acrylamide, methacrylamide, N-methylol acrylamide, N-methylol methacrylamide, and N,N-dimethylacrylamide.

　ビニルピリジン系単量体としては、２－ビニルピリジン、３－ビニルピリジン、４－ビニルピリジン、２－メチル－５－ビニルピリジン等が挙げられる。 Examples of vinylpyridine-based monomers include 2-vinylpyridine, 3-vinylpyridine, 4-vinylpyridine, and 2-methyl-5-vinylpyridine.

　共役ジエン系単量体としては、１，３－ブタジエン、２－メチル－１，３－ブタジエン、２，３－ジメチル－１，３－ブタジエン、２－クロル－１，３－ブタジエン、置換直鎖共役ペンタジエン類、置換および側鎖共役ヘキサジエン類等が挙げられる。 Conjugated diene-based monomers include 1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 2-chloro-1,3-butadiene, substituted linear Conjugated pentadienes, substituted and side chain conjugated hexadienes, and the like.

　中でも、芳香族ビニル系単量体と共重合可能な他の単量体としては、アクリル酸、メタクリル酸、フマル酸、イタコン酸、アクリロニトリル、メタクリロニトリル、メチルメタクリレート、ブチルアクリレート、β－ヒドロキシエチルアクリレート、アクリルアミドまたはメタクリルアミド、２－ビニルピリジン、１，３－ブタジエンの使用が好ましい。 Among others, other monomers copolymerizable with aromatic vinyl monomers include acrylic acid, methacrylic acid, fumaric acid, itaconic acid, acrylonitrile, methacrylonitrile, methyl methacrylate, butyl acrylate, and β-hydroxyethyl. Preference is given to using acrylates, acrylamides or methacrylamides, 2-vinylpyridine, 1,3-butadiene.

　全単量体中の芳香族ビニル系単量体の含有量は、４０～９８．５重量％であり、４５～９５重量％であることが好ましく、４７～９０重量％であることがより好ましい。この範囲に調整することで樹脂含浸繊維と熱可塑性樹脂との接着性に優れる傾向にある。 The content of the aromatic vinyl monomer in the total monomer is 40 to 98.5% by weight, preferably 45 to 95% by weight, more preferably 47 to 90% by weight. . By adjusting it within this range, the adhesion between the resin-impregnated fiber and the thermoplastic resin tends to be excellent.

　全単量体中の「芳香族ビニル系単量体と共重合可能な他の単量体」の含有量は、芳香族ビニル系樹脂エマルジョン１００重量％に対して、１．５～６０重量％であり、５～５５重量％であることが好ましく、１０～５３重量％であることがより好ましい。この範囲に調整することで樹脂含浸繊維と熱可塑性樹脂との接着性に優れる傾向にある。 The content of "other monomers copolymerizable with the aromatic vinyl monomer" in all monomers is 1.5 to 60% by weight with respect to 100% by weight of the aromatic vinyl resin emulsion. and preferably 5 to 55% by weight, more preferably 10 to 53% by weight. By adjusting it within this range, the adhesion between the resin-impregnated fiber and the thermoplastic resin tends to be excellent.

　熱可塑性樹脂エマルジョンの各単量体の好ましい組成比率としては、芳香族ビニル系単量体６０～９５重量％、シアン化ビニル系単量体４～３９重量％、エチレン系不飽和カルボン酸単量体１～１５重量％が挙げられ、さらに好ましい組成比率としては、芳香族ビニル系単量体８０～９４重量％、シアン化ビニル系単量体５～１５重量％、エチレン系不飽和カルボン酸単量体１～５重量％が挙げられる。 The preferable composition ratio of each monomer in the thermoplastic resin emulsion is 60 to 95% by weight of aromatic vinyl monomer, 4 to 39% by weight of vinyl cyanide monomer, and ethylenically unsaturated carboxylic acid monomer. 1 to 15% by weight of aromatic vinyl monomers, 5 to 15% by weight of vinyl cyanide monomers, and ethylenically unsaturated carboxylic acid monomers. from 1 to 5% by weight.

　本発明４の繊維集束用組成物に含まれる熱可塑性樹脂エマルジョンは、乳化重合により得られる場合、本発明４の目的を損なわない範囲であれば特に制限はなく公知の乳化重合法、例えば、一括添加方法、分割添加方法、連続添加方法、多段階重合法、シード重合法、パワーフィード重合法等の何れを採用してもよい。中でも重合時の安定性や分子量の調整の容易さから連続添加方法が好ましい。 When the thermoplastic resin emulsion contained in the fiber bundling composition of the present invention 4 is obtained by emulsion polymerization, it is not particularly limited as long as it does not impair the purpose of the present invention 4. Any of an addition method, a divided addition method, a continuous addition method, a multistage polymerization method, a seed polymerization method, a power feed polymerization method, and the like may be employed. Among them, the continuous addition method is preferable from the standpoint of stability during polymerization and ease of adjustment of the molecular weight.

　本発明４の繊維集束用組成物に含まれる熱可塑性樹脂エマルジョンを乳化重合の際には、ｎ－ヘキシルメルカプタン、ｎ－オクチルメルカプタン、ｔ－オクチルメルカプタン、ｎ－ドデシルメルカプタン、ｔ－ドデシルメルカプタン、ｎ－ステアリルメルカプタン等のアルキルメルカプタン、ジメチルキサントゲンジサルファイド、ジイソプロピルキサントゲンジサルファイド等のキサントゲン化合物、テトラメチルチウラムジスルフィド、テトラエチルチウラムジスルフィド、テトラメチルチウラムモノスルフィド等のチウラム系化合物、２，６－ジ－ｔ－ブチル－４－メチルフェノール、スチレン化フェノール等のフェノール系化合物、アリルアルコール等のアリル化合物、ジクロルメタン、ジブロモメタン、四臭化炭素等のハロゲン化炭化水素化合物、α－ベンジルオキシスチレン、α－ベンジルオキシアクリロニトリル、α－ベンジルオキシアクリルアミド等のビニルエーテル、トリフェニルエタン、ペンタフェニルエタン、アクロレイン、メタアクロレイン、チオグリコール酸、チオリンゴ酸、２－エチルヘキシルチオグリコレート、α－メチルスチレンダイマー、ターピノレン等の連鎖移動剤や過硫酸カリウム、過硫酸ナトリウム、過硫酸アンモニウム等の水溶性重合開始剤、クメンハイドロパーオキサイド、過酸化ベンゾイル、t－ブチルハイドロパーオキサイド、アセチルパーオキサイド、ジイソプロピルベンゼンハイドロパーオキサイド、１，１，３，３－テトラメチルブチルハイドロパーオキサイド等の油溶性重合開始剤、還元剤である硫酸第一鉄、亜硫酸塩、亜硫酸水素塩、ピロ亜硫酸塩、亜ニチオン酸塩、ニチオン酸塩、チオ硫酸塩、また、ホルムアルデヒドスルホン酸塩、ベンズアルデヒドスルホン酸塩などの還元性スルホン酸塩、更にはＬ－アスコルビン酸、酒石酸、クエン酸などのカルボン酸類、更にはデキストロース、サッカロースなどの還元糖類、更にはジメチルアニリン、トリエタノールアミンなどのアミン類の各々１種または２種以上の添加剤を使用することも可能である。これらの添加剤の使用量に特に制限は無いが、製品コストや最終製品の外観への影響を考えると、全単量体１００重量部に対して、各々０．０１～５重量部の範囲で使用することが好ましい。 When emulsifying the thermoplastic resin emulsion contained in the fiber bundling composition of the present invention 4, n-hexylmercaptan, n-octylmercaptan, t-octylmercaptan, n-dodecylmercaptan, t-dodecylmercaptan, n - alkyl mercaptans such as stearyl mercaptan; xanthogen compounds such as dimethylxanthogen disulfide and diisopropyl xanthogen disulfide; thiuram compounds such as tetramethylthiuram disulfide, tetraethylthiuram disulfide and tetramethylthiuram monosulfide; Phenolic compounds such as butyl-4-methylphenol and styrenated phenol, allyl compounds such as allyl alcohol, halogenated hydrocarbon compounds such as dichloromethane, dibromomethane, and carbon tetrabromide, α-benzyloxystyrene, α-benzyloxy Acrylonitrile, vinyl ethers such as α-benzyloxyacrylamide, chain transfer agents such as triphenylethane, pentaphenylethane, acrolein, methacrolein, thioglycolic acid, thiomalic acid, 2-ethylhexylthioglycolate, α-methylstyrene dimer, and terpinolene and water-soluble polymerization initiators such as potassium persulfate, sodium persulfate and ammonium persulfate, cumene hydroperoxide, benzoyl peroxide, t-butyl hydroperoxide, acetyl peroxide, diisopropylbenzene hydroperoxide, 1,1,3 , an oil-soluble polymerization initiator such as 3-tetramethylbutyl hydroperoxide, a reducing agent ferrous sulfate, sulfite, hydrogen sulfite, pyrosulfite, nitionite, nitionate, thiosulfate, In addition, reducing sulfonates such as formaldehyde sulfonate and benzaldehyde sulfonate, further carboxylic acids such as L-ascorbic acid, tartaric acid and citric acid, further reducing sugars such as dextrose and saccharose, further dimethylaniline, It is also possible to use one or more additives each of amines such as triethanolamine. There is no particular limit to the amount of these additives used, but considering the effect on the product cost and the appearance of the final product, each in the range of 0.01 to 5 parts by weight per 100 parts by weight of the total monomers. It is preferred to use

　本発明４の繊維集束用組成物に含まれる熱可塑性樹脂エマルジョンを乳化重合する際に使用される乳化剤に特に制限はなく、例えば、高級アルコールの硫酸エステル塩、アルキルベンゼンスルホン酸塩、アルキルジフェニルエーテルスルホン酸塩、脂肪族スルホン酸塩、脂肪族カルボン酸塩、非イオン性界面活性剤の硫酸エステル塩等のアニオン性界面活性剤あるいはポリエチレングリコールのアルキルエステル型、アルキルフェニルエーテル型、アルキルエーテル型等のノニオン性界面活性剤が挙げられ、これらを１種又は２種以上使用することができ、全単量体１００重量部に対して、０．０５～１０重量部の範囲で使用するのが好ましい。０．０５重量部未満では重合液の安定性に劣り、１０重量部を越えると最終製品での成型の際にガスが多量に発生し、成形品表面を損なう不具合が発生する。好ましくは０．１～８重量部、より好ましくは０．５～５重量部の範囲である。 The emulsifier used in the emulsion polymerization of the thermoplastic resin emulsion contained in the fiber bundling composition of the present invention 4 is not particularly limited. Salts, aliphatic sulfonates, aliphatic carboxylates, anionic surfactants such as sulfuric acid ester salts of nonionic surfactants, or nonions such as alkyl ester types, alkylphenyl ether types, and alkyl ether types of polyethylene glycol One or more of these may be used, and it is preferable to use them in the range of 0.05 to 10 parts by weight per 100 parts by weight of the total monomers. If it is less than 0.05 parts by weight, the stability of the polymerization liquid is poor, and if it exceeds 10 parts by weight, a large amount of gas is generated during the molding of the final product, resulting in damage to the surface of the molded product. The range is preferably 0.1 to 8 parts by weight, more preferably 0.5 to 5 parts by weight.

　更に、重合時には、公知の電解質、重合促進剤、キレート剤等を使用することができる。 Furthermore, known electrolytes, polymerization accelerators, chelating agents, etc. can be used during polymerization.

　本発明４の繊維集束用組成物に含まれる熱可塑性樹脂エマルジョンのガラス転移温度は１１０℃以下であることが、繊維間への含浸の点から好ましい。特に好ましくは１０５℃以下である。尚、ガラス転移温度は通常のＤＳＣ法により測定することが可能である。 The glass transition temperature of the thermoplastic resin emulsion contained in the fiber bundling composition of the present invention 4 is preferably 110°C or less from the viewpoint of impregnation between fibers. Particularly preferably, it is 105° C. or less. Incidentally, the glass transition temperature can be measured by a normal DSC method.

　上記、ガラス転移温度の調整は、単量体の混合比率、重合時に用いる添加剤の種類や量、重合温度、重合後に添加する添加剤等により調整することが可能である。 The above glass transition temperature can be adjusted by adjusting the mixing ratio of the monomers, the types and amounts of additives used during polymerization, the polymerization temperature, additives added after polymerization, and the like.

　熱可塑性樹脂エマルジョンの平均粒子径は、１５０ｎｍ以下であり、１３０ｎｍ以下であることが好ましく、１２７ｎｍ以下であることがより好ましく、１００ｎｍ以下であることがさらに好ましい。 The average particle size of the thermoplastic resin emulsion is 150 nm or less, preferably 130 nm or less, more preferably 127 nm or less, and even more preferably 100 nm or less.

　熱可塑性樹脂エマルジョンの平均粒子径が１５０ｎｍを超えると、炭素繊維に繊維集束用組成物が浸透しにくくなり、含浸性が低下する。また、熱可塑性樹脂エマルジョンの平均粒子径が７０ｎｍ未満であると、熱可塑性樹脂エマルジョンの分散安定性が低下する。 When the average particle size of the thermoplastic resin emulsion exceeds 150 nm, it becomes difficult for the fiber bundling composition to permeate the carbon fibers, resulting in a decrease in impregnability. Further, when the average particle size of the thermoplastic resin emulsion is less than 70 nm, the dispersion stability of the thermoplastic resin emulsion is lowered.

　熱可塑性樹脂エマルジョンの平均粒子径は、例えば、実施例に記載されている方法で測定することができる。 The average particle size of the thermoplastic resin emulsion can be measured, for example, by the method described in Examples.

　また、熱可塑性樹脂エマルジョンの粒子径は、その乳化重合時の乳化剤量や重合時の使用重合水を変えることによって調整することも可能である。乳化剤量は、全単量体１００重量部に対して、１．８～２．５重量部であることが好ましい。また、乳化剤は２段以上で添加することが好ましく、１段目に全添加量の１５～９５重量％を添加することが好ましく、３０～９０重量％を添加することがより好ましい。使用重合水量は、９０～２７０重量部であることが好ましく、１４０～２５０重量部であることがより好ましい。 Also, the particle size of the thermoplastic resin emulsion can be adjusted by changing the amount of emulsifier during emulsion polymerization and the polymerization water used during polymerization. The amount of emulsifier is preferably 1.8 to 2.5 parts by weight with respect to 100 parts by weight of all monomers. The emulsifier is preferably added in two or more stages, preferably 15 to 95% by weight of the total amount added in the first stage, more preferably 30 to 90% by weight. The amount of polymerization water used is preferably 90 to 270 parts by weight, more preferably 140 to 250 parts by weight.

　また、本発明４の繊維集束用組成物には、ポリエステル系樹脂エマルジョン、ポリウレタン系樹脂エマルジョン、酢酸ビニル系樹脂エマルジョン、塩化ビニリデン系樹脂エマルジョン、ポリアミド系樹脂エマルジョン、芳香族ビニル系樹脂エマルジョン、アクリル系樹脂エマルジョン、オレフィン系樹脂エマルジョンなどの他の熱可塑性樹脂エマルジョン、分散剤、レベリング剤、滑剤、消泡剤、濡れ剤、防腐剤、酸化防止剤、紫外線吸収剤、光安定化剤、着色剤、帯電防止剤、可塑剤等を本発明４の効果を損なわない範囲に配合して使用することが可能である。 In addition, the fiber bundling composition of the present invention 4 includes a polyester resin emulsion, a polyurethane resin emulsion, a vinyl acetate resin emulsion, a vinylidene chloride resin emulsion, a polyamide resin emulsion, an aromatic vinyl resin emulsion, and an acrylic resin emulsion. Other thermoplastic resin emulsions such as resin emulsions and olefin resin emulsions, dispersants, leveling agents, lubricants, antifoaming agents, wetting agents, preservatives, antioxidants, UV absorbers, light stabilizers, colorants, An antistatic agent, a plasticizer, etc. can be blended and used within a range that does not impair the effects of the present invention 4.

　本発明４の繊維集束用組成物中の熱可塑性樹脂エマルジョンの含有割合（固形分換算）は、８０重量％以上であることが好ましく、９０重量％以上であることがより好ましい。また、繊維集束用組成物中の他の樹脂エマルジョンの含有割合（固形分換算）は、２０重量％以下であることが好ましく、１０重量％以下であることがより好ましい。 The content of the thermoplastic resin emulsion (in terms of solid content) in the fiber bundling composition of the present invention 4 is preferably 80% by weight or more, more preferably 90% by weight or more. The content of the other resin emulsion in the fiber bundling composition (in terms of solid content) is preferably 20% by weight or less, more preferably 10% by weight or less.

　本発明４の繊維集束用組成物を繊維に集束させる方法には特に制限はなく、スプレー法や塗布法または含浸法等の方法から１種または２種以上組み合わせて選択することが可能である。 The method for bundling the fiber bundling composition of the present invention 4 into fibers is not particularly limited, and it is possible to select one or a combination of two or more from methods such as a spray method, a coating method, and an impregnation method.

　本発明４の繊維集束用組成物を集束させる繊維としては、炭素繊維、ガラス繊維、硼素繊維、炭化ケイ素繊維、あるいはアルミウム繊維、ステンレス繊維、銅繊維、ニッケル繊維などの金属繊維、ポリアミド繊維、ポリエステル繊維、ポリアリレート繊維、ポリイミド繊維、（ナノ）セルロース繊維などの有機繊維等を用いることが出来る。さらにこれらの繊維は１種または２種以上を組み合わせて用いることも可能である。中でも、炭素繊維が最も好ましい。炭素繊維には、通常の炭素繊維に加えて、ニッケルなどの金属で被覆処理した炭素繊維なども含まれ、かつその形態に特に制限はなく、連続繊維、チョップド繊維、ミルド形状や不織布等、目的に応じて任意の形態のものを選ぶことが可能である。 Examples of fibers for bundling the fiber bundling composition of the present invention 4 include carbon fiber, glass fiber, boron fiber, silicon carbide fiber, metal fiber such as aluminum fiber, stainless steel fiber, copper fiber, nickel fiber, polyamide fiber, and polyester. Organic fibers such as fibers, polyarylate fibers, polyimide fibers, and (nano)cellulose fibers can be used. Furthermore, these fibers can be used singly or in combination of two or more. Among them, carbon fiber is most preferable. In addition to ordinary carbon fibers, carbon fibers include carbon fibers coated with metal such as nickel, and there are no particular restrictions on the form thereof, and may be continuous fibers, chopped fibers, milled shapes, non-woven fabrics, etc. Any form can be selected according to the requirements.

　本発明４における繊維集束用組成物と繊維の含有比率には特に制限は無いが、熱可塑性樹脂との接着性や最終製品の強度面から、固形分換算で、繊維集束用組成物１～２０重量部、繊維９９～８０重量部の範囲で含浸させることが好ましい。 Although there is no particular limitation on the content ratio of the fiber bundling composition and the fiber in the present invention 4, from the standpoint of adhesiveness with the thermoplastic resin and strength of the final product, the fiber bundling composition is 1 to 20 in terms of solid content. It is preferable to impregnate in the range of 99 to 80 parts by weight of fibers.

　本発明４の樹脂含浸繊維における、繊維に繊維集束用組成物を集束させた後の水分の蒸発方法については特に制限はなく、例えば乾燥機を使用する方法、赤外線を照射する方法、連続的に乾燥機を通過させる方法等を目的に応じて採用することが可能である。中でも、水分の蒸発だけではなく、集束した繊維集束用組成物を溶融させ、繊維表面を更に均一に被覆させるために、繊維集束用組成物のガラス転移温度＋６０℃以上に調整された１ｍ以上の行路を持つ乾燥機内を０．５ｍ/分以上の速度で連続的に通過させながら乾燥することが好ましい。 In the resin-impregnated fiber of the present invention 4, the method of evaporating the moisture after the fiber bundling composition is bundled is not particularly limited. A method of passing through a dryer or the like can be employed depending on the purpose. Above all, in order not only to evaporate the moisture but also to melt the bundled fiber bundling composition and more uniformly coat the fiber surface, the glass transition temperature of the fiber bundling composition + 1 m or more adjusted to 60 ° C. or higher It is preferable to dry while continuously passing through a dryer having tracks at a speed of 0.5 m/min or more.

　本発明４の樹脂含浸繊維は、熱可塑性樹脂と溶融混練し、繊維強化熱可塑性樹脂組成物として用いることができる。さらに、熱可塑性樹脂シートまたはフィルムと積層させた積層品として用いることもできる。 The resin-impregnated fiber of the present invention 4 can be melt-kneaded with a thermoplastic resin and used as a fiber-reinforced thermoplastic resin composition. Furthermore, it can also be used as a laminate laminated with a thermoplastic resin sheet or film.

　本発明４の樹脂含浸繊維と組み合わせる熱可塑性樹脂としては、例えば、ポリスチレン（ＰＳ）、耐衝撃性ポリスチレン（ＨＩＰＳ）、アクリロニトリル－ブタジエンゴム－スチレン共重合体（ＡＢＳ）、アクリロニトリル－エチレンプロピレンゴム－スチレン共重合体（ＡＥＳ）、アクリロニトリル－アクリルゴム－スチレン共重合体（ＡＳＡ）、アクリロニトリル－スチレン共重合体（ＡＳ）等のスチレン系樹脂、ポリエチレン（ＰＥ）、ポリプロピレン（ＰＰ）等のポリオレフィン樹脂、ポリカーボネート（ＰＣ）、ポリエチレンテレフタレート（ＰＥＴ）、ポリブチレンテレフタレート（ＰＢＴ）等のポリエステル樹脂、ポリメチルメタクリレート樹脂（ＰＭＭＡ）、ポリアミド樹脂（ＰＡ）、熱可塑性ポリウレタン樹脂（ＴＰＵ）、ポリ乳酸樹脂（ＰＬＡ）、ポリエーテルサルフォン（ＰＥＳ）、ポリフェニレンサルファイド（ＰＰＳ）あるいはスチレン系樹脂と、ポリカーボネート（ＰＣ）、ポリアミド樹脂（ＰＡ）、及びポリ乳酸樹脂（ＰＬＡ）から選ばれる１種以上の樹脂とのアロイが例示され、最終製品の要求性能に合わせて１種又は２種以上組み合わせて用いることが可能である。中でもスチレン系樹脂、ポリエステル樹脂、ポリアミド樹脂、およびスチレン系樹脂とポリエステル樹脂またはポリアミドとのアロイが、最終製品の成形性と強度のバランスの点で好ましく、ポリエステル樹脂またはポリアミドがより好ましい。 Examples of the thermoplastic resin to be combined with the resin-impregnated fiber of the present invention 4 include polystyrene (PS), high-impact polystyrene (HIPS), acrylonitrile-butadiene rubber-styrene copolymer (ABS), acrylonitrile-ethylene propylene rubber-styrene. Copolymer (AES), acrylonitrile-acrylic rubber-styrene copolymer (ASA), acrylonitrile-styrene copolymer (AS) and other styrene resins, polyethylene (PE), polypropylene (PP) and other polyolefin resins, polycarbonate (PC), polyethylene terephthalate (PET), polyester resins such as polybutylene terephthalate (PBT), polymethyl methacrylate resin (PMMA), polyamide resin (PA), thermoplastic polyurethane resin (TPU), polylactic acid resin (PLA), Examples include alloys of polyether sulfone (PES), polyphenylene sulfide (PPS) or styrenic resin and one or more resins selected from polycarbonate (PC), polyamide resin (PA) and polylactic acid resin (PLA). It is possible to use one type or a combination of two or more types according to the required performance of the final product. Among them, styrene resins, polyester resins, polyamide resins, and alloys of styrene resins and polyester resins or polyamides are preferred from the viewpoint of the balance between moldability and strength of the final product, and polyester resins or polyamides are more preferred.

　本発明４の樹脂含浸繊維と組み合せる熱可塑性樹脂には、例えば、光安定剤、酸化防止剤、熱安定剤、紫外線吸収剤、滑剤、難燃剤、難燃助剤、可塑剤、顔料、染料等の各種添加剤を含むこともできる。 The thermoplastic resin to be combined with the resin-impregnated fiber of the present invention 4 includes, for example, light stabilizers, antioxidants, heat stabilizers, ultraviolet absorbers, lubricants, flame retardants, flame retardant aids, plasticizers, pigments, dyes. Various additives such as can also be included.

　本発明４の樹脂含浸繊維と熱可塑性樹脂とを溶融混練して得られた繊維強化熱可塑性樹脂組成物は、例えば、射出成形、多層押し出し成形、フィルム成形、シート成形、インフレーション成形、プレス成形、ＳＭＣ成形法、ＬＦＴ－Ｄ法等、目的に応じた加工法を採用することで成形品を得ることが可能である。また、場合によっては予備賦形を行う工程を挟むことも可能である。 The fiber-reinforced thermoplastic resin composition obtained by melt-kneading the resin-impregnated fiber of the present invention 4 and a thermoplastic resin can be, for example, injection molding, multilayer extrusion molding, film molding, sheet molding, inflation molding, press molding, A molded article can be obtained by adopting a processing method according to the purpose, such as the SMC molding method and the LFT-D method. In some cases, it is also possible to interpose a step of pre-shaping.

　本発明４の樹脂含浸繊維からなる層を熱可塑性樹脂シートまたはフィルムと積層させた積層体は、プレス成型等により成形品を得ることができる。また、場合によっては予備賦形を行う工程を挟むことも可能である。 A laminate obtained by laminating a layer made of the resin-impregnated fiber of the present invention 4 with a thermoplastic resin sheet or film can be molded by press molding or the like. In some cases, it is also possible to interpose a step of pre-shaping.

　成形品の加工温度に特に制限はなく、使用される熱可塑性樹脂の特性により任意の温度を選択することが可能であるが、成形サイクルの点から１８０～２７０℃の範囲で成形することが好ましく、更に好ましくは１８０～２５０℃の範囲である。 There is no particular limitation on the processing temperature of the molded product, and it is possible to select any temperature according to the properties of the thermoplastic resin used, but it is preferable to mold in the range of 180 to 270 ° C. , and more preferably in the range of 180 to 250°C.

　＜本発明５＞
　以下、本発明５につき詳細に説明する。 <Invention 5>
Hereinafter, the present invention 5 will be described in detail.

　本発明５の繊維集束用組成物は、熱可塑性樹脂エマルジョンを含むものである。 The fiber bundling composition of the present invention 5 contains a thermoplastic resin emulsion.

　本発明５の繊維集束用組成物に含まれる熱可塑性樹脂エマルジョンは、熱可塑性樹脂の水分散体であれば特に制限なく、例えば、ポリエステル系樹脂エマルジョン、ポリウレタン系樹脂エマルジョン、酢酸ビニル系樹脂エマルジョン、塩化ビニリデン系樹脂エマルジョン、ポリアミド系樹脂エマルジョン、芳香族ビニル系樹脂エマルジョン、アクリル系樹脂エマルジョン、オレフィン系樹脂エマルジョンなどが挙げられる。 The thermoplastic resin emulsion contained in the fiber bundling composition of the present invention 5 is not particularly limited as long as it is an aqueous dispersion of a thermoplastic resin. Examples include polyester resin emulsion, polyurethane resin emulsion, vinyl acetate resin emulsion, Examples include vinylidene chloride resin emulsions, polyamide resin emulsions, aromatic vinyl resin emulsions, acrylic resin emulsions, and olefin resin emulsions.

　中でも、集束された繊維の取り扱いの容易さや最終製品の性能の点から、熱可塑性樹脂エマルジョンは、好ましくは、エチレン系不飽和カルボン酸単量体を含有する複数の単量体が重合した共重合体を含有する。 Among them, the thermoplastic resin emulsion is preferably a copolymer obtained by polymerizing a plurality of monomers containing an ethylenically unsaturated carboxylic acid monomer, from the viewpoint of ease of handling of bundled fibers and performance of the final product. Contains coalescence.

　エチレン系不飽和カルボン酸単量体としては、アクリル酸、メタクリル酸及びクロトン酸などのモノカルボン酸単量体、マレイン酸、フマル酸及びイタコン酸などのジカルボン酸単量体並びにこれらの無水物が挙げられる。これらの単量体は１種を単独でまたは２種以上を組み合わせて使用することができる。特にアクリル酸、メタクリル酸、イタコン酸の使用が好ましい。 Ethylenically unsaturated carboxylic acid monomers include monocarboxylic acid monomers such as acrylic acid, methacrylic acid and crotonic acid, dicarboxylic acid monomers such as maleic acid, fumaric acid and itaconic acid, and their anhydrides. mentioned. These monomers can be used individually by 1 type or in combination of 2 or more types. The use of acrylic acid, methacrylic acid and itaconic acid is particularly preferred.

　エチレン系不飽和カルボン酸単量体と共重合可能な他の単量体としては、芳香族ビニル系単量体、シアン化ビニル系単量体、アルキルエステル系単量体、ヒドロキシアルキル基を含有する不飽和単量体、不飽和カルボン酸アミド系単量体、ビニルピリジン系単量体、オキサゾリン系単量体、共役ジエン系単量体等が挙げられ、目的に応じて各々1種または2種以上混合して使用することが可能である。 Other monomers copolymerizable with ethylenically unsaturated carboxylic acid monomers include aromatic vinyl monomers, vinyl cyanide monomers, alkyl ester monomers, and hydroxyalkyl group-containing monomers. unsaturated monomers, unsaturated carboxylic acid amide-based monomers, vinylpyridine-based monomers, oxazoline-based monomers, and conjugated diene-based monomers. It is possible to use a mixture of more than one species.

　芳香族ビニル系単量体としては、スチレン、α－メチルスチレン、ビニルトルエンおよびジビニルベンゼン等が挙げられ、これらを１種または２種以上使用することができる。 The aromatic vinyl-based monomers include styrene, α-methylstyrene, vinyltoluene, divinylbenzene, and the like, and one or more of these can be used.

　シアン化ビニル系単量体としては、アクリロニトリル、メタクリロニトリル、α－クロルアクリロニトリル、α－エチルアクリロニトリル等が挙げられ、これらを１種または２種以上使用することができる。 Examples of vinyl cyanide-based monomers include acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, α-ethylacrylonitrile, and the like, and one or more of these can be used.

　アルキルエステル系単量体としては、メチルアクリレート、メチルメタクリレート、エチルアクリレート、エチルメタクリレート、ブチルアクリレート、グリシジルメタクリレート、ジメチルフマレート、ジエチルフマレート、ジメチルマレエート、ジエチルマルエート、ジメチルイタコネート、モノメチルフマレート、モノエチルフマレート、２－エチルヘキシルアクリレート等が挙げられ、これらを１種または２種以上使用することができる。 Alkyl ester monomers include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, glycidyl methacrylate, dimethyl fumarate, diethyl fumarate, dimethyl maleate, diethyl malate, dimethyl itaconate, and monomethyl fumarate. , monoethyl fumarate, 2-ethylhexyl acrylate and the like, and one or more of these can be used.

　ヒドロキシアルキル基を含有する不飽和単量体としては、β－ヒドロキシエチルアクリレート、β－ヒドロキシエチルメタクリレート、ヒドロキシプロピルアクリレート、ヒドロキシプロピルメタクリレート、ヒドロキシブチルアクリレート、ヒドロキシブチルメタクリレート、３－クロロ－２－ヒドロキシプロピルメタクリレート、ジ－（エチレングリコール）マレエート、ジ－（エチレングリコール）イタコネート、２－ヒドロキシエチルマレエート、ビス（２－ヒドロキシエチル）マレエート、２－ヒドロキシエチルメチルフマレート等が挙げられ、これらを１種または２種以上使用することができる。 Unsaturated monomers containing hydroxyalkyl groups include β-hydroxyethyl acrylate, β-hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, hydroxybutyl methacrylate, 3-chloro-2-hydroxypropyl methacrylate, di-(ethylene glycol) maleate, di-(ethylene glycol) itaconate, 2-hydroxyethyl maleate, bis(2-hydroxyethyl) maleate, 2-hydroxyethyl methyl fumarate and the like, one of which Or 2 or more types can be used.

　不飽和カルボン酸アミド系単量体としては、アクリルアミド、メタクリルアミド、Ｎ－メチロールアクリルアミド、Ｎ－メチロールメタクリルアミド、Ｎ，Ｎ－ジメチルアクリルアミド等が挙げられ、これらを１種または２種以上使用することができる。 Examples of unsaturated carboxylic acid amide-based monomers include acrylamide, methacrylamide, N-methylol acrylamide, N-methylol methacrylamide, N,N-dimethylacrylamide and the like, and one or more of these may be used. can be done.

　ビニルピリジン系単量体としては、２－ビニルピリジン、３－ビニルピリジン、４－ビニルピリジン、２－メチル－５－ビニルピリジン等が挙げられ、これらを１種または２種以上使用することができる。 Vinylpyridine-based monomers include 2-vinylpyridine, 3-vinylpyridine, 4-vinylpyridine, 2-methyl-5-vinylpyridine and the like, and one or more of these may be used. .

　オキサゾリン系単量体としては、例えば２－ビニル－２－オキサゾリンや４，４－ジメチル－２－ビニル－２－オキサゾリン－５－オン等が挙げられ、これらを１種または２種以上使用することができる。 Examples of oxazoline-based monomers include 2-vinyl-2-oxazoline and 4,4-dimethyl-2-vinyl-2-oxazoline-5-one, and one or more of these may be used. can be done.

　共役ジエン系単量体としては、１，３－ブタジエン、２－メチル－１，３－ブタジエン、２，３－ジメチル－１，３－ブタジエン、２－クロル－１，３－ブタジエン等が挙げられ、これらを１種または２種以上使用することができる。 Conjugated diene monomers include 1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 2-chloro-1,3-butadiene and the like. , these can be used alone or in combination of two or more.

　中でも、エチレン系不飽和カルボン酸単量体と共重合可能な他の単量体として、スチレン、α－メチルスチレン、アクリロニトリル、メチルメタクリレート、ブチルアクリレート、β－ヒドロキシエチルアクリレート、アクリルアミドまたはメタクリルアミド、２－ビニルピリジン、１，３－ブタジエンの使用が好ましい。 Among others, other monomers copolymerizable with ethylenically unsaturated carboxylic acid monomers include styrene, α-methylstyrene, acrylonitrile, methyl methacrylate, butyl acrylate, β-hydroxyethyl acrylate, acrylamide or methacrylamide, 2 -Vinylpyridine, 1,3-butadiene is preferred.

　全単量体中のエチレン系不飽和カルボン酸単量体の含有量は、０．１～２０重量％であることが好ましく、０．５～１８重量％がより好ましく、０．５～１６重量％がさらに好ましい。この範囲に調整することで、集束性と樹脂含浸繊維の熱可塑性樹脂への分散性のバランスに優れる傾向にある。 The content of the ethylenically unsaturated carboxylic acid monomer in all monomers is preferably 0.1 to 20% by weight, more preferably 0.5 to 18% by weight, and 0.5 to 16% by weight. % is more preferred. By adjusting it within this range, there tends to be an excellent balance between the bundling property and the dispersibility of the resin-impregnated fibers in the thermoplastic resin.

　熱可塑性樹脂エマルジョンの各単量体の好ましい組成比率としては、芳香族系ビニル単量体６０～９５重量％、シアン化ビニル系単量体４～３９重量％、エチレン系不飽和カルボン酸単量体１～１５重量％が挙げられ、さらに好ましい組成比率としては、芳香族系ビニル単量体８０～９４重量％、シアン化ビニル系単量体５～１５重量％、エチレン系不飽和カルボン酸単量体１～１０重量％が挙げられる。 The preferable composition ratio of each monomer in the thermoplastic resin emulsion is 60 to 95% by weight of aromatic vinyl monomer, 4 to 39% by weight of vinyl cyanide monomer, and ethylenically unsaturated carboxylic acid monomer. 1 to 15% by weight of aromatic vinyl monomer, 5 to 15% by weight of vinyl cyanide monomer, and ethylenically unsaturated carboxylic acid monomer. from 1 to 10% by weight.

　本発明５の繊維集束用組成物に含まれる熱可塑性樹脂エマルジョンが、乳化重合法により得られる場合、公知の乳化重合法、例えば、一括添加方法、分割添加方法、連続添加方法、多段階重合法、シード重合法、パワーフィード重合法等、目的に応じて任意の方法を採用してもよいが、中でも重合時の安定性や分子量の調整の容易さから連続添加方法が好ましい。 When the thermoplastic resin emulsion contained in the fiber bundling composition of the present invention 5 is obtained by an emulsion polymerization method, a known emulsion polymerization method such as a batch addition method, a divided addition method, a continuous addition method, and a multistage polymerization method is used. , a seed polymerization method, a power feed polymerization method, and the like may be employed depending on the intended purpose, but the continuous addition method is preferred from the standpoint of stability during polymerization and ease of molecular weight adjustment.

　本発明５の繊維集束用組成物に含まれる熱可塑性樹脂エマルジョンを乳化重合する際に用いられる界面活性剤としては、例えば、直鎖アルキルベンゼンスルホン酸塩、ポリオキシエチレンアルキルエーテル硫酸塩、α－オレフィンスルホン酸塩、アルカンスルホン酸塩、ポリオキシエチレンアルキルエーテル酢酸塩、脂肪酸塩、α－スルホ脂肪酸メチルエステル塩、ジアルキルスルホコハク酸塩及びアルキル硫酸塩等の陰イオン系界面活性剤や、非イオン系界面活性剤、例えば、アセチレングリコール系界面活性剤、アセチレンアルコール系界面活性剤、ポリオキシエチレンノニルフェニルエーテル、ポリオキシエチレンオクチルフェニルエーテル、ポリオキシエチレンドデシルフェニルエーテル、ポリオキシエチレンアルキルアリルエーテル、ポリオキシエチレンオレイルエーテル、ポリオキシエチレンラウリルエーテル、ポリオキシエチレンアルキルエーテル、ポリオキシアルキレンアルキルエーテルなどのエーテル系、ポリオキシエチレンオレイン酸、ポリオキシエチレンオレイン酸エステル、ポリオキシエチレンジステアリン酸エステル、ソルビタンラウレート、ソルビタンモノステアレート、ソルビタンモノオレエート、ソルビタンセスキオレート、ポリオキシエチレンモノオレエート、ポリオキシエチレンステアレート等のエステル系、ジメチルポリシロキサン等のシリコン系界面活性剤、その他フッ素アルキルエステル、パーフルオロアルキルカルボン酸塩等の含フッ素系界面活性剤、非イオン性界面活性剤の硫酸エステル塩等のアニオン性界面活性剤あるいはポリエチレングリコールのアルキルエステル型、アルキルフェニルエーテル型、アルキルエーテル型等のノニオン性界面活性剤が挙げられ、各々１種または２種以上混合して用いることが可能である。 Examples of surfactants used in emulsion polymerization of the thermoplastic resin emulsion contained in the fiber bundling composition of the present invention 5 include linear alkylbenzene sulfonates, polyoxyethylene alkyl ether sulfates, and α-olefins. Anionic surfactants such as sulfonates, alkanesulfonates, polyoxyethylene alkyl ether acetates, fatty acid salts, α-sulfo fatty acid methyl ester salts, dialkylsulfosuccinates and alkyl sulfates, and nonionic surfactants Active agents such as acetylene glycol-based surfactants, acetylene alcohol-based surfactants, polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene dodecylphenyl ether, polyoxyethylene alkylallyl ether, polyoxyethylene Ethers such as oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene alkyl ether, polyoxyalkylene alkyl ether, polyoxyethylene oleic acid, polyoxyethylene oleate, polyoxyethylene distearate, sorbitan laurate, sorbitan Esters such as monostearate, sorbitan monooleate, sorbitan sesquioleate, polyoxyethylene monooleate, polyoxyethylene stearate, silicone surfactants such as dimethylpolysiloxane, other fluorine alkyl esters, perfluoroalkyl carboxylic acids Fluorine-containing surfactants such as acid salts, anionic surfactants such as sulfate ester salts of nonionic surfactants, or nonionic surfactants such as alkyl ester types, alkylphenyl ether types, and alkyl ether types of polyethylene glycol agents, each of which can be used singly or in combination of two or more.

　中でも、直鎖アルキルベンゼンスルホン酸塩、ポリオキシエチレンアルキルエーテル硫酸塩、α－オレフィンスルホン酸塩、アルカンスルホン酸塩、ジアルキルスルホコハク酸塩、アルキル硫酸塩及び非イオン系界面活性剤から選ばれた少なくとも１種を用いることが好ましく、直鎖アルキルベンゼンスルホン酸塩であることがより好ましい。 Among them, at least one selected from linear alkylbenzenesulfonates, polyoxyethylene alkyl ether sulfates, α-olefinsulfonates, alkanesulfonates, dialkylsulfosuccinates, alkyl sulfates and nonionic surfactants It is preferred to use seeds, more preferably linear alkylbenzene sulfonates.

　乳化重合の際に使用される界面活性剤は、全単量体１００重量部に対して、０．０５～１０重量部の範囲で使用するのが好ましい。０．０５部未満ではエマルジョンの安定性に劣るため含浸処理の際の歩留まりが低下し、１０重量部を越えると最終製品の成型の際にガスが多量に発生し成形品表面を損なう不具合や最終製品の強度低下が発生する傾向がある。好ましくは０．０６～８重量部、より好ましくは０．０８～５重量部の範囲である。 The surfactant used during emulsion polymerization is preferably used in the range of 0.05 to 10 parts by weight with respect to 100 parts by weight of all the monomers. If it is less than 0.05 part by weight, the stability of the emulsion is poor and the yield at the time of impregnation treatment is lowered. Product strength tends to decrease. The range is preferably 0.06 to 8 parts by weight, more preferably 0.08 to 5 parts by weight.

　本発明５の繊維集束用組成物に含まれる熱可塑性樹脂エマルジョンを乳化重合する際に用いられる重合開始剤としては、例えば、過硫酸リチウム、過硫酸カリウム、過硫酸ナトリウム、過硫酸アンモニウム等の水溶性重合開始剤、クメンハイドロパーオキサイド、過酸化ベンゾイル、ｔ－ブチルハイドロパーオキサイド、アセチルパーオキサイド、ジイソプロピルベンゼンハイドロパーオキサイド、及び１，１，３，３－テトラメチルブチルハイドロパーオキサイド等の油溶性重合開始剤が挙げられる。これらは１種を単独でまたは２種以上を組み合わせて使用することができる。これらのうち、過硫酸カリウム、過硫酸ナトリウム、クメンハイドロパーオキサイド、又はｔ－ブチルハイドロパーオキサイドを用いることが好ましい。重合開始剤の配合量は、単量体組成、重合反応系のｐＨ、他の添加剤などの組み合わせを考慮して適宜調整される。 Examples of polymerization initiators used for emulsion polymerization of the thermoplastic resin emulsion contained in the fiber bundling composition of the present invention 5 include water-soluble agents such as lithium persulfate, potassium persulfate, sodium persulfate and ammonium persulfate. Oil-soluble polymerization initiators such as cumene hydroperoxide, benzoyl peroxide, t-butyl hydroperoxide, acetyl peroxide, diisopropylbenzene hydroperoxide, and 1,1,3,3-tetramethylbutyl hydroperoxide initiators. These can be used individually by 1 type or in combination of 2 or more types. Among these, it is preferable to use potassium persulfate, sodium persulfate, cumene hydroperoxide, or t-butyl hydroperoxide. The amount of the polymerization initiator to be blended is appropriately adjusted in consideration of the monomer composition, the pH of the polymerization reaction system, the combination of other additives, and the like.

　本発明５の繊維集束用組成物に含まれる熱可塑性樹脂エマルジョンを乳化重合する際に用いられる連鎖移動剤としては、例えば、ｎ－ヘキシルメルカプタン、ｎ－オクチルメルカプタン、ｔ－オクチルメルカプタン、ｎ－ドデシルメルカプタン、ｔ－ドデシルメルカプタン、ｎ－ステアリルメルカプタン等のアルキルメルカプタン；ジメチルキサントゲンジサルファイド、ジイソプロピルキサントゲンジサルファイド等のキサントゲン化合物；テトラメチルチウラムジスルフィド、テトラエチルチウラムジスルフィド、テトラメチルチウラムモノスルフィド等のチウラム系化合物；２，６－ジ－ｔ－ブチル－４－メチルフェノール、スチレン化フェノール等のフェノール系化合物；アリルアルコール等のアリル化合物；ジクロルメタン、ジブロモメタン、四臭化炭素等のハロゲン化炭化水素化合物；α－ベンジルオキシスチレン、α－ベンジルオキシアクリロニトリル、α－ベンジルオキシアクリルアミド等のビニルエーテル；トリフェニルエタン、ペンタフェニルエタン、アクロレイン、メタアクロレイン、チオグリコール酸、チオリンゴ酸、２－エチルヘキシルチオグリコレート、ターピノレン、α－メチルスチレンダイマーなどの連鎖移動剤が挙げられる。これらは１種を単独でまたは２種以上を組み合わせて使用することができる。連鎖移動剤の配合量は、他の添加剤などの組み合わせを考慮して適宜調整することができる。 Examples of chain transfer agents used in emulsion polymerization of the thermoplastic resin emulsion contained in the fiber bundling composition of the present invention 5 include n-hexylmercaptan, n-octylmercaptan, t-octylmercaptan, and n-dodecyl. Alkyl mercaptans such as mercaptan, t-dodecyl mercaptan and n-stearyl mercaptan; xanthogen compounds such as dimethylxanthogen disulfide and diisopropyl xanthogen disulfide; thiuram compounds such as tetramethylthiuram disulfide, tetraethylthiuram disulfide and tetramethylthiuram monosulfide; Phenolic compounds such as 2,6-di-t-butyl-4-methylphenol and styrenated phenol; Allyl compounds such as allyl alcohol; Dichloromethane, dibromomethane, halogenated hydrocarbon compounds such as carbon tetrabromide; Vinyl ethers such as benzyloxystyrene, α-benzyloxyacrylonitrile, α-benzyloxyacrylamide; Chain transfer agents such as methylstyrene dimer are included. These can be used individually by 1 type or in combination of 2 or more types. The blending amount of the chain transfer agent can be appropriately adjusted in consideration of the combination with other additives.

　本発明５の繊維集束用組成物に含まれる熱可塑性樹脂エマルジョンを乳化重合する際に用いられる還元剤としては、例えば、亜硫酸塩、亜硫酸水素塩、ピロ亜硫酸塩、亜ニチオン酸塩、ニチオン酸塩、チオ硫酸塩、ホルムアルデヒドスルホン酸塩、ベンズアルデヒドスルホン酸塩；Ｌ－アスコルビン酸、エリソルビン酸、酒石酸、クエン酸などのカルボン酸類およびその塩；デキストロース、サッカロースなどの還元糖類；ジメチルアニリン、トリエタノールアミンなどのアミン類が挙げられる。これらは１種を単独でまたは２種以上を組み合わせて使用することができる。これらのうち、Ｌ－アスコルビン酸、エリソルビン酸が好ましい。還元剤の配合量は、他の添加剤などの組み合わせを考慮して適宜調整することができる。 Examples of the reducing agent used in the emulsion polymerization of the thermoplastic resin emulsion contained in the fiber bundling composition of the present invention 5 include sulfite, hydrogen sulfite, pyrosulfite, nitionite, and nitionate. , thiosulfate, formaldehyde sulfonate, benzaldehyde sulfonate; L-ascorbic acid, erythorbic acid, tartaric acid, citric acid and other carboxylic acids and salts thereof; dextrose, saccharose and other reducing sugars; dimethylaniline, triethanolamine, etc. amines of. These can be used individually by 1 type or in combination of 2 or more types. Among these, L-ascorbic acid and erythorbic acid are preferred. The blending amount of the reducing agent can be appropriately adjusted in consideration of the combination with other additives.

　また、本実施形態に係る反応系には、共重合体の分子量及び架橋構造を制御する目的で、ペンタン、ヘキサン、ヘプタン、オクタン、シクロヘキサン、シクロヘプタン等の飽和炭化水素；ペンテン、ヘキセン、ヘプテン、シクロペンテン、シクロヘキセン、シクロヘプテン、４－メチルシクロヘキセン、１－メチルシクロヘキセン等の不飽和炭化水素；ベンゼン、トルエン、キシレン等の芳香族炭化水素などの炭化水素化合物を配合することができる。これらは１種を単独でまたは２種以上を組み合わせて使用することができる。これらのうち、シクロヘキセン、トルエンを用いることが好ましい。 For the purpose of controlling the molecular weight and crosslinked structure of the copolymer, the reaction system according to the present embodiment contains saturated hydrocarbons such as pentane, hexane, heptane, octane, cyclohexane, and cycloheptane; pentene, hexene, heptene, Hydrocarbon compounds such as unsaturated hydrocarbons such as cyclopentene, cyclohexene, cycloheptene, 4-methylcyclohexene and 1-methylcyclohexene; aromatic hydrocarbons such as benzene, toluene and xylene can be blended. These can be used individually by 1 type or in combination of 2 or more types. Among these, it is preferable to use cyclohexene and toluene.

　エチレン系不飽和カルボン酸単量体や界面活性剤の添加方法には特に制限は無く、初期に必要量を全量添加する、重合中に連続あるいは断続的に添加する、あるいは重合時に一部を使用した後、重合完了後に残りを追添する方法等、目的に応じて方法を採用することができる。重合完了後に界面活性剤を追加添加する場合には、重合時に使用した界面活性剤と同種のものを使う以外に、異なる種類の界面活性剤を１種または２種以上混合し添加することも可能である。 There are no particular restrictions on the method of adding the ethylenically unsaturated carboxylic acid monomer or surfactant, and the necessary amount is added in the initial stage, added continuously or intermittently during polymerization, or partly used during polymerization. After that, a method such as a method of adding the remainder after the polymerization is completed can be employed depending on the purpose. When additional surfactant is added after polymerization is completed, in addition to using the same type of surfactant used during polymerization, it is also possible to add one or a mixture of two or more different types of surfactants. is.

　また、乳化重合する際の重合温度は、３０～８５℃の範囲で行うことが好ましく、重合時間は、３～２０時間の範囲であることが好ましい。 The polymerization temperature during emulsion polymerization is preferably in the range of 30 to 85°C, and the polymerization time is preferably in the range of 3 to 20 hours.

　本発明５の繊維集束用組成物中の熱可塑性樹脂エマルジョンの固形分のガラス転移温度に特に制限はないが、３０～２００℃の範囲であることが最終製品の強度の点から好ましい。より好ましくは３５～１９０℃、さらに好ましくは６０～１４０℃、特に好ましくは８０～１２０℃の範囲である。このガラス転移温度はＪＩＳ　Ｋ７１２１―２０１２に準拠して測定することができる。なお、この熱可塑性樹脂エマルジョン中の固形分の抽出方法に特に制限はないが、例えば熱可塑性樹脂エマルジョンを９０℃に調整された乾燥機中で１０時間乾燥することにより得ることができる。 Although there is no particular limitation on the glass transition temperature of the solid content of the thermoplastic resin emulsion in the fiber bundling composition of the present invention 5, it is preferably in the range of 30 to 200°C from the standpoint of the strength of the final product. The range is more preferably 35 to 190°C, still more preferably 60 to 140°C, and particularly preferably 80 to 120°C. This glass transition temperature can be measured according to JIS K7121-2012. The method for extracting the solid content in the thermoplastic resin emulsion is not particularly limited, but it can be obtained, for example, by drying the thermoplastic resin emulsion in a dryer adjusted to 90° C. for 10 hours.

　本発明５の繊維集束用組成物には、熱可塑性樹脂エマルジョン以外に、分散剤、滑剤、消泡剤、防腐剤、酸化防止剤、紫外線吸収剤、光安定化剤、着色剤、帯電防止剤、可塑剤等を、本発明５の効果を損なわない範囲に配合して使用することが可能である。 In addition to the thermoplastic resin emulsion, the fiber bundling composition of the present invention 5 contains a dispersant, a lubricant, an antifoaming agent, a preservative, an antioxidant, an ultraviolet absorber, a light stabilizer, a coloring agent, and an antistatic agent. , a plasticizer, etc., can be mixed and used within a range that does not impair the effects of the present invention 5.

　本発明５の繊維集束用組成物中の熱可塑性樹脂エマルジョンの含有割合（固形分換算）は、８０重量％以上であることが好ましく、９０重量％以上であることがより好ましい。 The content of the thermoplastic resin emulsion (in terms of solid content) in the fiber bundling composition of the present invention 5 is preferably 80% by weight or more, more preferably 90% by weight or more.

　本発明５の繊維集束用組成物のｐＨは、４～７の範囲であり、４～６．４であることが好ましく、４．１～５．５であることがより好ましい。ｐＨが４未満または７を超える場合、マトリックス樹脂であるポリエステル樹脂の加水分解が著しく進行する傾向にある。 The pH of the fiber bundling composition of the present invention 5 is in the range of 4 to 7, preferably 4 to 6.4, more preferably 4.1 to 5.5. If the pH is less than 4 or more than 7, hydrolysis of the polyester resin, which is the matrix resin, tends to proceed remarkably.

　繊維集束用組成物のｐＨは、熱可塑性樹脂エマルジョンを重合する際のエチレン系不飽和カルボン酸単量体の種類や添加量、重合時または重合完了時に添加される水酸化ナトリウムや水酸化カリウム等のアルカリ物質の添加量、酢酸や硫酸、塩酸、リン酸等の酸性物質の添加量によって調整することが可能である。 The pH of the fiber bundling composition depends on the type and amount of the ethylenically unsaturated carboxylic acid monomer added when polymerizing the thermoplastic resin emulsion, sodium hydroxide, potassium hydroxide, etc. added during polymerization or at the completion of polymerization. It is possible to adjust the addition amount of the alkaline substance and the addition amount of the acidic substance such as acetic acid, sulfuric acid, hydrochloric acid and phosphoric acid.

　本発明５の繊維集束用組成物により繊維を集束させる方法には特に制限はなく、スプレー法や塗布法または含浸法等の公知の方法から１種または２種以上組み合わせて選択することが可能である。 The method for bundling fibers with the fiber bundling composition of the present invention 5 is not particularly limited, and it is possible to select one or a combination of two or more from known methods such as spraying, coating, and impregnation. be.

　本発明５の繊維集束用組成物により集束させる繊維としては、炭素繊維、ガラス繊維、硼素繊維、炭化ケイ素繊維、あるいはアルミウム繊維、ステンレス繊維、銅繊維、ニッケル繊維などの金属繊維、ポリアミド繊維、ポリエステル繊維、ポリアリレート繊維、ポリイミド繊維、（ナノ）セルロース繊維などの有機繊維等を用いることが出来る。さらにこれらの繊維は１種または２種以上を組み合わせて用いることも可能である。中でも、炭素繊維、ガラス繊維が好ましい。炭素繊維には、通常の炭素繊維に加えて、ニッケルなどの金属で被覆処理した炭素繊維なども含まれ、かつその形態に特に制限はなく、連続繊維、チョップド繊維、ミルド形状や不織布等、目的に応じて任意の形態のものを選ぶことが可能である。 Fibers to be bundled by the composition for fiber bundling of the present invention 5 include carbon fiber, glass fiber, boron fiber, silicon carbide fiber, metal fiber such as aluminum fiber, stainless fiber, copper fiber, nickel fiber, polyamide fiber, and polyester. Organic fibers such as fibers, polyarylate fibers, polyimide fibers, and (nano)cellulose fibers can be used. Furthermore, these fibers can be used singly or in combination of two or more. Among them, carbon fiber and glass fiber are preferred. In addition to ordinary carbon fibers, carbon fibers include carbon fibers coated with metal such as nickel, and there are no particular restrictions on the form thereof, and may be continuous fibers, chopped fibers, milled shapes, non-woven fabrics, etc. Any form can be selected according to the requirements.

　本発明５における繊維集束用組成物と繊維の含浸比率に特に制限は無いが、最終製品の強度面から、固形分換算で、繊維集束用組成物１～２０重量部、繊維９９～８０重量部の範囲で含浸させることが好ましい。 Although there is no particular limitation on the impregnation ratio of the composition for fiber bundling and the fiber in Invention 5, from the standpoint of the strength of the final product, the composition for fiber bundling is 1 to 20 parts by weight and the fiber is 99 to 80 parts by weight in terms of solid content. is preferably impregnated in the range of

　本発明５の樹脂含浸繊維における、繊維集束用組成物により集束させた繊維の水分の蒸発方法については特に制限はなく、乾燥機を使用する方法、赤外線を照射する方法、連続的に乾燥機を通過させる方法等、目的に応じて採用することが可能である。尚、乾燥温度については、熱可塑性樹脂エマルジョンのガラス転移温度＋６０～８０℃に調整されることが、集束処理後の繊維を取り扱う上で好ましい。 In the resin-impregnated fiber of the present invention 5, the method for evaporating the moisture of the fiber bundled with the fiber bundling composition is not particularly limited, and includes a method using a dryer, a method of irradiating infrared rays, and a method of continuously using a dryer. It is possible to adopt a method such as passing through, depending on the purpose. The drying temperature is preferably adjusted to the glass transition temperature of the thermoplastic resin emulsion plus 60 to 80° C. for handling the fibers after the bundling treatment.

　本発明５の樹脂含浸繊維は、熱可塑性樹脂と溶融混練し、繊維強化熱可塑性樹脂組成物として用いることができる。さらに、熱可塑性樹脂シートまたはフィルムと積層させた積層品としても用いることもできる。 The resin-impregnated fiber of the present invention 5 can be melt-kneaded with a thermoplastic resin and used as a fiber-reinforced thermoplastic resin composition. Furthermore, it can also be used as a laminate laminated with a thermoplastic resin sheet or film.

　本発明５の樹脂含浸繊維と組み合わせる熱可塑性樹脂としては、例えば、ポリカーボネート（ＰＣ）、ポリエチレンテレフタレート（ＰＥＴ）、ポリブチレンテレフタレート（ＰＢＴ）、ポリ乳酸樹脂（ＰＬＡ）等のポリエステル樹脂、ポリスチレン（ＰＳ）、耐衝撃性ポリスチレン（ＨＩＰＳ）、アクリロニトリル－ブタジエンゴム－スチレン共重合体（ＡＢＳ）、アクリロニトリルーアクリルゴム－スチレン共重合体（ＡＳＡ）、アクリロニトリル－エチレンプロピレンゴム－スチレン共重合体（ＡＥＳ）、アクリロニトリル－スチレン共重合体（ＡＳ）等のスチレン系樹脂、ポリエチレン（ＰＥ）、ポリプロピレン（ＰＰ）等のポリオレフィン樹脂、ポリメチルメタクリレート（ＰＭＭＡ）、ポリアミド（ＰＡ）、熱可塑性ポリウレタン樹脂（ＴＰＵ）、ポリエーテルサルフォン（ＰＥＳ）、ポリフェニレンサルファイド（ＰＰＳ）等が挙げられ、1種または２種以上を組み合わせて使用することが可能である。中でも、ポリエステル樹脂を含む熱可塑性樹脂であることが、本発明５の効果をより顕著に得るために好ましい。 Examples of the thermoplastic resin to be combined with the resin-impregnated fiber of the present invention 5 include polyester resins such as polycarbonate (PC), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polylactic acid resin (PLA), and polystyrene (PS). , high-impact polystyrene (HIPS), acrylonitrile-butadiene rubber-styrene copolymer (ABS), acrylonitrile-acrylic rubber-styrene copolymer (ASA), acrylonitrile-ethylene propylene rubber-styrene copolymer (AES), acrylonitrile - Styrene resins such as styrene copolymer (AS), polyolefin resins such as polyethylene (PE) and polypropylene (PP), polymethyl methacrylate (PMMA), polyamide (PA), thermoplastic polyurethane resin (TPU), polyether Sulfone (PES), polyphenylene sulfide (PPS) and the like can be mentioned, and it is possible to use one or a combination of two or more. Among them, a thermoplastic resin containing a polyester resin is preferable in order to obtain the effect of the present invention 5 more remarkably.

　本発明５の樹脂含浸繊維と組み合せる熱可塑性樹脂には、例えば、光安定剤、酸化防止剤、熱安定剤、紫外線吸収剤、滑剤、難燃剤、難燃助剤、可塑剤、顔料、染料等の各種添加剤を含むこともできる。 The thermoplastic resin to be combined with the resin-impregnated fiber of the present invention 5 includes, for example, a light stabilizer, an antioxidant, a heat stabilizer, an ultraviolet absorber, a lubricant, a flame retardant, a flame retardant auxiliary, a plasticizer, a pigment, and a dye. Various additives such as can also be included.

　本発明５の樹脂含浸繊維と熱可塑性樹脂とを溶融混練して得られた繊維強化熱可塑性樹脂組成物は、例えば、射出成形、多層押し出し成形、フィルム成形、シート成形、インフレーション成形、プレス成形、ＳＭＣ成形法、ＬＦＴ－Ｄ法等、目的に応じた加工法を採用することで成形品を得ることが可能である。また、場合によっては予備賦形を行う工程を挟むことも可能である。 The fiber-reinforced thermoplastic resin composition obtained by melt-kneading the resin-impregnated fiber and the thermoplastic resin of the present invention 5 can be, for example, injection molding, multilayer extrusion molding, film molding, sheet molding, inflation molding, press molding, A molded article can be obtained by adopting a processing method according to the purpose, such as the SMC molding method and the LFT-D method. In some cases, it is also possible to interpose a step of pre-shaping.

　また、上記の加工法以外に、本発明５の樹脂含浸繊維からなる層を熱可塑性樹脂シートまたはフィルムと積層させた積層体を用いて、プレス成型、ＳＭＣ成形法等により成形品を得ることが可能である。また、場合によっては予備賦形を行う工程を挟むことも可能である。 In addition to the above-described processing methods, it is also possible to obtain a molded product by press molding, SMC molding, or the like using a laminate obtained by laminating a layer made of the resin-impregnated fiber of the present invention 5 with a thermoplastic resin sheet or film. It is possible. In some cases, it is also possible to interpose a step of pre-shaping.

　成形品の加工温度に特に制限はなく、使用される熱可塑性樹脂の特性により任意の温度を選択することが可能であるが、成形サイクルの点から１８０～３００℃の範囲で成形することが好ましく、更に好ましくは２００～２８０℃の範囲である。 There is no particular limitation on the processing temperature of the molded product, and it is possible to select any temperature according to the properties of the thermoplastic resin used, but it is preferable to mold in the range of 180 to 300 ° C. from the viewpoint of the molding cycle. , and more preferably in the range of 200 to 280°C.

　以下、本発明１～５を、それぞれの発明に対応する実施例及び比較例を用いてより具体的に説明するが、本発明１～５は以下の実施例によって何ら限定されるものではない。また、各実施例、比較例での各種物性の測定は次の方法による。 Hereinafter, Inventions 1 to 5 will be described more specifically using examples and comparative examples corresponding to each invention, but Inventions 1 to 5 are not limited by the following examples. Various physical properties in each example and comparative example are measured by the following methods.

　１．本発明１に関する実施例および比較例
　数平均分子量
　得られた共重合体エマルジョンを室温にて一昼夜乾燥後、７０℃のオーブンで１時間乾燥させることで測定サンプルとした。その後、測定サンプル０．０２ｇをテトラヒドロフラン（ＴＨＦ）１０ｍｌに溶解させた溶液をゲルパーミエーションクロマトグラム（ＧＰＣ）測定装置を用いて、下記条件で測定した。
検出器：ＵＶ
カラム：Ａｇｉｌｅｎｔ社製　ＭＩＸＤ－Ｂ
カラム温度：５０℃
溶媒：テトラヒドロフラン（ＴＨＦ）
流量：１ｍｌ／ｍｉｎ、
検出波長：２５４ｎｍ
標準試料：ポリスチレン
　シャルピー衝撃強度（ＮＣ）
　各実施例及び比較例で得られたペレットを用い、ＩＳＯ試験方法２９４に準拠して各種試験片を成形し、ＩＳＯ試験方法１７９に準拠し、４ｍｍ厚みで、ノッチ付きシャルピー衝撃値を測定した。単位：ｋＪ／ｍ２
　曲げ強度
　各実施例及び比較例で得られた試験片を用い、ＪＩＳ　Ｋ７０７４に準じて曲げ強度を測定した。単位：ＭＰａ
　＜共重合体エマルジョン－１の製造方法＞
　耐圧性の重合反応器に、脱イオン水４５部を添加した後、窒素置換を行った。その後、反応器を７５℃に昇温し、ドデシルベンゼンスルホン酸ナトリウム０．４部（固形分換算）、スチレン４．２部、アクリロニトリル０．５部、ｔ－ドデシルメルカプタン０．８部、を加えて十分攪拌した後、過硫酸カリウム０．１部を仕込み、８０℃にて重合を開始した。開始から１時間後にスチレン８３．８部、アクリロニトリル９．５部、アクリル酸２部を脱イオン水１８部に溶解させた溶液、ドデシルベンゼンスルホン酸ナトリウム１．７部（固形分換算）を脱イオン水３０部に溶解させた溶液と重炭酸ナトリウム０．７３部および過硫酸カリウム０．１部を７．５時間にわたって連続的に添加した。そのまま重合温度を８０℃で５時間保ち重合を終了した。次いで、共重合体エマルジョンを苛性ソーダ水溶液でｐＨを約７に調整した後、水蒸気蒸留により未反応単量体および他の低沸点化合物を除去し、固形分を４５％に調整し、共重合体エマルジョン－１を得た。 1. EXAMPLES AND COMPARATIVE EXAMPLES RELATING TO THE INVENTION 1 NUMBER AVERAGE MOLECULAR WEIGHT The obtained copolymer emulsion was dried at room temperature for a whole day and night, and then dried in an oven at 70°C for 1 hour to obtain a measurement sample. After that, a solution obtained by dissolving 0.02 g of the measurement sample in 10 ml of tetrahydrofuran (THF) was measured using a gel permeation chromatogram (GPC) measurement device under the following conditions.
Detector: UV
Column: MIXD-B manufactured by Agilent
Column temperature: 50°C
Solvent: Tetrahydrofuran (THF)
Flow rate: 1 ml/min,
Detection wavelength: 254 nm
Standard sample: Polystyrene Charpy impact strength (NC)
Using the pellets obtained in each example and comparative example, various test pieces were molded according to ISO test method 294, and the notched Charpy impact value was measured according to ISO test method 179 with a thickness of 4 mm. Unit: kJ/ m2
Bending Strength Bending strength was measured according to JIS K7074 using the test pieces obtained in Examples and Comparative Examples. Unit: MPa
<Method for producing copolymer emulsion-1>
After adding 45 parts of deionized water to a pressure-resistant polymerization reactor, the reactor was purged with nitrogen. After that, the reactor was heated to 75° C., and 0.4 parts of sodium dodecylbenzenesulfonate (in terms of solid content), 4.2 parts of styrene, 0.5 parts of acrylonitrile, and 0.8 parts of t-dodecylmercaptan were added. After sufficiently stirring the mixture with 0.1 part of potassium persulfate, polymerization was initiated at 80°C. One hour after the start, a solution of 83.8 parts of styrene, 9.5 parts of acrylonitrile, and 2 parts of acrylic acid dissolved in 18 parts of deionized water, and 1.7 parts of sodium dodecylbenzenesulfonate (as solid content) were deionized. A solution in 30 parts water and 0.73 parts sodium bicarbonate and 0.1 parts potassium persulfate were added continuously over 7.5 hours. The polymerization temperature was maintained at 80° C. for 5 hours to complete the polymerization. Next, after adjusting the pH of the copolymer emulsion to about 7 with an aqueous solution of caustic soda, unreacted monomers and other low boiling point compounds are removed by steam distillation, and the solid content is adjusted to 45%. -1 was obtained.

　得られた共重合体エマルジョンを１００℃のオーブンで乾燥した後、ＧＰＣにより数平均分子量を測定したところ２．５×１０４であり、テトラヒドロフラン不溶部は、０重量％であった。 After drying the obtained copolymer emulsion in an oven at 100° C., the number average molecular weight was measured by GPC to be 2.5×10 4 , and the tetrahydrofuran-insoluble portion was 0% by weight.

　＜共重合体エマルジョン－２の製造方法＞
　ｔ－ドデシルメルカプタン使用量を２部に変更した以外、共重合体エマルジョン－１と同じ重合方法で共重合体エマルジョン－２を得た。 <Method for producing copolymer emulsion-2>
Copolymer Emulsion-2 was obtained by the same polymerization method as Copolymer Emulsion-1, except that the amount of t-dodecylmercaptan used was changed to 2 parts.

　得られた共重合体エマルジョンを１００℃のオーブンで乾燥した後、ＧＰＣにより数平均分子量を測定したところ１．０×１０４であり、テトラヒドロフラン不溶部は、０重量％であった。 After drying the resulting copolymer emulsion in an oven at 100° C., the number average molecular weight was measured by GPC to be 1.0×10 4 , and the tetrahydrofuran-insoluble portion was 0% by weight.

　＜共重合体エマルジョン－３の製造方法＞
　ｔ－ドデシルメルカプタン使用量を０．４部に変更した以外、共重合体エマルジョン－１と同じ重合方法で共重合体エマルジョン－３を得た。 <Method for producing copolymer emulsion-3>
Copolymer emulsion-3 was obtained by the same polymerization method as for copolymer emulsion-1, except that the amount of t-dodecylmercaptan used was changed to 0.4 parts.

　得られた共重合体エマルジョンを１００℃のオーブンで乾燥した後、ＧＰＣにより数平均分子量を測定したところ３．９×１０４であり、テトラヒドロフラン不溶部は、０重量％であった。 After drying the resulting copolymer emulsion in an oven at 100° C., the number average molecular weight was measured by GPC to be 3.9×10 4 , and the tetrahydrofuran-insoluble portion was 0% by weight.

　＜共重合体エマルジョン－４の製造方法＞
　ｔ－ドデシルメルカプタン使用量を０．０６部に変更した以外、共重合体エマルジョン－１と同じ重合方法で共重合体エマルジョン－４を得た。 <Method for producing copolymer emulsion-4>
Copolymer emulsion-4 was obtained by the same polymerization method as for copolymer emulsion-1, except that the amount of t-dodecylmercaptan used was changed to 0.06 parts.

　得られた共重合体エマルジョンを１００℃のオーブンで乾燥した後、ＧＰＣにより数平均分子量を測定したところ８×１０４であり、テトラヒドロフラン不溶部は、０重量％であった。 After drying the resulting copolymer emulsion in an oven at 100° C., the number average molecular weight was measured by GPC to be 8×10 4 , and the tetrahydrofuran-insoluble portion was 0% by weight.

　＜チョップドストランド－１の製造方法＞
　布引装置を用いて、共重合体エマルジョン－１（固形分換算）を炭素繊維１００重量部に対して付着量が３重量部となるように含浸させた後、ペレタイザーを用いて切断を行い、１００℃に調整した棚式乾燥機を用いて水分量が０．１%以下になるまで乾燥を行い、チョップドストランド－１を得た。 <Method for producing chopped strand-1>
After impregnating 100 parts by weight of the carbon fiber with the copolymer emulsion-1 (solid content conversion) using a cloth binding device so that the adhesion amount is 3 parts by weight, the carbon fiber is cut using a pelletizer. Chopped strand-1 was obtained by drying until the moisture content became 0.1% or less using a shelf dryer adjusted to ℃.

　＜チョップドストランド－２～４の製造方法＞
　共重合体エマルジョン－１を共重合体エマルジョン－２～４に変更した以外は、チョップドストランド－１と同じ製法で、チョップドストランド－２～４を得た。 <Manufacturing method of chopped strands-2 to 4>
Chopped strands-2 to 4 were obtained in the same manner as chopped strand-1, except that copolymer emulsion-1 was changed to copolymer emulsions-2 to 4.

　＜連続樹脂含浸繊維－１の製造方法＞
　布引装置を用いて、共重合体エマルジョン－１（固形分換算）を炭素繊維１００重量部に対して付着量が１５重量部となるように含浸させ、その後得られた連続樹脂含浸繊維を１８０℃に調整した乾燥炉内を１ｍ／分の速さで３分間移動させることにより、水分を完全に除去し、最終の連続樹脂含浸繊維－１を得た。 <Method for producing continuous resin-impregnated fiber-1>
100 parts by weight of the carbon fibers were impregnated with the copolymer emulsion-1 (in terms of solid content) using a cloth drawing apparatus so that the adhesion amount was 15 parts by weight. Moisture was completely removed by moving in a drying oven adjusted to 1 m/min for 3 minutes to obtain the final continuous resin-impregnated fiber-1.

　＜連続樹脂含浸繊維－２～４の製造方法＞
　共重合体エマルジョン－１を共重合体エマルジョン－２～４に変更した以外は連続樹脂含浸繊維－１と同じ製法で、連続樹脂含浸繊維－２～４を得た。 <Method for producing continuous resin-impregnated fibers-2 to 4>
Continuous resin-impregnated fibers-2 to 4 were obtained in the same manner as the continuous resin-impregnated fiber-1, except that copolymer emulsion-1 was changed to copolymer emulsion-2 to 4.

　上述のチョップドストランド、連続樹脂含浸繊維に用いた炭素繊維は、帝人株式会社製　Ｔｅｎａｘ（登録商標）－Ｊ　ＳＴＳ４０　Ｆ１３　２４Ｋ　１６００ｔｅｘ
　熱可塑性樹脂―１
　日本エイアンドエル株式会社製　テクニエース（登録商標）ＴＡ－１５００
（ポリアミド樹脂とＡＢＳ樹脂のアロイ）
　熱可塑性樹脂―２
　日本エイアンドエル株式会社製　テクニエース（登録商標）ＰＡＸ－１４３９
（ポリカーボネート樹脂とＡＢＳ樹脂のアロイ）
　熱可塑性樹脂―３
　株式会社プライムポリマー製　プライムポリプロ（登録商標）Ｊ１０６Ｇ
（ホモのポリプロピレン樹脂）
　＜繊維強化熱可塑性樹脂組成物の製造方法＞
　熱可塑性樹脂およびチョップドストランドを表１に記載の配合割合で混合した後、フィーダーを２基有しているＳＴＥＥＲ社製ＯＭｅｇａ３０Ｈを用いて、Ｆ１より熱可塑性樹脂を、Ｆ２からチョップドストランドを投入し溶融混練して繊維強化熱可塑性樹脂組成物のペレットを得た。また、このペレットを用いてシャルピー衝撃強度用試験片を射出成形機にて成形した。 The carbon fiber used for the above chopped strands and continuous resin-impregnated fibers is Tenax (registered trademark)-J STS40 F13 24K 1600tex manufactured by Teijin Limited.
Thermoplastic resin-1
Techniace (registered trademark) TA-1500 manufactured by Nippon A&L Co., Ltd.
(Alloy of polyamide resin and ABS resin)
Thermoplastic resin-2
Techniace (registered trademark) PAX-1439 manufactured by Nippon A&L Co., Ltd.
(alloy of polycarbonate resin and ABS resin)
Thermoplastic resin-3
Prime Polypro (registered trademark) J106G manufactured by Prime Polymer Co., Ltd.
(Homo polypropylene resin)
<Method for producing fiber-reinforced thermoplastic resin composition>
After mixing the thermoplastic resin and chopped strands at the blending ratio shown in Table 1, using OMega30H manufactured by STEER, which has two feeders, the thermoplastic resin is fed from F1 and the chopped strands from F2, and melted. The pellets of the fiber-reinforced thermoplastic resin composition were obtained by kneading. Using the pellets, test pieces for Charpy impact strength were molded with an injection molding machine.

　＜樹脂含浸繊維と熱可塑性樹脂からなる積層品の製造方法＞
　樹脂含浸繊維を２０ｃｍ角のシートとなるように複数枚並列させた後、ナイロンフィルム（東レフィルム加工株式会社製　レイファン（登録商標）Ｎ０　１４０１　厚み４０μｍ）と炭素繊維含量が３０重量％になるように交互に積層させ、設定温度２５０℃の圧縮成型機ＮＦ３７型を用いて、圧力５ＭＰａをかけた状態で余熱を５分間行った後、圧力１５ＭＰａをかけた状態で５分間熱プレス処理を行い、厚みが２ｍｍの積層品を作製した。また、得られた積層品から幅１５ｍｍ×長さ１５０ｍｍの試験片を切り出し曲げ試験用試験片とした。 <Method for producing a laminate comprising resin-impregnated fibers and thermoplastic resin>
After arranging a plurality of resin-impregnated fibers in parallel to form a sheet of 20 cm square, nylon film (Rayfan (registered trademark) N0 1401, thickness 40 μm, manufactured by Toray Advanced Film Co., Ltd.) and carbon fiber content are 30% by weight. are laminated alternately, and after preheating for 5 minutes with a pressure of 5 MPa using a compression molding machine NF37 with a set temperature of 250 ° C., hot press treatment is performed for 5 minutes with a pressure of 15 MPa, Laminates with a thickness of 2 mm were produced. A test piece having a width of 15 mm and a length of 150 mm was cut out from the obtained laminated product and used as a test piece for a bending test.

　尚、積層品を作成する際には炭素繊維の方向は一方向に揃えてあり、また曲げ試験用試験片は炭素繊維の方向と試験片の長辺の方向が一致する方向で切り出しを行った。 When the laminated product was produced, the direction of the carbon fibers was aligned in one direction, and the test piece for the bending test was cut out in the direction in which the direction of the carbon fiber and the direction of the long side of the test piece coincided. .

Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003

Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004

　表１より、本発明の繊維集束用組成物を用いて製造されたチョップドストランドを配合した繊維強化熱可塑性樹脂組成物である実施例１～８は、シャルピー衝撃強度に優れるものであった。 From Table 1, Examples 1 to 8, which are fiber-reinforced thermoplastic resin compositions containing chopped strands produced using the fiber bundling composition of the present invention, were excellent in Charpy impact strength.

　比較例１は、本発明の繊維集束用組成物に含まれる共重合体エマルジョンの数平均分子量が規定範囲を満足しないため、シャルピー衝撃強度に劣るものであった。 Comparative Example 1 was inferior in Charpy impact strength because the number average molecular weight of the copolymer emulsion contained in the fiber bundling composition of the present invention did not satisfy the specified range.

　比較例２は、繊維集束用組成物を用いていないチョップドストランドを配合した繊維強化熱可塑性樹脂組成物であるため、シャルピー衝撃強度に劣るものであった。 Comparative Example 2 was inferior in Charpy impact strength because it was a fiber-reinforced thermoplastic resin composition containing chopped strands that did not use a fiber bundling composition.

　表２より、本発明の繊維集束用組成物を用いて製造された連続樹脂含浸繊維をナイロンフィルムと積層した実施例９～１１は、曲げ強度に優れるものであった。 From Table 2, Examples 9 to 11 in which continuous resin-impregnated fibers produced using the fiber bundling composition of the present invention were laminated with a nylon film were excellent in bending strength.

　比較例３は、本発明の繊維集束用組成物に含まれる共重合体エマルジョンの数平均分子量が規定範囲を満足しないため、曲げ強度に劣るものであった。 Comparative Example 3 was inferior in bending strength because the number average molecular weight of the copolymer emulsion contained in the fiber bundling composition of the present invention did not satisfy the specified range.

　２．本発明２に関する実施例および比較例
　重量平均分子量
　得られた熱可塑性樹脂エマルジョンを室温にて一昼夜乾燥後、７０℃のオーブンで１時間乾燥させることで測定サンプルとした。その後、測定サンプル０．０２ｇをテトラヒドロフラン（ＴＨＦ）１０ｍｌに溶解させた溶液をゲルパーミエーションクロマトグラム（ＧＰＣ）測定装置を用いて、下記条件で測定した。
検出器：ＵＶ
カラム：Ａｇｉｌｅｎｔ社製　ＭＩＸＤ－Ｂ
カラム温度：５０℃
溶媒：テトラヒドロフラン（ＴＨＦ）
流量：１ｍｌ／ｍｉｎ、
検出波長：２５４ｎｍ
標準試料：ポリスチレン
　ガラス転移温度
　得られた熱可塑性樹脂エマルジョンを９０℃のオーブンで１０時間乾燥させることで測定サンプルとした。その後、示差走査熱量計を用いてＪＩＳ　Ｋ７１２１―２０１２に準拠して測定した。 2. EXAMPLES AND COMPARATIVE EXAMPLES RELATING TO THE INVENTION 2 WEIGHT AVERAGE MOLECULAR WEIGHT The obtained thermoplastic resin emulsion was dried at room temperature for a whole day and night, and then dried in an oven at 70°C for 1 hour to obtain a measurement sample. After that, a solution obtained by dissolving 0.02 g of the measurement sample in 10 ml of tetrahydrofuran (THF) was measured using a gel permeation chromatogram (GPC) measurement device under the following conditions.
Detector: UV
Column: MIXD-B manufactured by Agilent
Column temperature: 50°C
Solvent: Tetrahydrofuran (THF)
Flow rate: 1 ml/min,
Detection wavelength: 254 nm
Standard sample: polystyrene glass transition temperature The resulting thermoplastic resin emulsion was dried in an oven at 90°C for 10 hours to prepare a measurement sample. After that, it was measured according to JIS K7121-2012 using a differential scanning calorimeter.

　表面張力
　繊維集束用組成物に純水を加えて固形分濃度３０％に調整した後、自動表面張力計Ｋ１１（ＫＲＵＳＳ社製）を用いて３０℃で測定した。 Pure water was added to the surface tension fiber bundling composition to adjust the solid content to 30%, and then the surface tension was measured at 30°C using an automatic surface tension meter K11 (manufactured by KRUSS).

　集束性の評価
　各実施例及び比較例で得られた繊維強化熱可塑性樹脂組成物の製造の際、チョップドストランドを投入するＦ２に設置したシューター内部でのチョップドストランドの状態を目視観察し下記のように評価した。
×：著しく手羽立ちが発生
△：一部毛羽立ちが発生
〇：毛羽立ちは確認できない
　また、各実施例及び比較例で得られた連続樹脂含浸繊維では、２０ｃｍの長さに切り出し、直径３０ｍｍのパイプに添わせる形で曲げた際の繊維の状態を目視で観察し、下記のように評価した。
×：著しく繊維のほつれが発生
△：一部繊維のほつれが発生
〇：異常は確認できない
　なお、集束性の評価が良いほど、取り扱い性が良好であることを示す。 Evaluation of bundling property During the production of the fiber-reinforced thermoplastic resin compositions obtained in each example and comparative example, the state of the chopped strands inside the shooter installed in F2 for charging the chopped strands was visually observed, and the following was performed. evaluated to
×: Significant fluffing △: Partial fluffing 〇: No fluffing confirmed In addition, the continuous resin-impregnated fibers obtained in each example and comparative example were cut into a length of 20 cm and cut into a pipe with a diameter of 30 mm. The state of the fiber when it was bent in the form of being attached was visually observed and evaluated as follows.
×: Significant fraying of fibers occurred △: Partial fraying of fibers occurred ○: Abnormality was not confirmed The better the evaluation of bundling property, the better the handleability.

　開繊性の評価
　各実施例及び比較例で得られた開繊性の評価に用いる試験片をＸ線ＣＴ装置（Ｂｒｕｋｅｒ社製　ＳｋｙＳｃａｎ１２７２）を用いて内部の炭素繊維の分散状態を観察した。
なお、開繊性の評価が良いほど、分散性が良好であることを示す。
×：著しく炭素繊維が偏在している
△：一部の炭素繊維が未分散状態
〇：均一に炭素繊維が分散している
　＜熱可塑性樹脂エマルジョン（１）の製造方法＞
　重合反応器に純水４５重量部を添加した後、窒素置換を行った。その後、昇温を開始し７５℃に到達した時点で過硫酸カリウム０．２重量部を添加した。更に反応器が８０℃に到達した時点でドデシルベンゼンスルホン酸ナトリウム２．１重量部（固形分換算）を純水３０重量部に溶解させた溶液、スチレン８８重量部、アクリロニトリル１０重量部、アクリル酸２重量部、ｔ－ドデシルメルカプタン０．８重量部からなる単量体混合物の７．５時間にわたる連続添加を開始した。その間反応器の温度は８０℃を保ち、連続添加終了後は更に重合を完了させるため温度を８０℃で５時間保持した。その後純水を用いて固形分を４５％に調整し、熱可塑性樹脂エマルジョン（１）を得た。 Evaluation of Openability The test pieces used for evaluation of openability obtained in each of the Examples and Comparative Examples were observed for the dispersion state of the carbon fibers inside using an X-ray CT apparatus (SkyScan 1272 manufactured by Bruker).
In addition, the better the evaluation of the openability, the better the dispersibility.
×: Carbon fibers are remarkably unevenly distributed △: Some carbon fibers are not dispersed ○: Carbon fibers are uniformly dispersed <Method for producing thermoplastic resin emulsion (1)>
After adding 45 parts by weight of pure water to the polymerization reactor, the reactor was purged with nitrogen. Thereafter, the temperature was started to rise, and when the temperature reached 75°C, 0.2 parts by weight of potassium persulfate was added. Furthermore, when the reactor reached 80° C., a solution of 2.1 parts by weight of sodium dodecylbenzenesulfonate (in terms of solid content) dissolved in 30 parts by weight of pure water, 88 parts by weight of styrene, 10 parts by weight of acrylonitrile, and acrylic acid were added. A continuous addition of a monomer mixture consisting of 2 parts by weight and 0.8 parts by weight of t-dodecyl mercaptan was initiated over a period of 7.5 hours. The temperature of the reactor was maintained at 80° C. during that time, and after the continuous addition was completed, the temperature was maintained at 80° C. for 5 hours in order to complete the polymerization. After that, pure water was used to adjust the solid content to 45% to obtain a thermoplastic resin emulsion (1).

　熱可塑性樹脂エマルジョン（１）中の固形分の重量平均分子量は５．４×１０４、ガラス転移温度は１０２℃であった。 The solid content in the thermoplastic resin emulsion (1) had a weight average molecular weight of 5.4×10 4 and a glass transition temperature of 102°C.

　＜熱可塑性樹脂エマルジョン（２）の製造方法＞
　単量体混合物をスチレン８６重量部、アクリロニトリル９重量部、ｔ－ドデシルメルカプタン０．８重量部、メタアクリル酸５重量部に変更した以外は熱可塑性樹脂エマルジョン（１）と同様の方法にて熱可塑性樹脂エマルジョン（２）を得た。 <Method for producing thermoplastic resin emulsion (2)>
Heating was performed in the same manner as the thermoplastic resin emulsion (1) except that the monomer mixture was changed to 86 parts by weight of styrene, 9 parts by weight of acrylonitrile, 0.8 parts by weight of t-dodecylmercaptan, and 5 parts by weight of methacrylic acid. A plastic resin emulsion (2) was obtained.

　熱可塑性樹脂エマルジョン（２）中の固形分の重量平均分子量は５．２×１０４、ガラス転移温度は１０３℃であった。 The solid content in the thermoplastic resin emulsion (2) had a weight average molecular weight of 5.2×10 4 and a glass transition temperature of 103°C.

　＜熱可塑性樹脂エマルジョン（３）の製造方法＞
　単量体混合物をスチレン９０重量部、アクリロニトリル１０重量部、ｔ－ドデシルメルカプタン０．８重量部に変更した以外は熱可塑性樹脂エマルジョン（１）と同様の方法にて熱可塑性樹脂エマルジョン（３）を得た。 <Method for producing thermoplastic resin emulsion (3)>
Thermoplastic resin emulsion (3) was prepared in the same manner as thermoplastic resin emulsion (1) except that the monomer mixture was changed to 90 parts by weight of styrene, 10 parts by weight of acrylonitrile, and 0.8 parts by weight of t-dodecylmercaptan. Obtained.

　熱可塑性樹脂エマルジョン（３）中の固形分の重量平均分子量は５．０×１０４、ガラス転移温度は１００℃であった。 The solid content in the thermoplastic resin emulsion (3) had a weight average molecular weight of 5.0×10 4 and a glass transition temperature of 100°C.

　＜繊維集束用組成物（１）の製造方法＞
　熱可塑性樹脂エマルジョン（１）を繊維集束用組成物（１）とした。上述の方法で測定した表面張力は４０ｍＮ／ｍであった。 <Method for producing fiber bundling composition (1)>
The thermoplastic resin emulsion (1) was used as the fiber bundling composition (1). The surface tension measured by the method described above was 40 mN/m.

　＜繊維集束用組成物（２）の製造方法＞
　熱可塑性樹脂エマルジョン（１）１００重量部(固形分)に対し、アセチレングリコール型非イオン性界面活性剤（日信化学工業（株）製　サーフィノール（登録商標）１０４Ｅ）を１重量部添加した後十分に攪拌し、繊維集束用組成物（２）を得た。上述の方法で測定した表面張力は２７ｍＮ／ｍであった。 <Method for producing fiber bundling composition (2)>
After adding 1 part by weight of acetylene glycol-type nonionic surfactant (Surfinol (registered trademark) 104E manufactured by Nissin Chemical Industry Co., Ltd.) to 100 parts by weight (solid content) of thermoplastic resin emulsion (1) The mixture was sufficiently stirred to obtain a fiber bundling composition (2). The surface tension measured by the method described above was 27 mN/m.

　＜繊維集束用組成物（３）の製造方法＞
　熱可塑性樹脂エマルジョン（１）１００重量部（固形分）に対し、ドデシルベンゼンスルホン酸ナトリウムを２重量部添加した後十分に攪拌し、繊維集束用組成物（３）を得た。上述の方法で測定した表面張力は２９ｍＮ／ｍであった。 <Method for producing fiber bundling composition (3)>
After adding 2 parts by weight of sodium dodecylbenzenesulfonate to 100 parts by weight (solid content) of thermoplastic resin emulsion (1), the mixture was sufficiently stirred to obtain a fiber bundling composition (3). The surface tension measured by the method described above was 29 mN/m.

　＜繊維集束用組成物（４）の製造方法＞
　熱可塑性樹脂エマルジョン（１）１００重量部（固形分）に対し、ジアルキルスルホコハク酸塩系陰イオン界面活性剤（三洋化成工業（株）製サンモリン（登録商標）ＯＴ－７０）を１重量部添加した後十分に攪拌し、繊維集束用組成物（４）を得た。上述の方法で測定した表面張力は２７ｍＮ／ｍであった。 <Method for producing fiber bundling composition (4)>
To 100 parts by weight (solid content) of thermoplastic resin emulsion (1), 1 part by weight of a dialkylsulfosuccinate-based anionic surfactant (Sanmorin (registered trademark) OT-70 manufactured by Sanyo Chemical Industries, Ltd.) was added. After that, the mixture was sufficiently stirred to obtain a fiber bundling composition (4). The surface tension measured by the method described above was 27 mN/m.

　＜繊維集束用組成物（５）の製造方法＞
　熱可塑性樹脂エマルジョン（２）を繊維集束用組成物（５）とした。上述の方法で測定した表面張力は３６ｍＮ／ｍであった。 <Method for producing fiber bundling composition (5)>
The thermoplastic resin emulsion (2) was used as a fiber bundling composition (5). The surface tension measured by the method described above was 36 mN/m.

　＜繊維集束用組成物（６）の製造方法＞
　熱可塑性樹脂エマルジョン（３）を繊維集束用組成物（６）とした。上述の方法で測定した表面張力は５５ｍＮ／ｍであった。 <Method for producing fiber bundling composition (6)>
The thermoplastic resin emulsion (3) was used as a fiber bundling composition (6). The surface tension measured by the method described above was 55 mN/m.

　＜繊維集束用組成物（７）の製造方法＞
　熱可塑性樹脂エマルジョン（１）１００重量部に対し、ジアルキルスルホコハク酸塩系陰イオン界面活性剤（三洋化成工業（株）製サンモリン（登録商標）ＯＴ－７０）を４重量部添加し、十分に攪拌し繊維集束用組成物（７）を得た。上述の方法で測定した表面張力は２４ｍＮ／ｍであった。 <Method for producing fiber bundling composition (7)>
To 100 parts by weight of the thermoplastic resin emulsion (1), 4 parts by weight of a dialkylsulfosuccinate-based anionic surfactant (Sanmorin (registered trademark) OT-70 manufactured by Sanyo Chemical Industries, Ltd.) was added and thoroughly stirred. A fiber bundling composition (7) was obtained. The surface tension measured by the method described above was 24 mN/m.

　＜チョップドストランド（１）の製造方法＞
　繊維集束用組成物（１）（固形分換算）を連続炭素繊維１００重量部に対して付着量が３重量部となるように集束させた後、ペレタイザーを用いて切断を行い、１００℃に調整した棚式乾燥機を用いて水分量が０．１%以下になるまで乾燥を行い、チョップドストランド（１）を得た。 <Method for producing chopped strand (1)>
After bundling the fiber bundling composition (1) (in terms of solid content) so that the adhesion amount is 3 parts by weight with respect to 100 parts by weight of continuous carbon fibers, cutting is performed using a pelletizer, and the temperature is adjusted to 100 ° C. Drying was carried out using a rack type dryer until the moisture content became 0.1% or less to obtain Chopped Strand (1).

　＜チョップドストランド（２）～（７）の製造方法＞
　繊維集束用組成物（１）を繊維集束用組成物（２）～（７）に変更した以外は、チョップドストランド（１）と同じ製法で、チョップドストランド（２）～（７）を得た。 <Method for producing chopped strands (2) to (7)>
Chopped strands (2) to (7) were obtained in the same manner as the chopped strand (1) except that the fiber bundling composition (1) was changed to the fiber bundling composition (2) to (7).

　＜連続樹脂含浸繊維（１）の製造方法＞
　布引装置を用いて、繊維集束用組成物（１）（固形分換算）を炭素繊維１００重量部に対して付着量が１０重量部（固形分換算）となるように集束させ、その後得られた連続樹脂含浸繊維を１８０℃に調整した乾燥炉内を１ｍ／分の速さで３分間移動させることにより水分を完全に除去し、最終の連続樹脂含浸繊維（１）を得た。 <Method for producing continuous resin-impregnated fiber (1)>
Using a cloth binding device, the fiber bundling composition (1) (converted to solid content) was bundled so that the adhesion amount was 10 parts by weight (converted to solid content) with respect to 100 parts by weight of carbon fiber, and then obtained The continuous resin-impregnated fiber was moved in a drying oven adjusted to 180° C. at a speed of 1 m/min for 3 minutes to completely remove moisture, thereby obtaining the final continuous resin-impregnated fiber (1).

　＜連続樹脂含浸繊維（２）～（７）の製造方法＞
　繊維集束用組成物（１）を繊維集束用組成物（２）～（７）に変更した以外は、連続樹脂含浸繊維（１）と同じ製法で、連続樹脂含浸繊維（２）～（７）を得た。 <Method for producing continuous resin-impregnated fibers (2) to (7)>
Continuous resin-impregnated fibers (2) to (7) are produced in the same manner as the continuous resin-impregnated fiber (1) except that the fiber bundling composition (1) is changed to the fiber bundling composition (2) to (7). got

　上述のチョップドストランド、連続樹脂含浸繊維に用いた炭素繊維は、帝人株式会社製　Ｔｅｎａｘ（登録商標）－Ｊ　ＳＴＳ４０　Ｆ１３　２４Ｋ　１６００ｔｅｘである。 The carbon fiber used for the above chopped strands and continuous resin-impregnated fibers is Tenax (registered trademark)-J STS40 F13 24K 1600 tex manufactured by Teijin Limited.

　熱可塑性樹脂（１）
日本エイアンドエル株式会社製　クララスチック（登録商標）ＧＡ－５０１
（ＡＢＳ樹脂）
　熱可塑性樹脂（２）
日本エイアンドエル株式会社製　テクニエース（登録商標）ＴＡ－１５００
（ポリアミド樹脂とＡＢＳ樹脂のアロイ）
　熱可塑性樹脂（３）
日本エイアンドエル株式会社製　テクニエース（登録商標）ＰＡＸ－１４３９
（ポリカーボネート樹脂とＡＢＳ樹脂のアロイ）
　＜繊維強化熱可塑性樹脂組成物の製造方法＞
　熱可塑性樹脂およびチョップドストランドを表３に記載の配合割合で混合した後、２６０℃に設定したフィーダーを２基有しているＳＴＥＥＲ社製ＯＭｅｇａ３０Ｈを用いて、Ｆ１より熱可塑性樹脂を、Ｆ２からチョップドストランドを投入し溶融混練して繊維強化熱可塑性樹脂組成物のペレットを得た。また、このペレットを用いてシャルピー衝撃強度用試験片を射出成形機にて成形し、得られた成形品の中央部から５ｍｍ×５ｍｍ×４ｍｍの試験を切り出し、開繊性の評価に用いた。 Thermoplastic resin (1)
Nippon A&L Co., Ltd. Clarastick (registered trademark) GA-501
(ABS resin)
Thermoplastic resin (2)
Techniace (registered trademark) TA-1500 manufactured by Nippon A&L Co., Ltd.
(Alloy of polyamide resin and ABS resin)
Thermoplastic resin (3)
Techniace (registered trademark) PAX-1439 manufactured by Nippon A&L Co., Ltd.
(alloy of polycarbonate resin and ABS resin)
<Method for producing fiber-reinforced thermoplastic resin composition>
After mixing the thermoplastic resin and the chopped strands at the blending ratio shown in Table 3, the thermoplastic resin was chopped from F1 and the chopped strands from F2 using OMega30H manufactured by STEER, which has two feeders set at 260°C. A strand was added and melt-kneaded to obtain pellets of a fiber-reinforced thermoplastic resin composition. Using the pellets, a test piece for Charpy impact strength was molded with an injection molding machine, and a test piece of 5 mm × 5 mm × 4 mm was cut from the center of the obtained molded product and used for evaluation of openability.

　＜連続樹脂含浸繊維と熱可塑性樹脂からなる積層品の製造方法＞
　連続樹脂含浸繊維を２０ｃｍ角のシートとなるように複数枚並列させた後、ポリアミド樹脂フィルム（東レフィルム加工株式会社製　レイファン（登録商標）ＮO １４０１　厚み４０μｍ）と炭素繊維含量が３０重量％になるように交互に積層させ、設定温度２５０℃の圧縮成型機ＮＦ３７型を用いて、圧力５ＭＰａをかけた状態で余熱を５分間行った後、圧力１５ＭＰａをかけた状態で５分間熱プレス処理を行い、厚みが２ｍｍの積層品を作製した。得られた積層品から幅５ｍｍ×長さ５ｍｍの試験片を切り出し、開繊性の評価に用いた。 <Method for producing a laminated product composed of continuous resin-impregnated fibers and thermoplastic resin>
After arranging a plurality of continuous resin-impregnated fibers in parallel to form a 20 cm square sheet, a polyamide resin film (Rayfan (registered trademark) NO 1401, thickness 40 μm, manufactured by Toray Advanced Film Co., Ltd.) and a carbon fiber content of 30% by weight. After preheating for 5 minutes with a pressure of 5 MPa using a compression molding machine NF37 with a set temperature of 250 ° C., hot press treatment is performed for 5 minutes with a pressure of 15 MPa. to produce a laminate having a thickness of 2 mm. A test piece having a width of 5 mm and a length of 5 mm was cut out from the obtained laminated product and used for the evaluation of openability.

Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000005

Figure JPOXMLDOC01-appb-T000006
Figure JPOXMLDOC01-appb-T000006

　実施例１～１５は、本発明で規定する表面張力を満足する繊維集束用組成物であるため、集束性および開繊性のバランスに優れるものであった。 Examples 1 to 15 were compositions for fiber bundling that satisfied the surface tension specified in the present invention, and therefore had an excellent balance between bundling and opening properties.

　比較例１～４は、本発明で規定する表面張力を満足しない繊維集束用組成物であるため、集束性および開繊性に劣るものであった。 Comparative Examples 1 to 4 were fiber bundling compositions that did not satisfy the surface tension specified in the present invention, and were inferior in bundling and opening properties.

　３．本発明３に関する実施例および比較例
　重量平均分子量
　得られた熱可塑性樹脂エマルジョンを室温にて一昼夜乾燥後、７０℃のオーブンで１時間乾燥させることで測定サンプルとした。その後、測定サンプル０．０２ｇをテトラヒドロフラン（ＴＨＦ）１０ｍｌに溶解させた溶液をゲルパーミエーションクロマトグラム（ＧＰＣ）測定装置を用いて、下記条件で測定した。
検出器：ＵＶ
カラム：Ａｇｉｌｅｎｔ社製　ＭＩＸＤ－Ｂ
カラム温度：５０℃
溶媒：テトラヒドロフラン（ＴＨＦ）
流量：１ｍｌ／ｍｉｎ、
検出波長：２５４ｎｍ
標準試料：ポリスチレン
　ガラス転移温度
得られた熱可塑性樹脂エマルジョンを９０℃のオーブンで１０時間乾燥させることで測定サンプルとした。その後、示差走査熱量計を用いてＪＩＳ　Ｋ７１２１―２０１２に準拠して測定した。 3. Example and Comparative Example Weight Average Molecular Weight The obtained thermoplastic resin emulsion was dried at room temperature for a whole day and night, and then dried in an oven at 70° C. for 1 hour to obtain a measurement sample. After that, a solution obtained by dissolving 0.02 g of the measurement sample in 10 ml of tetrahydrofuran (THF) was measured using a gel permeation chromatogram (GPC) measurement device under the following conditions.
Detector: UV
Column: MIXD-B manufactured by Agilent
Column temperature: 50°C
Solvent: Tetrahydrofuran (THF)
Flow rate: 1 ml/min,
Detection wavelength: 254 nm
Standard sample: polystyrene glass transition temperature The obtained thermoplastic resin emulsion was dried in an oven at 90°C for 10 hours to prepare a measurement sample. After that, it was measured according to JIS K7121-2012 using a differential scanning calorimeter.

　動的表面張力
　サンプル濃度を６％に調整し、バブルプレッシャー式動的表面張力計（ＫＲＵＳＳ社製　ＢＰ１００）を用いて、最大泡圧法により、温度３０℃、キャピラリー径０．２ｍｍのキャピラリー、表面寿命時間１００ｍｓの条件で測定した。単位：ｍＮ／ｍ
　曲げ強度
　各実施例及び比較例で得られた試験片を用い、ＪＩＳ　Ｋ７０７４に準じて曲げ強度を測定した。単位：ＭＰａ
　＜熱可塑性樹脂エマルジョンの製造方法＞
　耐圧性の重合反応器に、脱イオン水４５部を添加した後、窒素置換を行った。スチレン８８部、アクリロニトリル１０部、ｔ－ドデシルメルカプタン０．８部からなる単量体混合物A１００部を準備し、これを単量体混合物Ａ１００重量％あたり５重量％の単量体混合物Ａ－１と９５重量％の単量体混合物Ａ－２に分けた。 Adjusting the dynamic surface tension sample concentration to 6%, using a bubble pressure dynamic surface tension meter (KRUSS BP100), the maximum bubble pressure method, temperature 30 ° C., capillary diameter 0.2 mm, surface life Measurement was performed under the condition of 100 ms. Unit: mN/m
Bending Strength Bending strength was measured according to JIS K7074 using the test pieces obtained in Examples and Comparative Examples. Unit: MPa
<Method for producing thermoplastic resin emulsion>
After adding 45 parts of deionized water to a pressure-resistant polymerization reactor, the reactor was purged with nitrogen. 100 parts of a monomer mixture A consisting of 88 parts of styrene, 10 parts of acrylonitrile, and 0.8 parts of t-dodecylmercaptan was prepared, and this was mixed with 5% by weight of monomer mixture A-1 per 100% by weight of monomer mixture A. It was divided into 95% by weight monomer mixture A-2.

　次いで反応器を７５℃に昇温し、ドデシルベンゼンスルホン酸ナトリウム０．４部（固形分換算）および単量体混合物Ａ－１加えて十分攪拌した後、過硫酸カリウム０．１部を仕込み、８０℃にて重合を開始した。 Then, the temperature of the reactor is raised to 75° C., 0.4 part of sodium dodecylbenzenesulfonate (in terms of solid content) and monomer mixture A-1 are added and sufficiently stirred, then 0.1 part of potassium persulfate is charged, Polymerization was initiated at 80°C.

　開始から１時間後に残りの単量体混合物Ａ－２、アクリル酸2部を脱イオン水１８部に溶解させた溶液、ドデシルベンゼンスルホン酸ナトリウム１．７部（固形分換算）と過硫酸カリウム０．１部を脱イオン水３０部に溶解させた溶液を７．５時間にわたって連続的に添加した。そのまま重合温度を８０℃で５時間保ち重合を終了した。次いで、熱可塑性樹脂エマルジョンを苛性ソーダ水溶液でｐＨを約７に調整した後、水蒸気蒸留により未反応単量体および他の低沸点化合物を除去し、固形分を４５％に調整し、熱可塑性樹脂エマルジョンを得た。 After 1 hour from the start, the remaining monomer mixture A-2, a solution of 2 parts of acrylic acid dissolved in 18 parts of deionized water, 1.7 parts of sodium dodecylbenzenesulfonate (solid content conversion) and 0 potassium persulfate A solution of .1 part in 30 parts deionized water was added continuously over a period of 7.5 hours. The polymerization temperature was maintained at 80° C. for 5 hours to complete the polymerization. Next, after adjusting the pH of the thermoplastic resin emulsion to about 7 with an aqueous solution of caustic soda, unreacted monomers and other low boiling point compounds are removed by steam distillation, the solid content is adjusted to 45%, and the thermoplastic resin emulsion is got

　熱可塑性樹脂エマルジョンの固形分の重量平均分子量は５．４×１０４、ガラス転移温度は１０２℃であった。 The solid content of the thermoplastic resin emulsion had a weight average molecular weight of 5.4×10 4 and a glass transition temperature of 102°C.

　＜繊維集束用組成物－１の製造方法＞
　熱可塑性樹脂エマルジョン１００重量部（固形分換算）に、アセチレングリコール系非イオン界面活性剤（製品名「サーフィノール（登録商標）１０４Ｅ」）を１重量部（固形分換算）添加し、十分に攪拌し繊維集束用組成物－１を得た。上述の方法で測定した動的表面張力は４０ｍＮ／ｍであった。 <Method for producing fiber bundling composition-1>
1 part by weight (converted to solid content) of an acetylene glycol-based nonionic surfactant (product name “Surfinol (registered trademark) 104E”) is added to 100 parts by weight (converted to solid content) of a thermoplastic resin emulsion, and the mixture is sufficiently stirred. Then, a fiber bundling composition-1 was obtained. The dynamic surface tension measured by the method described above was 40 mN/m.

　サーフィノール（登録商標）１０４Ｅ：日信化学工業（株）製　　物質名：２，４，７，９－テトラメチル－５－デシン－４，７－ジオール
　＜繊維集束用組成物－２の製造方法＞
　アセチレングリコール系非イオン界面活性剤（製品名「サーフィノール（登録商標）１０４Ｅ」）の添加量を１重量部から３重量部に変更した以外は繊維集束用組成物－１と同様の方法で行った。上述の方法で測定した動的表面張力は２９ｍＮ／ｍであった。 Surfynol (registered trademark) 104E: manufactured by Nissin Chemical Industry Co., Ltd. Substance name: 2,4,7,9-tetramethyl-5-decyne-4,7-diol <Production method of fiber bundling composition-2 ＞
Performed in the same manner as the fiber bundling composition-1 except that the amount of acetylene glycol-based nonionic surfactant (product name “Surfinol (registered trademark) 104E”) added was changed from 1 part by weight to 3 parts by weight. rice field. The dynamic surface tension measured by the method described above was 29 mN/m.

　＜繊維集束用組成物－３の製造方法＞
　アセチレングリコール系非イオン界面活性剤（製品名「サーフィノール（登録商標）１０４Ｅ」）をジアルキルスルホコハク酸塩系陰イオン界面活性剤（製品名「サンモリン（登録商標）ＯＴ－７０」）に変更した以外は繊維集束用組成物－１と同様の方法で行った。 <Method for producing fiber bundling composition-3>
Except for changing the acetylene glycol-based nonionic surfactant (product name “Surfinol (registered trademark) 104E”) to a dialkyl sulfosuccinate-based anionic surfactant (product name “Sanmorin (registered trademark) OT-70”) was performed in the same manner as the fiber bundling composition-1.

　上述の方法で測定した動的表面張力は４４ｍＮ／ｍであった。 The dynamic surface tension measured by the above method was 44 mN/m.

　サンモリン（登録商標）ＯＴ－７０：三洋化成工業（株）製　物質名：ジオクチルスルホコハク酸ナトリウム
　＜繊維集束用組成物－４の製造方法＞
　アセチレングリコール系非イオン界面活性剤（製品名「サーフィノール（登録商標）１０４Ｅ」）をジアルキルスルホコハク酸塩系陰イオン界面活性剤（製品名「サンモリン（登録商標）ＯＴ－７０」）に変更した以外は繊維集束用組成物－２と同様の方法で行った。 Sanmorin (registered trademark) OT-70: manufactured by Sanyo Chemical Industries, Ltd. Substance name: sodium dioctyl sulfosuccinate <Method for producing fiber bundling composition-4>
Except for changing the acetylene glycol-based nonionic surfactant (product name “Surfinol (registered trademark) 104E”) to a dialkyl sulfosuccinate-based anionic surfactant (product name “Sanmorin (registered trademark) OT-70”) was performed in the same manner as the fiber bundling composition-2.

　上述の方法で測定した動的表面張力は３０ｍＮ／ｍであった。 The dynamic surface tension measured by the above method was 30 mN/m.

　＜繊維集束用組成物－５の製造方法＞
　熱可塑性樹脂エマルジョンを繊維集束剤組成物－５とした。上述の方法で測定した動的表面張力は６２ｍＮ／ｍであった。 <Method for producing fiber bundling composition-5>
A thermoplastic resin emulsion was used as a fiber sizing agent composition-5. The dynamic surface tension measured by the method described above was 62 mN/m.

　＜連続樹脂含浸繊維－１の製造方法＞
　布引装置を用いて、繊維集束用組成物－１（固形分換算）を炭素繊維１００重量部に対して含有量が１５重量部となるように集束させ、その後得られた連続樹脂含浸繊維を１８０℃に調整した乾燥炉内を１ｍ／分の速さで３分間移動させることにより、水分を完全に除去し、最終の連続樹脂含浸繊維－１を得た。 <Method for producing continuous resin-impregnated fiber-1>
Using a cloth binding device, fiber bundling composition-1 (in terms of solid content) is bundled so that the content is 15 parts by weight with respect to 100 parts by weight of carbon fiber, and then the obtained continuous resin-impregnated fiber is 180 parts by weight. C. for 3 minutes at a speed of 1 m/min to completely remove moisture, thereby obtaining a final continuous resin-impregnated fiber-1.

　＜連続樹脂含浸繊維－２～５の製造方法＞
　繊維集束用組成物－１を繊維集束剤組成物２～５に変更した以外は連続樹脂含浸繊維－１と同じ製法で、連続樹脂含浸繊維－２～５を得た。 <Method for producing continuous resin-impregnated fibers-2 to 5>
Continuous resin-impregnated fibers-2 to 5 were obtained in the same manner as the continuous resin-impregnated fiber-1, except that the fiber bundling composition-1 was changed to fiber sizing agent compositions 2-5.

　上述の連続樹脂含浸繊維に用いた炭素繊維は、帝人株式会社製　Ｔｅｎａｘ（登録商標）－Ｊ　ＳＴＳ４０　Ｆ１３　２４Ｋ　１６００ｔｅｘ
　＜連続樹脂含浸繊維と熱可塑性樹脂からなる積層品の製造方法＞
　連続樹脂含浸繊維を２０ｃｍ角のシートとなるように複数枚並列させた後、ポリアミド樹脂フィルム（東レフィルム加工株式会社製　レイファン（登録商標）Ｎ０　１４０１　厚み４０μｍ）と炭素繊維含量が３０重量％になるように交互に積層させ、設定温度２５０℃の圧縮成型機ＮＦ３７型を用いて、圧力５ＭＰａをかけた状態で余熱を５分間行った後、圧力１５ＭＰａをかけた状態で５分間熱プレス処理を行い、厚みが２ｍｍの積層品を作製した。また、得られた積層品から幅１５ｍｍ×長さ１５０ｍｍの試験片を切り出し曲げ試験用試験片とした。 The carbon fiber used for the above-mentioned continuous resin-impregnated fiber is Tenax (registered trademark)-J STS40 F13 24K 1600tex manufactured by Teijin Limited.
<Method for producing a laminated product composed of continuous resin-impregnated fibers and thermoplastic resin>
After arranging a plurality of continuous resin-impregnated fibers in parallel to form a 20 cm square sheet, a polyamide resin film (Rayfan (registered trademark) N0 1401, thickness 40 μm, manufactured by Toray Advanced Film Co., Ltd.) and a carbon fiber content of 30% by weight. After preheating for 5 minutes with a pressure of 5 MPa using a compression molding machine NF37 with a set temperature of 250 ° C., hot press treatment is performed for 5 minutes with a pressure of 15 MPa. to produce a laminate having a thickness of 2 mm. A test piece having a width of 15 mm and a length of 150 mm was cut out from the obtained laminated product and used as a test piece for a bending test.

　尚、積層品を作成する際には炭素繊維の方向は一方向に揃えてあり、また曲げ試験用試験片は炭素繊維の方向と試験片の長辺の方向が一致する方向で切り出しを行った。 When the laminated product was produced, the direction of the carbon fibers was aligned in one direction, and the test piece for the bending test was cut out in the direction in which the direction of the carbon fiber and the direction of the long side of the test piece coincided. .

Figure JPOXMLDOC01-appb-T000007
Figure JPOXMLDOC01-appb-T000007

　表５より、本発明の繊維集束用組成物を用いて製造された連続樹脂含浸繊維をポリアミド樹脂フィルムと積層した実施例１～４は、曲げ強度に優れるものであった。 From Table 5, Examples 1 to 4 in which continuous resin-impregnated fibers produced using the fiber bundling composition of the present invention were laminated with a polyamide resin film were excellent in bending strength.

　比較例１は、本発明の繊維集束用組成物の動的表面張力が規定範囲を満足しないため、曲げ強度に劣るものであった。 Comparative Example 1 was inferior in bending strength because the dynamic surface tension of the fiber bundling composition of the present invention did not satisfy the specified range.

　４．本発明４に関する実施例および比較例
　平均粒子径
　光子相関法による平均粒子径の測定によって行い、ＦＰＡＲ－１０００（大塚電子製）を使用し、ＪＩＳ　Ｚ８８２６に準拠した方法で測定した。 4. Examples and Comparative Examples Relating to Invention 4 Average particle size The average particle size was measured by the photon correlation method, using FPAR-1000 (manufactured by Otsuka Electronics Co., Ltd.), and measured according to JIS Z8826.

　衝撃エネルギー吸収
　各実施例及び比較例で得られた試験片を用い、ＪＩＳ　Ｋ７０７４に準じて得られた曲げ応力－歪曲線図において、終点を５％歪とし、応力－歪曲線に囲まれた面積で求めた。単位：Ｊ
　曲げ強度
　各実施例及び比較例で得られた試験片を用い、ＪＩＳ　Ｋ７０７４に準じて曲げ強度を測定した。単位：ＭＰａ
　＜熱可塑性樹脂エマルジョン（１）＞
　耐圧性の重合反応機に、脱イオン水１００部を添加した後、窒素置換を行った。スチレン８８部、アクリロニトリル１０部、ｔ－ドデシルメルカプタン０．７部からなる単量体混合物Ａ１００部を準備し、これを単量体混合物Ａ１００重量％あたり５重量％の単量体混合物Ａ－１と９５重量％の単量体混合物Ａ－２に分けた。 Impact energy absorption Bending stress-strain curve diagram obtained according to JIS K7074 using the test pieces obtained in each example and comparative example, the end point is 5% strain, and the area surrounded by the stress-strain curve I asked for it. Unit: J
Bending Strength Bending strength was measured according to JIS K7074 using the test pieces obtained in Examples and Comparative Examples. Unit: MPa
<Thermoplastic resin emulsion (1)>
After 100 parts of deionized water was added to the pressure-resistant polymerization reactor, nitrogen substitution was performed. Prepare 100 parts of a monomer mixture A consisting of 88 parts of styrene, 10 parts of acrylonitrile, and 0.7 parts of t-dodecylmercaptan, and add 5% by weight of monomer mixture A-1 to 100% by weight of monomer mixture A. It was divided into 95% by weight monomer mixture A-2.

　次いで、反応器を７５℃に昇温し、ドデシルベンゼンスルホン酸ナトリウム０．７部（固形分換算）および単量体混合物Ａ―１を加えて十分攪拌した後、過硫酸カリウム０．１部を仕込み、８０℃にて重合を開始した。 Next, the reactor was heated to 75° C., 0.7 parts of sodium dodecylbenzenesulfonate (in terms of solid content) and the monomer mixture A-1 were added and sufficiently stirred, and then 0.1 parts of potassium persulfate was added. After charging, polymerization was started at 80°C.

　開始から１時間後に残りの単量体混合物Ａ―２と、アクリル酸２部を脱イオン水１８部に溶解させた溶液と、ドデシルベンゼンスルホン酸ナトリウム１．４部（固形分換算）、重炭酸ナトリウム０．７部および過硫酸カリウム０．１部を脱イオン水３０部に溶解させた溶液とを、７．５時間にわたって連続的に添加した。 After 1 hour from the start, the remaining monomer mixture A-2, a solution obtained by dissolving 2 parts of acrylic acid in 18 parts of deionized water, 1.4 parts of sodium dodecylbenzenesulfonate (solid content conversion), bicarbonate A solution of 0.7 parts sodium and 0.1 parts potassium persulfate in 30 parts deionized water was added continuously over 7.5 hours.

　そのまま重合温度を８０℃に５時間保ち重合を終了した。次いで、熱可塑性樹脂エマルジョンを苛性ソーダ水溶液でｐＨを約７に調整した後、水蒸気蒸留により未反応単量体および他の低沸点化合物を除去し、固形分を４５％に調整し、熱可塑性樹脂エマルジョン（１）を得た。上述の方法で平均粒子径を測定したところ、１２６ｎｍであった。 The polymerization temperature was maintained at 80°C for 5 hours to complete the polymerization. Next, after adjusting the pH of the thermoplastic resin emulsion to about 7 with an aqueous solution of caustic soda, unreacted monomers and other low boiling point compounds are removed by steam distillation, the solid content is adjusted to 45%, and the thermoplastic resin emulsion is (1) was obtained. The average particle size measured by the method described above was 126 nm.

　＜熱可塑性樹脂エマルジョン（２）＞
　耐圧性の重合反応機に、脱イオン水１２０部を添加した後、窒素置換を行った。スチレン８８部、アクリロニトリル１０部、ｔ－ドデシルメルカプタン０．８部からなる単量体混合物Ａ１００部を準備し、これを単量体混合物Ａ１００重量％あたり５重量％の単量体混合物Ａ－１と９５重量％の単量体混合物Ａ－２に分けた。 <Thermoplastic resin emulsion (2)>
After adding 120 parts of deionized water to a pressure-resistant polymerization reactor, nitrogen substitution was performed. Prepare 100 parts of a monomer mixture A consisting of 88 parts of styrene, 10 parts of acrylonitrile, and 0.8 parts of t-dodecyl mercaptan, and add 5% by weight of monomer mixture A-1 to 100% by weight of monomer mixture A. It was divided into 95% by weight monomer mixture A-2.

　次いで反応器を７５℃に昇温し、ドデシルベンゼンスルホン酸ナトリウム１．０部（固形分換算）および単量体混合物Ａ―１加えて十分攪拌した後、過硫酸カリウム０．１部を仕込み、８０℃にて重合を開始した。 Next, the reactor was heated to 75° C., 1.0 parts of sodium dodecylbenzenesulfonate (in terms of solid content) and the monomer mixture A-1 were added and sufficiently stirred, then 0.1 part of potassium persulfate was charged, Polymerization was initiated at 80°C.

　開始から１時間後に残りの単量体混合物Ａ―２、アクリル酸２部を脱イオン水１８部に溶解させた溶液、ドデシルベンゼンスルホン酸ナトリウム１．１部（固形分換算）と重炭酸ナトリウム０．７部および過硫酸カリウム０．１部を脱イオン水３０部に溶解させた溶液を７．５時間にわたって連続的に添加した。 One hour after the start, the remaining monomer mixture A-2, a solution prepared by dissolving 2 parts of acrylic acid in 18 parts of deionized water, 1.1 parts of sodium dodecylbenzenesulfonate (solid content conversion) and 0 sodium bicarbonate. A solution of .7 parts and 0.1 parts potassium persulfate in 30 parts deionized water was added continuously over 7.5 hours.

　そのまま重合温度を８０℃に５時間保ち重合を終了した。次いで、熱可塑性樹脂エマルジョンを苛性ソーダ水溶液でｐＨを約７に調整した後、水蒸気蒸留により未反応単量体および他の低沸点化合物を除去し、固形分を４５％に調整し、熱可塑性樹脂エマルジョン（２）を得た。上述の方法で平均粒子径を測定したところ、９９ｎｍであった。 The polymerization temperature was maintained at 80°C for 5 hours to complete the polymerization. Next, after adjusting the pH of the thermoplastic resin emulsion to about 7 with an aqueous solution of caustic soda, unreacted monomers and other low boiling point compounds are removed by steam distillation, the solid content is adjusted to 45%, and the thermoplastic resin emulsion is (2) was obtained. When the average particle size was measured by the method described above, it was 99 nm.

　＜熱可塑性樹脂エマルジョン（３）＞
　耐圧性の重合反応機に、脱イオン水１４０部を添加した後、窒素置換を行った。スチレン８８部、アクリロニトリル１０部、ｔ－ドデシルメルカプタン０．８部からなる単量体混合物Ａ１００部を準備し、これを単量体混合物Ａ１００重量％あたり５重量％の単量体混合物Ａ－１と９５重量％の単量体混合物Ａ－２に分けた。 <Thermoplastic resin emulsion (3)>
After 140 parts of deionized water was added to the pressure-resistant polymerization reactor, nitrogen substitution was performed. Prepare 100 parts of a monomer mixture A consisting of 88 parts of styrene, 10 parts of acrylonitrile, and 0.8 parts of t-dodecyl mercaptan, and add 5% by weight of monomer mixture A-1 to 100% by weight of monomer mixture A. It was divided into 95% by weight monomer mixture A-2.

　次いで反応器を７５℃に昇温し、ドデシルベンゼンスルホン酸ナトリウム１．３部（固形分換算）および単量体混合物Ａ－１加えて十分攪拌した後、過硫酸カリウム０．１部を仕込み、８０℃にて重合を開始した。 Then, the temperature of the reactor is raised to 75° C., 1.3 parts of sodium dodecylbenzenesulfonate (in terms of solid content) and the monomer mixture A-1 are added and sufficiently stirred, then 0.1 part of potassium persulfate is charged, Polymerization was initiated at 80°C.

　開始から１時間後に残りの単量体混合物Ａ－２、アクリル酸2部を脱イオン水１８部に溶解させた溶液、ドデシルベンゼンスルホン酸ナトリウム０．８部（固形分換算）と重炭酸ナトリウム０．７部および過硫酸カリウム０．１部を脱イオン水３０部に溶解させた溶液を７．５時間にわたって連続的に添加した。 After 1 hour from the start, the remaining monomer mixture A-2, a solution of 2 parts of acrylic acid dissolved in 18 parts of deionized water, 0.8 parts of sodium dodecylbenzenesulfonate (solid content conversion) and 0 parts of sodium bicarbonate A solution of .7 parts and 0.1 parts potassium persulfate in 30 parts deionized water was added continuously over 7.5 hours.

　そのまま重合温度を８０℃に５時間保ち重合を終了した。次いで、熱可塑性樹脂エマルジョンを苛性ソーダ水溶液でｐＨを約７に調整した後、水蒸気蒸留により未反応単量体および他の低沸点化合物を除去し、固形分を４５％に調整し、共重合体エマルジョン（３）を得た。上述の方法で平均粒子径を測定したところ、９４ｎｍであった。 The polymerization temperature was maintained at 80°C for 5 hours to complete the polymerization. Next, after adjusting the pH of the thermoplastic resin emulsion to about 7 with an aqueous solution of caustic soda, unreacted monomers and other low boiling point compounds are removed by steam distillation, and the solid content is adjusted to 45% to obtain a copolymer emulsion. (3) was obtained. When the average particle size was measured by the method described above, it was 94 nm.

　＜熱可塑性樹脂エマルジョン（４）＞
　耐圧性の重合反応機に、脱イオン水１９０部を添加した後、窒素置換を行った。スチレン８８部、アクリロニトリル１０部、ｔ－ドデシルメルカプタン０．８部からなる単量体混合物A１００部を準備し、これを単量体混合物Ａ１００重量％あたり５重量％の単量体混合物Ａ－１と９５重量％の単量体混合物Ａ－２に分けた。 <Thermoplastic resin emulsion (4)>
After adding 190 parts of deionized water to a pressure-resistant polymerization reactor, nitrogen substitution was performed. 100 parts of a monomer mixture A consisting of 88 parts of styrene, 10 parts of acrylonitrile, and 0.8 parts of t-dodecylmercaptan was prepared, and this was mixed with 5% by weight of monomer mixture A-1 per 100% by weight of monomer mixture A. It was divided into 95% by weight monomer mixture A-2.

　次いで反応器を７５℃に昇温し、ドデシルベンゼンスルホン酸ナトリウム１．８部（固形分換算）および単量体混合物Ａ－１加えて十分攪拌した後、過硫酸カリウム０．１部を仕込み、８０℃にて重合を開始した。 Next, the temperature of the reactor is raised to 75° C., 1.8 parts of sodium dodecylbenzenesulfonate (in terms of solid content) and the monomer mixture A-1 are added and thoroughly stirred, then 0.1 part of potassium persulfate is charged, Polymerization was initiated at 80°C.

　開始から１時間後に残りの単量体混合物Ａ－２、アクリル酸2部を脱イオン水１８部に溶解させた溶液、ドデシルベンゼンスルホン酸ナトリウム０．３部（固形分換算）と重炭酸ナトリウム０．７部および過硫酸カリウム０．１部を脱イオン水３０部に溶解させた溶液を７．５時間にわたって連続的に添加した。 After 1 hour from the start, the remaining monomer mixture A-2, a solution of 2 parts of acrylic acid dissolved in 18 parts of deionized water, 0.3 parts of sodium dodecylbenzenesulfonate (solid content conversion) and 0 parts of sodium bicarbonate A solution of .7 parts and 0.1 parts potassium persulfate in 30 parts deionized water was added continuously over 7.5 hours.

　そのまま重合温度を８０℃に５時間保ち重合を終了した。次いで、熱可塑性樹脂エマルジョンを苛性ソーダ水溶液でｐＨを約７に調整した後、水蒸気蒸留により未反応単量体および他の低沸点化合物を除去し、固形分を４５％に調整し、熱可塑性樹脂エマルジョン（４）を得た。上述の方法で平均粒子径を測定したところ、７９ｎｍであった。 The polymerization temperature was maintained at 80°C for 5 hours to complete the polymerization. Next, after adjusting the pH of the thermoplastic resin emulsion to about 7 with an aqueous solution of caustic soda, unreacted monomers and other low boiling point compounds are removed by steam distillation, the solid content is adjusted to 45%, and the thermoplastic resin emulsion is (4) was obtained. When the average particle size was measured by the method described above, it was 79 nm.

　＜熱可塑性樹脂エマルジョンエマルジョン（５）＞
　耐圧性の重合反応機に、脱イオン水４５部を添加した後、窒素置換を行った。スチレン８８部、アクリロニトリル１０部、ｔ－ドデシルメルカプタン０．８部からなる単量体混合物Ａ１００部を準備し、これを単量体混合物Ａ１００重量％あたり５重量％の単量体混合物Ａ－１と９５重量％の単量体混合物Ａ－２に分けた。 <Thermoplastic resin emulsion emulsion (5)>
After adding 45 parts of deionized water to the pressure-resistant polymerization reactor, nitrogen substitution was performed. Prepare 100 parts of a monomer mixture A consisting of 88 parts of styrene, 10 parts of acrylonitrile, and 0.8 parts of t-dodecyl mercaptan, and add 5% by weight of monomer mixture A-1 to 100% by weight of monomer mixture A. It was divided into 95% by weight monomer mixture A-2.

　次いで反応器を７５℃に昇温し、ドデシルベンゼンスルホン酸ナトリウム０．４部（固形分換算）および単量体混合物Ａ－１加えて十分攪拌した後、過硫酸カリウム０．１部を仕込み、８０℃にて重合を開始した。 Then, the temperature of the reactor is raised to 75° C., 0.4 part of sodium dodecylbenzenesulfonate (in terms of solid content) and monomer mixture A-1 are added and sufficiently stirred, then 0.1 part of potassium persulfate is charged, Polymerization was initiated at 80°C.

　開始から１時間後に残りの単量体混合物Ａ－２、アクリル酸2部を脱イオン水１８部に溶解させた溶液、ドデシルベンゼンスルホン酸ナトリウム１．７部（固形分換算）と重炭酸ナトリウム０．７部および過硫酸カリウム０．１部を脱イオン水３０部に溶解させた溶液を７．５時間にわたって連続的に添加した。 After 1 hour from the start, the remaining monomer mixture A-2, a solution of 2 parts of acrylic acid dissolved in 18 parts of deionized water, 1.7 parts of sodium dodecylbenzenesulfonate (solid content conversion) and 0 sodium bicarbonate A solution of .7 parts and 0.1 parts potassium persulfate in 30 parts deionized water was added continuously over 7.5 hours.

　そのまま重合温度を８０℃に５時間保ち重合を終了した。次いで、熱可塑性樹脂エマルジョンを苛性ソーダ水溶液でｐＨを約７に調整した後、水蒸気蒸留により未反応単量体および他の低沸点化合物を除去し、固形分を４５％に調整し、熱可塑性樹脂エマルジョン（５）を得た。上述の方法で平均粒子径を測定した結果、１４５ｎｍであった。 The polymerization temperature was maintained at 80°C for 5 hours to complete the polymerization. Next, after adjusting the pH of the thermoplastic resin emulsion to about 7 with an aqueous solution of caustic soda, unreacted monomers and other low boiling point compounds are removed by steam distillation, the solid content is adjusted to 45%, and the thermoplastic resin emulsion is (5) was obtained. As a result of measuring the average particle size by the method described above, it was 145 nm.

　＜熱可塑性樹脂エマルジョン（６）＞
　耐圧性の重合反応機に、脱イオン水４５部を添加した後、窒素置換を行った。スチレン８８部、アクリロニトリル１０部、ｔ－ドデシルメルカプタン０．８部からなる単量体混合物Ａ１００部を準備し、これを単量体混合物Ａ１００重量％あたり５重量％の単量体混合物Ａ－１と９５重量％の単量体混合物Ａ－２に分けた。 <Thermoplastic resin emulsion (6)>
After adding 45 parts of deionized water to the pressure-resistant polymerization reactor, nitrogen substitution was performed. Prepare 100 parts of a monomer mixture A consisting of 88 parts of styrene, 10 parts of acrylonitrile, and 0.8 parts of t-dodecyl mercaptan, and add 5% by weight of monomer mixture A-1 to 100% by weight of monomer mixture A. It was divided into 95% by weight monomer mixture A-2.

　次いで反応器を７５℃に昇温し、ドデシルベンゼンスルホン酸ナトリウム０．２部（固形分換算）および単量体混合物Ａ－１加えて十分攪拌した後、過硫酸カリウム０．１部を仕込み、８０℃にて重合を開始した。 Then, the temperature of the reactor is raised to 75° C., 0.2 parts of sodium dodecylbenzenesulfonate (in terms of solid content) and the monomer mixture A-1 are added and sufficiently stirred, then 0.1 parts of potassium persulfate are charged, Polymerization was initiated at 80°C.

　開始から１時間後に残りの単量体混合物Ａ－２、アクリル酸2部を脱イオン水１８部に溶解させた溶液、ドデシルベンゼンスルホン酸ナトリウム１．５部（固形分換算）と重炭酸ナトリウム０．７部および過硫酸カリウム０．１部を脱イオン水３０部に溶解させた溶液を７．５時間にわたって連続的に添加した。 After 1 hour from the start, the remaining monomer mixture A-2, a solution of 2 parts of acrylic acid dissolved in 18 parts of deionized water, 1.5 parts of sodium dodecylbenzenesulfonate (solid content conversion) and 0 sodium bicarbonate A solution of .7 parts and 0.1 parts potassium persulfate in 30 parts deionized water was added continuously over 7.5 hours.

　そのまま重合温度を８０℃に５時間保ち重合を終了した。次いで、熱可塑性樹脂エマルジョンを苛性ソーダ水溶液でｐＨを約７に調整した後、水蒸気蒸留により未反応単量体および他の低沸点化合物を除去し、固形分を４５％に調整し、熱可塑性樹脂エマルジョン（６）を得た。上述の方法で平均粒子径を測定したところ、１６０ｎｍであった。 The polymerization temperature was maintained at 80°C for 5 hours to complete the polymerization. Next, after adjusting the pH of the thermoplastic resin emulsion to about 7 with an aqueous solution of caustic soda, unreacted monomers and other low boiling point compounds are removed by steam distillation, the solid content is adjusted to 45%, and the thermoplastic resin emulsion is (6) was obtained. The average particle size measured by the method described above was 160 nm.

　得られた熱可塑性樹脂エマルジョン（１）～（６）を、繊維集束用組成物（１）～（６）として用いた。 The obtained thermoplastic resin emulsions (1) to (6) were used as fiber bundling compositions (1) to (6).

　＜連続樹脂含浸繊維（１）の製造方法＞
　布引装置を用いて、繊維集束用組成物（１）（固形分換算）を炭素繊維１００重量部に対して付着量が１５重量部となるように含浸させ、その後得られた連続樹脂含浸繊維を１８０℃に調整した乾燥炉内を１ｍ／分の速さで３分間移動させることにより、水分を完全に除去し、最終の連続樹脂含浸繊維（１）を得た。 <Method for producing continuous resin-impregnated fiber (1)>
100 parts by weight of the carbon fiber is impregnated with the fiber bundling composition (1) (in terms of solid content) using a cloth binding apparatus so that the adhesion amount is 15 parts by weight, and then the obtained continuous resin-impregnated fiber is Moisture was completely removed by moving in a drying oven adjusted to 180° C. for 3 minutes at a speed of 1 m/min to obtain a final continuous resin-impregnated fiber (1).

　＜連続樹脂含浸繊維（２）～（６）の製造方法＞
　繊維集束用組成物（１）を繊維集束用組成物（２）～（６）に変更した以外は連続樹脂含浸繊維（１）と同じ製法で、連続樹脂含浸繊維（２）～（６）を得た。 <Method for producing continuous resin-impregnated fibers (2) to (6)>
Continuous resin-impregnated fibers (2) to (6) are produced in the same manner as the continuous resin-impregnated fiber (1) except that the fiber bundling composition (1) is changed to the fiber bundling composition (2) to (6). Obtained.

　上述の連続樹脂含浸繊維に用いた炭素繊維は、帝人株式会社製　Ｔｅｎａｘ（登録商標）－Ｊ　ＳＴＳ４０　Ｆ１３　２４Ｋ　１６００ｔｅｘ
　＜連続樹脂含浸繊維と熱可塑性樹脂からなる積層品の製造方法＞
　連続樹脂含浸繊維を２０ｃｍ角のシートとなるように複数枚並列させた後、ポリアミド樹脂フィルム（東レフィルム加工株式会社製　レイファン（登録商標）Ｎ０　１４０１　厚み４０μｍ）と炭素繊維含量が３０重量％になるように交互に積層させ、設定温度２５０℃の圧縮成型機ＮＦ３７型を用いて、圧力５ＭＰａをかけた状態で余熱を５分間行った後、圧力１５ＭＰａをかけた状態で５分間熱プレス処理を行い、厚みが２ｍｍの積層品を作製した。また、得られた積層品から幅１５ｍｍ×長さ１５０ｍｍの試験片を切り出し曲げ試験用試験片とした。 The carbon fiber used for the above-mentioned continuous resin-impregnated fiber is Tenax (registered trademark)-J STS40 F13 24K 1600tex manufactured by Teijin Limited.
<Method for producing a laminated product composed of continuous resin-impregnated fibers and thermoplastic resin>
After arranging a plurality of continuous resin-impregnated fibers in parallel to form a 20 cm square sheet, a polyamide resin film (Rayfan (registered trademark) N0 1401, thickness 40 μm, manufactured by Toray Advanced Film Co., Ltd.) and a carbon fiber content of 30% by weight. After preheating for 5 minutes with a pressure of 5 MPa using a compression molding machine NF37 with a set temperature of 250 ° C., hot press treatment is performed for 5 minutes with a pressure of 15 MPa. to produce a laminate having a thickness of 2 mm. A test piece having a width of 15 mm and a length of 150 mm was cut out from the obtained laminated product and used as a test piece for a bending test.

　尚、積層品を作成する際には炭素繊維の方向は一方向に揃えてあり、また曲げ試験用試験片は炭素繊維の方向と試験片の長辺の方向が一致する方向で切り出しを行った。 When the laminated product was produced, the direction of the carbon fibers was aligned in one direction, and the test piece for the bending test was cut out in the direction in which the direction of the carbon fiber and the direction of the long side of the test piece coincided. .

Figure JPOXMLDOC01-appb-T000008
Figure JPOXMLDOC01-appb-T000008

　表６より、本発明の繊維集束用組成物を用いて製造された連続樹脂含浸繊維をポリアミド樹脂フィルムと積層した実施例１～５は、衝撃吸収エネルギー、曲げ強度に優れるものであった。 From Table 6, Examples 1 to 5 in which continuous resin-impregnated fibers produced using the fiber bundling composition of the present invention were laminated with a polyamide resin film were excellent in impact absorption energy and bending strength.

　比較例１は、本発明の繊維集束用組成物に含まれる熱可塑性樹脂エマルジョンの平均粒子径が規定範囲を満足しないため、衝撃吸収エネルギー、曲げ強度に劣るものであった。 In Comparative Example 1, since the average particle size of the thermoplastic resin emulsion contained in the fiber bundling composition of the present invention did not satisfy the specified range, the impact absorption energy and bending strength were inferior.

　５．本発明５に関する実施例および比較例
　ガラス転移温度
　得られた熱可塑性樹脂エマルジョンを９０℃のオーブンで１０時間乾燥させることで測定サンプルとした。その後、示差走査熱量計を用いてＪＩＳ　Ｋ７１２１―２０１２に準拠して測定した。 5. Examples and comparative examples relating to the present invention 5 The obtained thermoplastic resin emulsion was dried in an oven at 90°C for 10 hours to prepare a measurement sample. After that, it was measured according to JIS K7121-2012 using a differential scanning calorimeter.

　ｐＨの測定
　各実施例及び比較例で得られた繊維集束用組成物をＪＩＳ　Ｚ－８８０２に準拠して液温２５℃でのｐＨを測定した。ｐＨの測定には、卓上型電気伝導率計（東亜ＤＫＫ（株）製　ＣＭ－２５Ｒ）を用いた。 Measurement of pH The pH of the fiber bundling compositions obtained in Examples and Comparative Examples was measured according to JIS Z-8802 at a liquid temperature of 25°C. A desktop electrical conductivity meter (CM-25R manufactured by Toa DKK Co., Ltd.) was used for pH measurement.

　加水分解性の評価（１）
　各実施例及び比較例で得られたペレットを１００℃で４時間乾燥した後、ＩＳＯ１１３３に準じてメルトフローレート（ＭＦＲ－０）を測定した。また、８５℃、相対湿度９５％の恒温恒湿槽に５００時間保管した後、１００℃で４時間乾燥した後のメルトフローレート（ＭＦＲ―５００）も測定した。得られた測定値を基に、下記式（１）を用いてメルトフローレート上昇率を求めた。数値は大きいほど加水分解が進んでいることを示す。
メルトフローレート上昇率（％）＝ＭＦＲ－５００／ＭＦＲ－０×１００・・・（式１）
尚、ＭＦＲの測定は、下記条件で行った。
熱可塑性樹脂（１）を用いた繊維強化熱可塑性樹脂組成物：３００℃、１．２ｋｇ
熱可塑性樹脂（２）を用いた繊維強化熱可塑性樹脂組成物：２４０℃、１０ｋｇ
熱可塑性樹脂（３）を用いた繊維強化熱可塑性樹脂組成物：２２０℃、１０ｋｇ
　加水分解性の評価（２）
　各実施例及び比較例で得られたペレットを用いてＩＳＯダンベルを作成し、ＩＳＯ１７８に準じて曲げ強度（ＦＳ－０）を測定した。また、加水分解性の評価（１）と同様に、８５℃、相対湿度９５％の恒温恒湿槽に５００時間保管した後の曲げ強度（ＦＳ－５００）も測定した。吸湿前の曲げ強度（ＦＳ－０）と吸湿後の曲げ強度（ＦＳ－５００）から下記式（２）を用いて曲げ強度保持率を求めた。数値は小さいほど加水分解が進んでいることを示す。
曲げ強度保持率（％）＝ＦＳ－５００／ＦＳ－０×１００・・・（式２）
　加水分解性の評価（３）
　各実施例及び比較例で得られた積層品から幅１５ｍｍ×長さ１５０ｍｍの試験片を切り出し、ＪＩＳＫ７０７４に準じて曲げ強度（ＦＳ）を測定し、加水分解性の評価（２）と同様に、吸湿前の曲げ強度（ＦＳ－０）と吸湿後の曲げ強度（ＦＳ－５００）から曲げ強度保持率を求めた。 Evaluation of hydrolysis (1)
After drying the pellets obtained in each example and comparative example at 100° C. for 4 hours, the melt flow rate (MFR-0) was measured according to ISO1133. The melt flow rate (MFR-500) was also measured after being stored in a thermo-hygrostat at 85° C. and a relative humidity of 95% for 500 hours and then dried at 100° C. for 4 hours. Based on the measured values obtained, the rate of increase in melt flow rate was determined using the following formula (1). A larger value indicates that the hydrolysis is progressing.
Melt flow rate increase rate (%) = MFR-500/MFR-0 x 100 (Formula 1)
The measurement of MFR was performed under the following conditions.
Fiber-reinforced thermoplastic resin composition using thermoplastic resin (1): 300° C., 1.2 kg
Fiber-reinforced thermoplastic resin composition using thermoplastic resin (2): 240° C., 10 kg
Fiber-reinforced thermoplastic resin composition using thermoplastic resin (3): 220° C., 10 kg
Evaluation of hydrolysis (2)
An ISO dumbbell was prepared using the pellets obtained in each example and comparative example, and the bending strength (FS-0) was measured according to ISO178. In addition, the flexural strength (FS-500) after storage for 500 hours in a constant temperature and humidity chamber at 85° C. and a relative humidity of 95% was also measured in the same manner as in hydrolyzability evaluation (1). The bending strength retention rate was obtained from the bending strength (FS-0) before moisture absorption and the bending strength (FS-500) after moisture absorption using the following formula (2). A smaller value indicates that the hydrolysis is progressing.
Bending strength retention rate (%) = FS-500/FS-0 x 100 (Formula 2)
Evaluation of hydrolysis (3)
A test piece having a width of 15 mm and a length of 150 mm was cut out from the laminate obtained in each example and comparative example, and the bending strength (FS) was measured according to JISK7074. The bending strength retention rate was obtained from the bending strength (FS-0) before moisture absorption and the bending strength (FS-500) after moisture absorption.

　＜熱可塑性樹脂エマルジョン（１）の製造方法＞
　重合反応器に純水４５重量部を添加した後、窒素置換を行った。その後、昇温を開始し７５℃に到達した時点で過硫酸カリウム０．２重量部を添加した。更に反応器が８０℃に到達した時点でドデシルベンゼンスルホン酸ナトリウム２．１重量部（固形分換算）を純水３０重量部に溶解させた溶液、スチレン８８重量部、アクリロニトリル１０重量部、アクリル酸２重量部、ｔ－ドデシルメルカプタン０．８重量部からなる単量体混合物の７．５時間にわたる連続添加を開始した。その間反応器の温度は８０℃を保ち、連続添加終了後は更に重合を完了させるため温度を８０℃で５時間保持した。その後純水を用いて固形分を４５％に調整し、熱可塑性樹脂エマルジョン（１）を得た。熱可塑性樹脂エマルジョン（１）中の固形分のガラス転移温度は１０２℃であった。 <Method for producing thermoplastic resin emulsion (1)>
After adding 45 parts by weight of pure water to the polymerization reactor, the reactor was purged with nitrogen. Thereafter, the temperature was started to rise, and when the temperature reached 75°C, 0.2 parts by weight of potassium persulfate was added. Furthermore, when the reactor reached 80° C., a solution of 2.1 parts by weight of sodium dodecylbenzenesulfonate (in terms of solid content) dissolved in 30 parts by weight of pure water, 88 parts by weight of styrene, 10 parts by weight of acrylonitrile, and acrylic acid were added. A continuous addition of a monomer mixture consisting of 2 parts by weight and 0.8 parts by weight of t-dodecyl mercaptan was initiated over a period of 7.5 hours. The temperature of the reactor was maintained at 80° C. during that time, and after the continuous addition was completed, the temperature was maintained at 80° C. for 5 hours in order to complete the polymerization. After that, pure water was used to adjust the solid content to 45% to obtain a thermoplastic resin emulsion (1). The glass transition temperature of the solid content in the thermoplastic resin emulsion (1) was 102°C.

　＜熱可塑性樹脂エマルジョン（２）の製造方法＞
　重合反応器に純水４５重量部を添加した後、窒素置換を行った。その後、昇温を開始し７５℃に到達した時点で過硫酸アンモニウム０．４重量部を添加した。更に反応器が８０℃に到達した時点でドデシルベンゼンスルホン酸アンモニウム３．０重量部（固形分換算）を純水３０重量部に溶解させた溶液、スチレン８９重量部、アクリロニトリル１０重量部、アクリル酸１重量部、ｔ－ドデシルメルカプタン０．８重量部からなる単量体混合物の７．５時間にわたる連続添加を開始した。その間反応器の温度は８０℃を保ち、連続添加終了後は更に重合を完了させるため温度を８０℃で５時間保持した。その後純水を用いて固形分を４５％に調整し、熱可塑性樹脂エマルジョン（２）を得た。熱可塑性樹脂エマルジョン（２）中の固形分のガラス転移温度は１００℃であった。 <Method for producing thermoplastic resin emulsion (2)>
After adding 45 parts by weight of pure water to the polymerization reactor, the reactor was purged with nitrogen. Thereafter, the temperature was started to rise, and when the temperature reached 75°C, 0.4 parts by weight of ammonium persulfate was added. Furthermore, when the reactor reaches 80° C., a solution of 3.0 parts by weight of ammonium dodecylbenzenesulfonate (in terms of solid content) dissolved in 30 parts by weight of pure water, 89 parts by weight of styrene, 10 parts by weight of acrylonitrile, and acrylic acid are added. A continuous addition of a monomer mixture consisting of 1 part by weight and 0.8 parts by weight of t-dodecyl mercaptan was initiated over a period of 7.5 hours. The temperature of the reactor was maintained at 80° C. during that time, and after the continuous addition was completed, the temperature was maintained at 80° C. for 5 hours in order to complete the polymerization. After that, pure water was used to adjust the solid content to 45% to obtain a thermoplastic resin emulsion (2). The glass transition temperature of the solid content in the thermoplastic resin emulsion (2) was 100°C.

　＜熱可塑性樹脂エマルジョン（３）の製造方法＞
　重合反応器に純水４５重量部を添加した後、窒素置換を行った。その後、昇温を開始し７５℃に到達した時点で過硫酸カリウム０．４重量部を添加した。更に反応器が８０℃に到達した時点でドデシルベンゼンスルホン酸ナトリウム３．０重量部（固形分換算）を純水３０重量部に溶解させた溶液、スチレン８０重量部、アクリロニトリル１０重量部、メタアクリル酸１０重量部、ｔ－ドデシルメルカプタン０．８重量部からなる単量体混合物の７．５時間にわたる連続添加を開始した。その間反応器の温度は８０℃を保ち、連続添加終了後は更に重合を完了させるため温度を８０℃で５時間保持した。その後純水を用いて固形分を４５％に調整し、熱可塑性樹脂エマルジョン（３）を得た。熱可塑性樹脂エマルジョン（３）中の固形分のガラス転移温度は１０５℃であった。 <Method for producing thermoplastic resin emulsion (3)>
After adding 45 parts by weight of pure water to the polymerization reactor, the reactor was purged with nitrogen. Thereafter, the temperature was started to rise, and when the temperature reached 75°C, 0.4 parts by weight of potassium persulfate was added. Further, when the reactor reaches 80° C., a solution of 3.0 parts by weight of sodium dodecylbenzenesulfonate (in terms of solid content) dissolved in 30 parts by weight of pure water, 80 parts by weight of styrene, 10 parts by weight of acrylonitrile, methacryl A continuous addition of a monomer mixture consisting of 10 parts by weight of acid and 0.8 parts by weight of t-dodecyl mercaptan was initiated over a period of 7.5 hours. The temperature of the reactor was maintained at 80° C. during that time, and after the continuous addition was completed, the temperature was maintained at 80° C. for 5 hours in order to complete the polymerization. After that, pure water was used to adjust the solid content to 45% to obtain a thermoplastic resin emulsion (3). The glass transition temperature of the solid content in the thermoplastic resin emulsion (3) was 105°C.

　＜繊維集束用組成物（１）の製造方法＞
　熱可塑性樹脂エマルジョン（１）を繊維集束用組成物（１）とした。上述の方法で測定したｐＨは４．８であった。 <Method for producing fiber bundling composition (1)>
The thermoplastic resin emulsion (1) was used as the fiber bundling composition (1). The pH measured by the method described above was 4.8.

　＜繊維集束用組成物（２）の製造方法＞
　熱可塑性樹脂エマルジョン（２）を繊維集束用組成物（２）とした。上述の方法で測定したｐＨは５．２であった。 <Method for producing fiber bundling composition (2)>
The thermoplastic resin emulsion (2) was used as the fiber bundling composition (2). The pH measured by the method described above was 5.2.

　＜繊維集束用組成物（３）の製造方法＞
　熱可塑性樹脂エマルジョン（３）を繊維集束用組成物（３）とした。上述の方法で測定したｐＨは４．２であった。 <Method for producing fiber bundling composition (3)>
The thermoplastic resin emulsion (3) was used as a fiber bundling composition (3). The pH measured by the method described above was 4.2.

　＜繊維集束用組成物（４）の製造方法＞
　熱可塑性樹脂エマルジョン（１）１００重量部（固形分）にアセチレングリコール型非イオン性界面活性剤（日信化学工業（株）製　サーフィノール（登録商標）１０４Ｅ）を１重量部添加した後、十分に攪拌し、繊維集束用組成物（４）を得た。上述の方法で測定したｐＨは５．２であった。 <Method for producing fiber bundling composition (4)>
After adding 1 part by weight of an acetylene glycol-type nonionic surfactant (Nissin Chemical Industry Co., Ltd., Surfynol (registered trademark) 104E) to 100 parts by weight (solid content) of thermoplastic resin emulsion (1), to obtain a fiber bundling composition (4). The pH measured by the method described above was 5.2.

　＜繊維集束用組成物（５）の製造方法＞
　熱可塑性樹脂エマルジョン（１）に１Ｎの水酸化ナトリウム水溶液を適量添加した後、十分に攪拌し、繊維集束用組成物（５）を得た。上述の方法で測定したｐＨは６．４であった。 <Method for producing fiber bundling composition (5)>
After adding an appropriate amount of 1N sodium hydroxide aqueous solution to the thermoplastic resin emulsion (1), the mixture was sufficiently stirred to obtain a fiber bundling composition (5). The pH measured by the method described above was 6.4.

　＜繊維集束用組成物（６）の製造方法＞
　熱可塑性樹脂エマルジョン（１）に１Ｎの水酸化ナトリウム水溶液を適量添加した後、十分に攪拌し、繊維集束用組成物（６）を得た。上述の方法で測定したｐＨは６．８であった。 <Method for producing fiber bundling composition (6)>
After adding an appropriate amount of 1N sodium hydroxide aqueous solution to the thermoplastic resin emulsion (1), the mixture was sufficiently stirred to obtain a fiber bundling composition (6). The pH measured by the method described above was 6.8.

　＜繊維集束用組成物（７）の製造方法＞
　熱可塑性樹脂エマルジョン（１）に１Ｎの水酸化ナトリウム水溶液を適量添加した後、十分に攪拌し、繊維集束用組成物（７）を得た。上述の方法で測定したｐＨは９．０であった。 <Method for producing fiber bundling composition (7)>
After adding an appropriate amount of 1N sodium hydroxide aqueous solution to the thermoplastic resin emulsion (1), the mixture was sufficiently stirred to obtain a fiber bundling composition (7). The pH measured by the method described above was 9.0.

　＜チョップドストランド（１）の製造方法＞
　繊維集束用組成物（１）（固形分換算）を連続炭素繊維１００重量部に対して付着量が３重量部となるように集束させた後、ペレタイザーを用いて切断を行い、１００℃に調整した棚式乾燥機を用いて水分量が０．１%以下になるまで乾燥を行い、チョップドストランド（１）を得た。 <Method for producing chopped strand (1)>
After bundling the fiber bundling composition (1) (in terms of solid content) so that the adhesion amount is 3 parts by weight with respect to 100 parts by weight of continuous carbon fibers, cutting is performed using a pelletizer, and the temperature is adjusted to 100 ° C. Drying was carried out using a rack type dryer until the moisture content became 0.1% or less to obtain Chopped Strand (1).

　＜チョップドストランド（２）～（７）の製造方法＞
　繊維集束用組成物（１）を繊維集束用組成物（２）～（７）に変更した以外は、チョップドストランド（１）と同じ製法で、チョップドストランド（２）～（７）を得た。 <Method for producing chopped strands (2) to (7)>
Chopped strands (2) to (7) were obtained in the same manner as the chopped strand (1) except that the fiber bundling composition (1) was changed to the fiber bundling composition (2) to (7).

　＜連続樹脂含浸繊維（１）の製造方法＞
　布引装置を用いて、各熱可塑性樹脂エマルジョンを連続炭素繊維１００重量部に対して付着量が１０重量部（固形分換算）となるように集束させ、その後得られた連続樹脂含浸繊維を１８０℃に調整した乾燥炉内を１ｍ／分の速さで３分間移動させることにより水分を完全に除去し、最終の連続樹脂含浸繊維（１）を得た。 <Method for producing continuous resin-impregnated fiber (1)>
Using a cloth binding device, each thermoplastic resin emulsion is bundled so that the adhesion amount is 10 parts by weight (converted to solid content) with respect to 100 parts by weight of continuous carbon fiber, and the continuous resin-impregnated fiber obtained after that is heated at 180 ° C. Moisture was completely removed by moving in a drying oven adjusted to 1 m/min for 3 minutes to obtain the final continuous resin-impregnated fiber (1).

　＜連続樹脂含浸繊維（２）～（７）の製造方法＞
　繊維集束用組成物（１）を繊維集束用組成物（２）～（７）に変更した以外は、連続樹脂含浸繊維（１）と同じ製法で、連続樹脂含浸繊維（２）～（７）を得た。 <Method for producing continuous resin-impregnated fibers (2) to (7)>
Continuous resin-impregnated fibers (2) to (7) are produced in the same manner as the continuous resin-impregnated fiber (1) except that the fiber bundling composition (1) is changed to the fiber bundling composition (2) to (7). got

　上述のチョップドストランド、連続樹脂含浸繊維に用いた炭素繊維は、帝人株式会社製　Ｔｅｎａｘ（登録商標）－Ｊ　ＳＴＳ４０　Ｆ１３　２４Ｋ　１６００ｔｅｘである。 The carbon fiber used for the above chopped strands and continuous resin-impregnated fibers is Tenax (registered trademark)-J STS40 F13 24K 1600 tex manufactured by Teijin Limited.

　熱可塑性樹脂（１）
住化ポリカーボネート株式会社製　ＳＤ　ＰＯＬＹＣＡ（登録商標）３０１－１０
　熱可塑性樹脂（２）
日本エイアンドエル株式会社製　テクニエース（登録商標）ＰＡＸ－１４３９
（ポリカーボネート樹脂とＡＢＳ樹脂のアロイ）
　熱可塑性樹脂（３）
ポリ乳酸樹脂とＡＢＳ樹脂のアロイ
　＜繊維強化熱可塑性樹脂組成物の製造方法＞
　熱可塑性樹脂およびチョップドストランドを表７に記載の配合割合で混合した後、２６０℃に設定したフィーダーを２基有しているＳＴＥＥＲ社製ＯＭｅｇａ３０Ｈを用いて、Ｆ１より熱可塑性樹脂を、Ｆ２からチョップドストランドを投入し溶融混練して繊維強化熱可塑性樹脂組成物のペレットを得た。得られたペレットを用いてＩＳＯダンベルを作成し、加水分解性の評価（２）に用いた。 Thermoplastic resin (1)
SD POLYCA (registered trademark) 301-10 manufactured by Sumika Polycarbonate Co., Ltd.
Thermoplastic resin (2)
Techniace (registered trademark) PAX-1439 manufactured by Nippon A&L Co., Ltd.
(alloy of polycarbonate resin and ABS resin)
Thermoplastic resin (3)
Alloy of polylactic acid resin and ABS resin <Method for producing fiber-reinforced thermoplastic resin composition>
After mixing the thermoplastic resin and chopped strands at the blending ratio shown in Table 7, the thermoplastic resin was chopped from F1 and the chopped strands were chopped from F2 using OMega30H manufactured by STEER, which has two feeders set at 260°C. A strand was added and melt-kneaded to obtain pellets of a fiber-reinforced thermoplastic resin composition. An ISO dumbbell was prepared using the obtained pellets and used for hydrolyzability evaluation (2).

　＜連続樹脂含浸連続繊維と熱可塑性樹脂からなる成形品の製造方法＞
　連続樹脂含浸繊維を２０ｃｍ角のシートとなるように複数枚並列させた後、公知のフィルム成形機を用いて作成されたポリカーボネート樹脂フィルム（厚み４０μｍ）と炭素繊維を、炭素繊維含量が２５重量％になるように交互に積層させ、設定温度２８０℃の圧縮成型機ＮＦ３７型を用いて、圧力５ＭＰａをかけた状態で余熱を５分間行った後、圧力１５ＭＰａをかけた状態で５分間熱プレス処理を行い、厚みが２ｍｍの積層品を作製した。得られた積層品からら幅１５ｍｍ×長さ１５０ｍｍの試験片を切り出し、加水分解性の評価（３）に用いた。 <Method for producing molded article composed of continuous resin-impregnated continuous fiber and thermoplastic resin>
After arranging a plurality of continuous resin-impregnated fibers in parallel to form a sheet of 20 cm square, a polycarbonate resin film (thickness 40 μm) prepared using a known film molding machine and carbon fibers were combined to form a carbon fiber content of 25% by weight. After preheating for 5 minutes with a pressure of 5 MPa using a compression molding machine NF37 with a set temperature of 280 ° C., hot press treatment for 5 minutes with a pressure of 15 MPa was performed to produce a laminate having a thickness of 2 mm. A test piece having a width of 15 mm and a length of 150 mm was cut out from the obtained laminate and used for hydrolyzability evaluation (3).

Figure JPOXMLDOC01-appb-T000009
Figure JPOXMLDOC01-appb-T000009

Figure JPOXMLDOC01-appb-T000010
Figure JPOXMLDOC01-appb-T000010

　実施例１～１５は、本発明で規定するｐＨを満足する繊維集束用組成物であるため、加水分解が抑制され、強度保持率に優れるものであった。 Since Examples 1 to 15 are fiber bundling compositions that satisfy the pH specified in the present invention, hydrolysis was suppressed and strength retention was excellent.

　比較例１および２は、本発明で規定するｐＨを満足しない繊維集束用組成物であるため、加水分解が進み、強度保持率に劣るものであった。 Comparative Examples 1 and 2 were fiber bundling compositions that did not satisfy the pH specified in the present invention, so hydrolysis proceeded and the strength retention rate was poor.

　本発明１～５は、成形体として、例えば、自動車部品や電化製品に好適である。 The present inventions 1 to 5 are suitable as molded articles, for example, for automobile parts and electric appliances.

Claims (17)

　樹脂含浸繊維と熱可塑性樹脂とが複合化した繊維強化熱可塑性樹脂複合材料の製造において、複数の繊維を集束して前記樹脂含浸繊維を製造するための繊維集束用組成物に配合される共重合体エマルジョンであり、
　芳香族ビニル系単量体４０～９８．５重量％と、前記芳香族ビニル系単量体と共重合可能な他の単量体１．５～６０重量％との共重合体を含有し、
　前記共重合体の数平均分子量が０．５×１０４～４×１０４であることを特徴とする共重合体エマルジョン。 In the production of a fiber-reinforced thermoplastic resin composite material in which a resin-impregnated fiber and a thermoplastic resin are combined, a copolymer is added to a fiber bundling composition for bundling a plurality of fibers to produce the resin-impregnated fiber. is a coalesced emulsion,
A copolymer of 40 to 98.5% by weight of an aromatic vinyl monomer and 1.5 to 60% by weight of another monomer copolymerizable with the aromatic vinyl monomer,
A copolymer emulsion, wherein the copolymer has a number average molecular weight of 0.5×10 4 to 4×10 4 . 　請求項１に記載の共重合体エマルジョンを含有することを特徴とする繊維集束用組成物。 A fiber bundling composition comprising the copolymer emulsion according to claim 1. 　熱可塑性樹脂エマルジョンを含み、かつ固形分濃度を３０％とした際の、３０℃でのリング法により測定された表面張力が２５～４５ｍＮ／ｍである繊維集束用組成物。 A composition for fiber bundling that contains a thermoplastic resin emulsion and has a surface tension of 25 to 45 mN/m as measured by the ring method at 30°C when the solid content concentration is 30%. 　前記熱可塑性樹脂エマルジョンが、エチレン系不飽和カルボン酸単量体０．１～２０重量％と、前記エチレン系不飽和カルボン酸単量体と共重合可能な他の単量体８０～９９．９重量％との共重合体を含有することを特徴とする請求項３に記載の繊維集束用組成物。 The thermoplastic resin emulsion contains 0.1 to 20% by weight of an ethylenically unsaturated carboxylic acid monomer and 80 to 99.9% of another monomer copolymerizable with the ethylenically unsaturated carboxylic acid monomer. 4. The composition for fiber bundling according to claim 3, characterized in that it contains a copolymer of . 　非イオン系界面活性剤または陰イオン系界面活性剤の少なくとも１種を含むことを特徴とする請求項４に記載の繊維集束用組成物。 The composition for fiber bundling according to claim 4, characterized by containing at least one of a nonionic surfactant and an anionic surfactant. 　熱可塑性樹脂エマルジョンと、アセチレングリコール系非イオン界面活性剤またはジアルキルスルホコハク酸塩系陰イオン界面活性剤の少なくとも１種を含む繊維集束用組成物であって、動的表面張力が２５～５５ｍＮ／ｍであることを特徴とする繊維集束用組成物。 A fiber bundling composition comprising a thermoplastic resin emulsion and at least one of an acetylene glycol-based nonionic surfactant and a dialkylsulfosuccinate-based anionic surfactant, and having a dynamic surface tension of 25 to 55 mN/m. A fiber bundling composition characterized by: 　前記熱可塑性樹脂エマルジョンが、芳香族ビニル系単量体４０～９８．５重量％と、前記芳香族ビニル系単量体と共重合可能な他の単量体１．５～６０重量％との共重合体を含むことを特徴とする請求項６に記載の繊維集束用組成物。 The thermoplastic resin emulsion contains 40 to 98.5% by weight of an aromatic vinyl monomer and 1.5 to 60% by weight of another monomer copolymerizable with the aromatic vinyl monomer. 7. The fiber bundling composition according to claim 6, comprising a copolymer. 　樹脂含浸繊維と熱可塑性樹脂とが複合化した繊維強化熱可塑性樹脂複合材料の製造において、複数の繊維を集束して前記樹脂含浸繊維を製造するための繊維集束用組成物に配合される熱可塑性樹脂エマルジョンであり、
　芳香族ビニル系単量体４０～９８．５重量％と、前記芳香族ビニル系単量体と共重合可能な他の単量体１．５～６０重量％との共重合体を含有し、
　前記共重合体の平均粒子径が、７０ｎｍ以上１５０ｎｍ以下であることを特徴とする熱可塑性樹脂エマルジョン。 In the production of a fiber-reinforced thermoplastic resin composite material in which a resin-impregnated fiber and a thermoplastic resin are combined, a thermoplastic compounded in a fiber bundling composition for bundling a plurality of fibers to produce the resin-impregnated fiber is a resin emulsion,
A copolymer of 40 to 98.5% by weight of an aromatic vinyl monomer and 1.5 to 60% by weight of another monomer copolymerizable with the aromatic vinyl monomer,
The thermoplastic resin emulsion, wherein the copolymer has an average particle size of 70 nm or more and 150 nm or less. 　請求項８に記載の熱可塑性樹脂エマルジョンを含有することを特徴とする繊維集束用組成物。 A fiber bundling composition comprising the thermoplastic resin emulsion according to claim 8. 　熱可塑性樹脂エマルジョンを含み、ｐＨが４～７である繊維集束用組成物。 A fiber bundling composition containing a thermoplastic resin emulsion and having a pH of 4-7. 　前記熱可塑性樹脂エマルジョンが、エチレン系不飽和カルボン酸単量体０．１～２０重量％と、前記エチレン系不飽和カルボン酸単量体と共重合可能な他の単量体８０～９９．９重量％との共重合体を含有することを特徴とする請求項１０に記載の繊維集束用組成物。 The thermoplastic resin emulsion contains 0.1 to 20% by weight of an ethylenically unsaturated carboxylic acid monomer and 80 to 99.9% of another monomer copolymerizable with the ethylenically unsaturated carboxylic acid monomer. 11. The composition for fiber bundling according to claim 10, characterized in that it contains a copolymer with weight %. 　直鎖アルキルベンゼンスルホン酸塩、ポリオキシエチレンアルキルエーテル硫酸塩、α－オレフィンスルホン酸塩、アルカンスルホン酸塩、ジアルキルスルホコハク酸塩及びアルキル硫酸塩から選ばれた少なくとも１種を含む請求項１０に記載の繊維集束用組成物。 11. The composition according to claim 10, comprising at least one selected from linear alkylbenzenesulfonates, polyoxyethylene alkyl ether sulfates, α-olefinsulfonates, alkanesulfonates, dialkylsulfosuccinates and alkyl sulfates. A composition for fiber bundling. 　非イオン系界面活性剤を含むことを特徴とする請求項１０に記載の繊維集束用組成物。 The composition for fiber bundling according to claim 10, characterized by containing a nonionic surfactant. 　請求項２～７、９～１３のいずれか一項に記載の繊維集束用組成物で集束された樹脂含浸繊維。 A resin-impregnated fiber bundled with the fiber bundling composition according to any one of claims 2 to 7 and 9 to 13. 　請求項１４に記載の樹脂含浸繊維と熱可塑性樹脂とを含む繊維強化熱可塑性樹脂組成物。 A fiber-reinforced thermoplastic resin composition comprising the resin-impregnated fiber according to claim 14 and a thermoplastic resin. 　請求項１５に記載の繊維強化熱可塑性樹脂組成物を成形してなる成形品。 A molded product obtained by molding the fiber-reinforced thermoplastic resin composition according to claim 15. 　請求項１４に記載の樹脂含浸繊維からなる層と熱可塑性樹脂層を含む積層体を成形してなる成形品。 A molded product obtained by molding a laminate including a layer made of the resin-impregnated fiber according to claim 14 and a thermoplastic resin layer.
PCT/JP2022/025818 2021-06-28 2022-06-28 Copolymer emulsion, thermoplastic resin emulsion, composition for fiber binding, resin-impregnated fiber using same, thermoplastic resin composition and molded article Ceased WO2023277034A1 (en)

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