WO2018216457A1 - 繊維集束剤、繊維材料、成形材料及び成形品 - Google Patents
繊維集束剤、繊維材料、成形材料及び成形品 Download PDFInfo
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- WO2018216457A1 WO2018216457A1 PCT/JP2018/017722 JP2018017722W WO2018216457A1 WO 2018216457 A1 WO2018216457 A1 WO 2018216457A1 JP 2018017722 W JP2018017722 W JP 2018017722W WO 2018216457 A1 WO2018216457 A1 WO 2018216457A1
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- fiber
- sizing agent
- resin
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- fiber sizing
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- 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
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- 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
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/564—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them
- D06M15/568—Reaction products of isocyanates with polyethers
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
- C03C25/10—Coating
- C03C25/12—General methods of coating; Devices therefor
- C03C25/16—Dipping
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
- C03C25/10—Coating
- C03C25/24—Coatings containing organic materials
- C03C25/26—Macromolecular compounds or prepolymers
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- 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
- C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
- C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
- C08F299/022—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polycondensates with side or terminal unsaturations
- C08F299/024—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polycondensates with side or terminal unsaturations the unsaturation being in acrylic or methacrylic groups
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/003—Polymeric products of isocyanates or isothiocyanates with epoxy compounds having no active hydrogen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/2805—Compounds having only one group containing active hydrogen
- C08G18/2815—Monohydroxy compounds
- C08G18/283—Compounds containing ether groups, e.g. oxyalkylated monohydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/58—Epoxy resins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
- C08G18/673—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen containing two or more acrylate or alkylacrylate ester groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
- C08G18/7621—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring being toluene diisocyanate including isomer mixtures
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
- C08G59/1438—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen
- C08G59/1455—Monocarboxylic acids, anhydrides, halides, or low-molecular-weight esters thereof
- C08G59/1461—Unsaturated monoacids
- C08G59/1466—Acrylic or methacrylic acids
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- 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
- C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
- C08J5/042—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with carbon fibres
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
- C08L75/14—Polyurethanes having carbon-to-carbon unsaturated bonds
- C08L75/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
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- 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
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- 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
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- 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
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/53—Polyethers
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- 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
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/55—Epoxy resins
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- 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
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/564—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them
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- 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
- C08J2333/00—Characterised by the use of homopolymers or 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 of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2333/04—Characterised by the use of homopolymers or 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 of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
- C08J2333/14—Characterised by the use of homopolymers or 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 of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
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- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/40—Fibres of carbon
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- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/40—Reduced friction resistance, lubricant properties; Sizing compositions
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- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
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- D10B2401/00—Physical properties
- D10B2401/06—Load-responsive characteristics
- D10B2401/063—Load-responsive characteristics high strength
Definitions
- the present invention relates to a fiber sizing agent, a fiber material, a molding material and a molded product useful for fiber sizing.
- matrix resins such as epoxy resins and vinyl ester resins (epoxy acrylates) and fiber reinforced plastics including glass fibers and carbon fibers are used. ing.
- the glass fiber or carbon fiber used for the fiber reinforced plastic usually, a fiber material focused to several thousand to several tens of thousands by a fiber sizing agent is often used from the viewpoint of imparting high strength.
- the fiber sizing agent for example, one containing an aliphatic epoxy compound and a compound having a terminal unsaturated group and a polar group in one molecule is known (for example, see Patent Document 1).
- this fiber sizing agent has a problem that the sizing property of carbon fibers is insufficient, and the strength of a molded product obtained from a molding material using carbon fibers treated with this fiber sizing agent is also insufficient. there were.
- the problem to be solved by the present invention is to provide a fiber sizing agent, a fiber material, a molding material, and a molded article thereof that are excellent in fiber sizing properties, and that can provide molded products having various physical properties such as bending strength, compressive strength, and interlaminar shear strength. Is to provide.
- the present invention relates to a fiber sizing agent comprising a vinyl ester resin (A) having an alkoxy polyoxyalkylene structure and a urethane bond, and an aqueous medium.
- the fiber sizing agent of the present invention is suitable for sizing agents such as glass fibers and carbon fibers because it can be used for the production of fiber materials capable of imparting excellent strength to molded products and has excellent fiber sizing properties. Can be used.
- the fiber sizing agent of the present invention contains a vinyl ester resin (A) having an alkoxypolyoxyalkylene structure and a urethane bond, and an aqueous medium.
- the vinyl ester resin (A) will be described.
- the vinyl ester resin (A) has an alkoxy polyoxyalkylene structure.
- the alkoxy polyoxyalkylene structure is a structure in which one end of a polyoxyalkylene chain is blocked with an alkoxy group.
- polyoxyalkylene chain examples include a polyoxyethylene chain, a polyoxypropylene chain, a polyoxybutylene chain, and the like, and those in which these are arranged in a block shape or a random shape are also included.
- alkoxy group blocking the end of the polyoxyalkylene chain examples include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group.
- the alkoxypolyoxyalkylene structure preferably has a structure composed of oxyethylene units in an amount of 35% by mass or more because the water dispersibility is further improved.
- the alkoxypolyoxyalkylene structure preferably has a number average molecular weight of 300 to 7,000 because water dispersibility is further improved.
- the alkoxypolyoxyalkylene structure is preferably present in the vinyl ester resin (A) in the range of 3 to 60% by mass, and more preferably in the range of 10 to 55% by mass because the water dispersibility is further improved. More preferably it is present.
- the vinyl ester resin (A) has a (meth) acryloyl group at the terminal, the focusing property is improved and a molded article with higher strength can be obtained. Therefore, the (meth) acryloyl equivalent is 500 to 3 The range is preferably 2,000 g / equivalent, more preferably 800 to 2,000 g / equivalent.
- (meth) acryloyl refers to one or both of acryloyl and methacryloyl
- (meth) acrylic acid refers to one or both of acrylic acid and methacrylic acid
- (meth) acrylate “Refers to one or both of acrylate and methacrylate
- acid (anhydride) refers to one or both of acid and acid anhydride.
- the vinyl ester resin (A) preferably has a structure derived from a bisphenol A type epoxy resin since the convergence is improved and a molded article having higher strength can be obtained.
- the vinyl ester resin (A) is obtained by, for example, reacting a urethane resin (a1) having an alkoxypolyoxyalkylene structure and an epoxy group with (meth) acrylic acid and / or (meth) acrylic anhydride (a2). Obtainable.
- the reaction between the epoxy group of the urethane resin (a1) and the (meth) acrylic acid and / or (meth) acrylic anhydride (a2) is preferably performed at 60 to 140 ° C. using an esterification catalyst. Done. Moreover, a polymerization inhibitor etc. can also be used.
- the urethane resin (a1) has an epoxy group, the sizing property is improved and a molded article having higher strength can be obtained. Therefore, the epoxy equivalent of the urethane resin (a1) is 250 to 2,000 g / An equivalent range is preferred.
- the urethane resin (a1) is, for example, a compound having an epoxy group and a hydroxyl group (a1-1), a polyisocyanate (a1-2), a polyoxyalkylene monoalkyl ether (a1) in the absence of a solvent or in the presence of an organic solvent. -3) If necessary, it can be produced by reacting a polyol (a1-4) other than the compound (a1-1) and a chain extender (a1-5) by a conventionally known method. . Specifically, in consideration of safety, the reaction is preferably performed at a reaction temperature of 50 to 120 ° C. for 1 to 15 hours.
- the compound (a1-1) having an epoxy group and a hydroxyl group for example, an epoxy resin having a hydroxyl group can be used.
- epoxy resin examples include bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolak type epoxy resin, ethylphenol novolak type epoxy resin, butylphenol novolak type epoxy resin, octylphenol novolak type epoxy resin, orthocresol novolak type epoxy resin, etc. Cresol novolak type epoxy resin, resorcinol novolak type epoxy resin, bisphenol A novolak type epoxy resin, bisphenol F novolak type epoxy resin, bisphenol AD novolak type epoxy resin, bisphenol S novolak type epoxy resin, etc.
- a phenol novolac type epoxy resin, cresol Type epoxy resin or bisphenol A type epoxy resin is preferably a bisphenol A type epoxy resin is more preferable.
- These epoxy resins can be used alone or in combination of two or more.
- the compound (a1-1) it is preferable to use a phenol novolac epoxy resin having a hydroxyl group, a cresol novolac epoxy resin having a hydroxyl group, or a bisphenol A epoxy resin having a hydroxyl group.
- the bisphenol A type epoxy resin having a hydroxyl group is more preferable because the property is improved and a molded article having higher strength can be obtained.
- those having an epoxy equivalent of 150 to 2,000 g / equivalent are preferred, those having an epoxy equivalent of 150 to 900 g / equivalent are more preferred, and 150 to 500 g / equivalent. It is more preferable to use an equivalent amount.
- the hydroxyl group possessed by the compound (a1-1) has improved convergence and a molded article having a higher strength can be obtained, so that the total amount of epoxy groups possessed by the urethane resin (A) is 5 to 5%. It is preferably in the range of 150 mol%, more preferably in the range of 5 to 130 mol%, still more preferably in the range of 5 to 120 mol%.
- polyisocyanate (a1-2) examples include 1,3- and 1,4-phenylene diisocyanate, 1-methyl-2,4-phenylene diisocyanate (2,4-TDI), and 1-methyl-2,6.
- -Phenylene diisocyanate (2,6-TDI) 1-methyl-2,5-phenylene diisocyanate, 1-methyl-2,6-phenylene diisocyanate, 1-methyl-3,5-phenylene diisocyanate, 1-ethyl-2, 4-phenylene diisocyanate, 1-isopropyl-2,4-phenylene diisocyanate, 1,3-dimethyl-2,4-phenylene diisocyanate, 1,3-dimethyl-4,6-phenylene diisocyanate, 1,4-dimethyl-2, 5-phenylene diisocyanate, diethylbenzene diisocyanate Nate, diisopropylbenzene diisocyanate, 1-methyl-3,5-diethylbenzen
- IPDI isophorone diisocyanate
- 4'-dicyclohexylmethane diisocyanate 4,4'-dicyclohexyl
- the polyoxyalkylene monoalkyl ether (a1-3) is represented by the following general formula (1).
- R 1 is an alkyl group
- R 2 is an alkylene group
- n is an integer of 1 or more.
- the polyoxyalkylene monoalkyl ether (a1-3) is one in which R 1 in the general formula (1) is a methyl group, an ethyl group, a propyl group, or a butyl group because the storage stability is further improved. Are preferred, and those that are methyl groups are more preferred.
- R 2 in the general formula (1) is preferably an ethylene group or a propylene group, more preferably an ethylene group, since the storage stability and the fiber focusing property are further improved.
- n is preferably an integer of 5 to 150, and is preferably an integer of 5 to 100, since storage stability, fiber convergence, and strength of the obtained molded product are further improved. More preferred.
- polyoxyalkylene monoalkyl ether (a1-3) preferably has a hydroxyl value in the range of 10 to 200, more preferably in the range of 15 to 200, since the storage stability is further improved. More preferred.
- polyoxyalkylene monoalkyl ether (a1-3)
- polyoxyethylene monoalkyl ether it is more preferable to use polyoxyethylene monoalkyl ether, and polyoxyethylene monomethyl ether is used because storage stability and fiber sizing property are further improved. It is particularly preferable to do this.
- polystyrene resin examples include polyether polyol, polycarbonate polyol, polyester polyol, ethylene glycol, 1,2-propanediol, 1,3-butanediol, 1,4-butanediol, 3-methyl- 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, neopentyl glycol, diethylene glycol, dipropylene glycol, glycerin, trimethylolpropane, an acrylic polyol obtained by introducing a hydroxyl group into an acrylic copolymer, Polybutadiene polyol, hydrogenated polybutadiene polyol, partially saponified ethylene-vinyl acetate copolymer, and the like, which are butadiene copolymers having a hydroxyl group in the molecule, can be used.
- polyether polyol for example, one obtained by addition polymerization of alkylene oxide using one or more compounds having two or more active hydrogen atoms as an initiator can be used.
- polycarbonate polyol for example, those obtained by reacting a carbonic acid ester with a polyol, or those obtained by reacting phosgene with bisphenol A or the like can be used.
- polyester polyol examples include a polyester polyol obtained by esterification of a low molecular weight polyol and a polycarboxylic acid, and a ring-opening polymerization reaction of a cyclic ester compound such as ⁇ -caprolactone or ⁇ -butyrolactone. Polyester obtained, these copolyesters, etc. can be used.
- the polyether polyol, polycarbonate polyol, and aliphatic polyester polyol preferably have a number average molecular weight of 300 to 4,000, more preferably 500 to 2,000.
- chain extender (a1-5) polyamine, other compounds having an active hydrogen atom, or the like can be used.
- polyamine examples include ethylenediamine, 1,2-propanediamine, 1,6-hexamethylenediamine, piperazine, 2,5-dimethylpiperazine, isophoronediamine, 4,4'-dicyclohexylmethanediamine, 3,3'- Diamines such as dimethyl-4,4′-dicyclohexylmethanediamine, 1,4-cyclohexanediamine; N-hydroxymethylaminoethylamine, N-hydroxyethylaminoethylamine, N-hydroxypropylaminopropylamine, N-ethylaminoethylamine, N-methylaminopropylamine; diethylenetriamine, dipropylenetriamine, triethylenetetramine; hydrazine, N, N′-dimethylhydrazine, 1,6-hexamethylenebishydrazine; disuccinate Dolazide, adipic acid dihydrazide, glutaric acid dihydrazide, sebacic
- Examples of the other active hydrogen-containing compounds include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, hexamethylene glycol, and saccharose.
- Glycol compounds such as methylene glycol, glycerin and sorbitol; phenol compounds such as bisphenol A, 4,4′-dihydroxydiphenyl, 4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxydiphenyl sulfone, hydrogenated bisphenol A, hydroquinone , And water can be used.
- the chain extender (a1-5) is preferably used, for example, in such a range that the equivalent ratio of the amino group and excess isocyanate group of the polyamine is 1.9 or less (equivalent ratio). It is more preferable to use within the range of -1.0 (equivalent ratio).
- the urethanization reaction can be carried out in the absence of a catalyst, but known catalysts such as stannous octylate, dibutyltin dilaurate, dibutyltin dimaleate, dibutyltin diphthalate, dibutyltin dimethoxide, dibutyltin diacetylacetate, dibutyl Tin compounds such as tin diversate, titanate compounds such as tetrabutyl titanate, tetraisopropyl titanate and triethanolamine titanate, other tertiary amine compounds, quaternary ammonium salts and the like may be used.
- catalysts such as stannous octylate, dibutyltin dilaurate, dibutyltin dimaleate, dibutyltin diphthalate, dibutyltin dimethoxide, dibutyltin diacetylacetate, dibutyl Tin compounds such as tin diversate, titanate compounds
- the fiber sizing agent of the present invention contains the vinyl ester resin (A) and an aqueous medium, but a higher-strength molded product is obtained, so that a vinyl ester other than the vinyl ester resin (A) is obtained. It is preferable to contain the resin (B).
- the vinyl ester resin (B) can be obtained, for example, by reacting an epoxy resin with (meth) acrylic acid.
- epoxy resin examples include bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol fluorene type epoxy resins, biscresol fluorene type bisphenol type epoxy resins, phenol novolac type epoxy resins, cresol novolak type epoxy resins and the like.
- Glycidyl ether of polyhydric alcohol such as diglycidyl ether of hydrogenated bisphenol A, 3,4-epoxy-6-me Alicyclic epoxy resins such as lucyclohexylmethyl-3,4-epoxy-6-methylcyclohexanecarboxylate, 1-epoxyethyl-3,4-epoxycyclohexane, diglycidyl phthalate, diglycidyl tetrahydrophthalate, diglycidyl- glycidyl esters such as p-oxybenzoic acid and dimer acid g
- a bifunctional aromatic epoxy resin is preferable because it is excellent in the strength of the molded product, the handleability of the molding material, and the fluidity during molding of the molding material, and the bisphenol A type epoxy resin and the bisphenol F type epoxy resin are more preferable. preferable.
- These epoxy resins can be used alone or in combination of two or more.
- the vinyl ester resin (B) is preferably in the range of 2 to 60% by mass in the solid of the fiber sizing agent of the present invention, since the strength of the resulting molded product is further improved. % Is more preferable.
- Examples of the aqueous medium include water, organic solvents miscible with water, and mixtures thereof.
- Examples of the organic solvent miscible with water include alcohol compounds such as methanol, ethanol and isopropanol; ketone compounds such as acetone and methyl ethyl ketone; polyalkylene glycol compounds such as ethylene glycol, diethylene glycol and propylene glycol; alkyl ether compounds of polyalkylene glycol And lactam compounds such as N-methyl-2-pyrrolidone.
- only water may be used, a mixture of water and an organic solvent miscible with water may be used, or only an organic solvent miscible with water may be used. From the viewpoint of safety and load on the environment, water alone or a mixture of water and an organic solvent miscible with water is preferable, and only water is particularly preferable.
- the fiber sizing agent of the present invention contains the vinyl ester resin (A) and an aqueous medium, and the vinyl ester resin (A) is preferably an aqueous dispersion dispersed in an aqueous medium. .
- the vinyl ester resin (A) and a mixed solution of the vinyl ester resin (B) and an emulsifier are mixed and stirred, and then the mixture and the aqueous medium are mixed. If necessary, it can be obtained by removing the solvent.
- the emulsifier examples include polyoxyalkylene alkyl ether, polyoxyalkylene phenyl ether, polyoxyalkylene alkyl phenyl ether, polyoxyalkylene benzyl phenyl ether, polyoxyalkylene styryl phenyl ether, polyoxyalkylene cumyl phenyl ether, polyoxyalkylene ether
- examples include alkylene naphthyl phenyl ether, polyoxyalkylene fatty acid ester, polyoxyethylene-polyoxypropylene block copolymer, and polyethylene glycol.
- polyoxyalkylene alkyl ether polyoxyalkylene styryl phenyl ether, and polyoxyethylene-polyoxypropylene block copolymer are preferred because the strength of the resulting molded article is further improved, and polyoxyalkylene alkyl ether, Polyoxyalkylene styryl phenyl ether is more preferred.
- emulsifiers can be used alone or in combination of two or more.
- polyoxyalkylene alkyl ether examples include polyoxyethylene hexyl ether, polyoxyethylene octyl ether, polyoxyethylene nonyl ether, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and polyoxyethylene eicosyl ether.
- Oxyethylene alkyl ether ; hexyl ether of polyoxyethylene-polyoxypropylene copolymer, octyl ether of polyoxyethylene-polyoxypropylene copolymer, nonyl ether of polyoxyethylene-polyoxypropylene copolymer, polyoxyethylene -Lauryl ether of polyoxypropylene copolymer, stearyl ether of polyoxyethylene-polyoxypropylene copolymer, polyoxy Styrene - polyoxyethylene eicosyl ether of polyoxypropylene copolymers - and alkyl ethers of polyoxypropylene copolymers.
- those having 8 to 18 carbon atoms in the alkyl group such as polyoxyethylene octyl ether, polyoxyethylene nonyl ether, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether and the like are improved because of improved emulsifiability. Particularly preferred.
- These polyoxyalkylene alkyl ethers can be used alone or in combination of two or more.
- polyoxyalkylene styryl phenyl ether examples include polyoxyethylene styryl phenyl ether having a styrene addition mole number of 1 to 3, such as polyoxyethylene monostyryl phenyl ether, polyoxyethylene distyryl phenyl ether, polyoxyethylene tristyryl phenyl ether, and the like.
- examples include phenyl ether and styryl phenyl ether of a polyoxyethylene polyoxypropylene copolymer having 1 to 3 moles of styrene added.
- Ethylene styryl phenyl ether is preferred.
- These polyoxyalkylene styryl ethers can be used alone or in combination of two or more.
- the polyoxyethylene-polyoxypropylene block copolymer preferably has an average molecular weight in the range of 1,000 to 30,000 and more preferably in the range of 5,000 to 20,000 because of improved emulsifiability. More preferred.
- the polyoxyethylene content is preferably in the range of 40 to 90% by mass, more preferably in the range of 50 to 80% by mass.
- the mass ratio of the aqueous medium in the fiber sizing agent of the present invention is preferably in the range of 10 to 98% by mass, and more preferably in the range of 20 to 90% by mass, since storage stability and coating workability are further improved. A range is more preferable.
- the mass ratio of the solid content in the fiber sizing agent of the present invention is preferably in the range of 2 to 80% by mass, since storage stability and coating workability are further improved, and in the range of 10 to 70% by mass. It is more preferable that
- the fiber sizing agent of the present invention includes a silane coupling agent, a curing catalyst, a lubricant, a filler, a thixotropic agent, a tackifier, a wax, a heat stabilizer, a light stabilizer, and a fluorescent brightening agent as necessary.
- Additives such as foaming agents, pH adjusters, leveling agents, anti-gelling agents, dispersion stabilizers, antioxidants, radical scavengers, heat resistance imparting agents, inorganic fillers, organic fillers, plasticizers, reinforcing agents , Catalyst, antibacterial agent, antifungal agent, rust preventive agent, thermoplastic resin, thermosetting resin, pigment, dye, conductivity imparting agent, antistatic agent, moisture permeability improver, water repellent agent, oil repellent agent, hollow foam Body, crystal water-containing compound, flame retardant, water absorbent, moisture absorbent, deodorant, foam stabilizer, antifoam, antifungal agent, antiseptic, algae inhibitor, pigment dispersant, antiblocking agent, hydrolysis prevention An agent can be used in combination.
- the fiber sizing agent of the present invention when used as a glass fiber sizing agent, it is preferable to use a silane coupling agent in combination in order to further improve the adhesive strength of the sizing agent to the glass fiber. .
- silane coupling agent examples include ⁇ - (2-aminoethyl) aminopropyltrimethoxysilane, ⁇ - (2-hydroxylethyl) aminopropyltrimethoxysilane, and ⁇ - (2-aminoethyl) aminopropyltriethoxy.
- the silane coupling agent is preferably used in the range of 1 to 30 parts by mass with respect to 100 parts by mass in total of the resin components in the fiber sizing agent.
- the fiber sizing agent of the present invention is, for example, an emulsion of vinyl acetate, ethylene vinyl acetate, acrylic, epoxy, urethane, polyester, polyamide, etc .; styrene-butadiene, acrylonitrile-butadiene, acrylic -It can also be used in combination with a latex such as butadiene, or a water-soluble resin such as poval or cellulose.
- the fiber sizing agent of the present invention can be used for bundling or surface treatment of a plurality of fibers, for example, for the purpose of preventing breakage or fluffing of glass fibers or carbon fibers.
- Examples of the fiber material that can be processed using the fiber sizing agent of the present invention include glass fiber, carbon fiber, silicon carbide fiber, pulp, hemp, cotton, nylon, polyester, acrylic, polyurethane, polyimide, Kevlar, Nomex, etc. And polyamide fibers made of aramid. Among these, glass fibers and carbon fibers are preferably used because of their high strength.
- the glass fiber that can be treated using the fiber sizing agent for example, those obtained using alkali-containing glass, low alkali glass, non-alkali glass or the like as a raw material can be used. It is preferable to use an alkali-free glass (E glass) that has few mechanical properties.
- E glass alkali-free glass
- the carbon fiber that can be treated using the fiber sizing agent generally, polyacrylonitrile-based, pitch-based, etc. carbon fibers can be used.
- said carbon fiber it is preferable to use a polyacrylonitrile-type carbon fiber from a viewpoint which provides the outstanding intensity
- carbon fiber those having a single yarn diameter of 0.5 to 20 ⁇ m are preferably used, and those having a fiber diameter of 2 to 15 ⁇ m are more preferable, from the viewpoint of imparting further excellent strength and the like. preferable.
- the carbon fiber for example, twisted yarn, spun yarn, spun processing, non-woven processing can be used. Further, as the carbon fiber, filaments, yarns, rovings, strands, chopped strands, felts, needle punches, cloths, roving cloths, milled fibers, and the like can be used.
- Examples of a method of focusing the glass fiber or carbon fiber using the fiber sizing agent of the present invention and forming a film on the surface of the glass fiber bundle or carbon fiber bundle include, for example, a fiber sizing agent using a kiss coater method, a roller. Examples thereof include a method of uniformly applying a fiber sizing agent to the fiber surface by other known methods such as a method, a dipping method, a spray method, and a brush.
- the fiber sizing agent contains an aqueous medium or an organic solvent as a solvent, it is preferably heated and dried using a heating roller, hot air, a hot plate or the like after the application.
- the amount of the coating formed on the surface of the fiber is preferably 0.1 to 5% by mass with respect to the total mass of the bundle of fibers that have been focused and subjected to surface treatment, and 0.3 to 1. More preferably, it is 5 mass%.
- the fiber material of the present invention that has been focused and surface-treated obtained by the above method is used as a molding material for producing a high-strength molded article by using it in combination with a matrix resin or the like described later. Can do.
- the fiber material of the present invention When used in combination with a matrix resin to form a molded product or the like, it can remarkably improve the adhesion at the interface between the fiber and the matrix resin, so that the strength of the molded product can be improved. is there.
- thermosetting resin for example, a thermosetting resin or a thermoplastic resin
- thermosetting resin phenol resin, polyimide resin, bismaleimide resin, unsaturated polyester resin, epoxy resin, vinyl ester resin, vinyl urethane resin and the like
- thermoplastic resin examples include saturated polyester resins such as polyethylene terephthalate and polybutylene terephthalate, polyamide resins such as polypropylene, polystyrene, polycarbonate, polyphenylene sulfide, polyphenylene oxide, 6-nylon and 6,6-nylon, and acrylonitrile-styrene. Copolymers, acrylonitrile-butadiene-styrene copolymers, polyacetals, polyether imides, polyether ether ketones, and the like can be used.
- thermosetting resin a thermosetting resin is preferable, and a vinyl ester resin and an unsaturated polyester resin are more preferable because a molded article with higher strength can be obtained.
- the molding material of the present invention contains the fiber material, the matrix resin, and, if necessary, a polymerizable monomer.
- resin transfer molding such as hand lay-up method, spray-up method, FRP lining method, etc.
- Various methods such as the RTM method (RTM method), resin injection method (RI method), vacuum assisted resin transfer molding method (VARTM method), infusion molding method, press molding method, autoclave molding method, filament winding method, pultrusion molding method, etc.
- RTM method resin injection method
- VARTM method vacuum assisted resin transfer molding method
- a high-strength molded product can be obtained by the molding method.
- a prepreg or sheet molding compound (SMC) shape can be used for molding.
- the prepreg is manufactured, for example, by applying the matrix resin on a release paper, placing a fiber material subjected to surface treatment on the application surface, and pressing and impregnating using a roller or the like as necessary. be able to.
- bisphenol A type epoxy resin bisphenol A type epoxy resin, glycidylamine type epoxy resin such as tetraglycidylaminodiphenylmethane, epoxy resin such as novolac type epoxy resin, vinyl ester resin, etc. Is preferred.
- the sheet molding compound for example, sufficiently impregnates the surface-treated fiber material with a mixture of the matrix resin and a polymerizable unsaturated monomer such as styrene, and processes the sheet into a sheet shape. Can be manufactured.
- a polymerizable unsaturated monomer such as styrene
- the curing of the molding material proceeds, for example, by radical polymerization by heating or light irradiation under pressure or normal pressure.
- a known thermosetting agent, photocuring agent, or the like can be used in combination.
- examples of the molding material include a material obtained by kneading the thermoplastic resin and the surface-treated fiber material under heating. Such a molding material can be used for secondary processing by, for example, injection molding.
- the prepreg made of the thermoplastic resin can be manufactured, for example, by placing a surface-treated fiber material in a sheet shape and impregnating the molten thermoplastic resin.
- thermoplastic resin prepreg can be used for secondary processing, for example, by laminating one or more sheets and then heating and molding under pressure or normal pressure.
- the molded product obtained using the molding material has high strength, it can be used for, for example, automobile members, aircraft members, windmill members, industrial members, and the like.
- the average molecular weight of the resin is measured under the following GPC measurement conditions.
- Measuring device High-speed GPC device (“HLC-8220GPC” manufactured by Tosoh Corporation) Column: The following columns manufactured by Tosoh Corporation were connected in series. "TSKgel G5000" (7.8 mm ID x 30 cm) x 1 "TSKgel G4000” (7.8 mm ID x 30 cm) x 1 "TSKgel G3000” (7.8 mm ID x 30 cm) x 1 “TSKgel G2000” (7.8 mm ID ⁇ 30 cm) ⁇ 1 detector: RI (differential refractometer) Column temperature: 40 ° C Eluent: Tetrahydrofuran (THF) Flow rate: 1.0 mL / min Injection amount: 100 ⁇ L (tetrahydrofuran solution with a sample concentration of 4 mg / mL) Standard sample: A calibration curve was prepared using the following monodisperse polystyrene.
- Example 1 Production and evaluation of fiber sizing agent (1)
- 124 parts by mass of polyoxyethylene monoethyl ether (“Uniox M-550” manufactured by NOF Corporation, hydroxyl value: 100)
- 99 parts by mass of bisphenol A type epoxy resin (“Epiclon 1050” manufactured by DIC Corporation, epoxy equivalent: 477 g / equivalent)
- 65 parts by mass of methyl ethyl ketone were added and sufficiently stirred and dissolved at 40 ° C.
- the carbon fiber cloth is impregnated with a fiber sizing agent (1) diluted with ion-exchanged water to a non-volatile content of 5% by mass so that the solid content is 1% by mass, and using a dryer.
- a carbon fiber cloth (1) was obtained by drying at 150 ° C. for 30 minutes.
- the molded product (1) obtained above was measured according to JIS K 7181 using a test piece having a width of 15 mm, a length of 100 mm, and a thickness of 2 mm.
- the molded product (1) obtained above was measured according to JIS K7074 using a dumbbell test piece having a width of 13 mm, a length of 77 mm, and a thickness of 2 mm.
- Example 2 Production and evaluation of fiber sizing agent (2)
- a thermometer a stirrer, a reflux condenser, and a dropping device
- 30 parts by mass and methyl ethyl ketone 64 parts by mass were added and sufficiently stirred and dissolved at 40 ° C.
- 47 parts by mass of tolylene diisocyanate was added at 40 ° C. and reacted at 75 ° C. for 2 hours.
- Example 2 Except that the fiber sizing agent (1) used in Example 1 was changed to the fiber sizing agent (2), a carbon fiber bundle (2) and a molded product (2) were produced in the same manner as in Example 1, and various types were produced. Evaluation was performed.
- Example 3 Production of fiber sizing agent (3)
- a bisphenol A type was prepared by adding 274 parts by mass of the vinyl ester resin (A-1) obtained in Example 1 to a four-necked flask equipped with a thermometer, a stirring device, a reflux condenser, and a dropping device, and adjusting the temperature to 40 ° C.
- 115 parts by mass of epoxy acrylate resin (“Unidic V-5500” manufactured by DIC Corporation, active ingredient 99% or more, hereinafter abbreviated as vinyl ester resin (B-1)
- Emulgen A-500 manufactured by Kao Corporation
- aqueous dispersion was concentrated by distillation under reduced pressure to obtain a fiber sizing agent (3) which is an aqueous dispersion of a vinyl ester resin having a nonvolatile content of 30% by mass.
- a carbon fiber bundle (3) and a molded product (3) were prepared in the same manner as in Example 1 except that the fiber sizing agent (1) used in Example 1 was changed to the fiber sizing agent (3). Evaluation was performed.
- Example 4 Production of fiber sizing agent (4)
- the temperature was adjusted to 40 ° C.
- Synthesis Example 1 150 parts by mass of the vinyl ester resin (B-2) obtained in the above and 21 parts by mass of polyoxyethylene distyrenated phenyl ether (“Emulgen A-500” manufactured by Kao Corporation) were added and sufficiently stirred.
- 1000 parts by mass of ion-exchanged water was added dropwise over 30 minutes, and the mixture was further stirred and mixed for 15 minutes.
- the aqueous dispersion was concentrated by distillation under reduced pressure to obtain a fiber sizing agent (4) which is an aqueous dispersion of a vinyl ester resin having a nonvolatile content of 30% by mass.
- Example 2 In the same manner as in Example 1, except that the fiber sizing agent (1) used in Example 1 was changed to the fiber sizing agent (4), the carbon fiber bundle (4) and the molded product (4) were obtained in the same manner. It produced and evaluated variously. *
- a carbon fiber bundle (R1) and a molded product (R1) were prepared in the same manner as in Example 1 except that the fiber sizing agent (1) used in Example 1 was changed to the fiber sizing agent (R1). Evaluation was performed.
- Table 1 shows the evaluation results of Examples 1 to 4 and Comparative Example 1 described above.
- the fiber sizing agent of Examples 1 to 4 which is the fiber sizing agent of the present invention was confirmed to be excellent in fiber sizing property, and a molded product obtained using this was excellent in strength.
- Comparative Example 1 is an example using an aliphatic epoxy compound and a compound containing a compound having a terminal unsaturated group and a polar group in one molecule, but the fiber focusing property is insufficient. It was confirmed that the strength of the molded product obtained by use was insufficient.
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Abstract
Description
測定装置:高速GPC装置(東ソー株式会社製「HLC-8220GPC」)
カラム:東ソー株式会社製の下記のカラムを直列に接続して使用した。
「TSKgel G5000」(7.8mmI.D.×30cm)×1本
「TSKgel G4000」(7.8mmI.D.×30cm)×1本
「TSKgel G3000」(7.8mmI.D.×30cm)×1本
「TSKgel G2000」(7.8mmI.D.×30cm)×1本
検出器:RI(示差屈折計)
カラム温度:40℃
溶離液:テトラヒドロフラン(THF)
流速:1.0mL/分
注入量:100μL(試料濃度4mg/mLのテトラヒドロフラン溶液)
標準試料:下記の単分散ポリスチレンを用いて検量線を作成した。
東ソー株式会社製「TSKgel 標準ポリスチレン A-500」
東ソー株式会社製「TSKgel 標準ポリスチレン A-1000」
東ソー株式会社製「TSKgel 標準ポリスチレン A-2500」
東ソー株式会社製「TSKgel 標準ポリスチレン A-5000」
東ソー株式会社製「TSKgel 標準ポリスチレン F-1」
東ソー株式会社製「TSKgel 標準ポリスチレン F-2」
東ソー株式会社製「TSKgel 標準ポリスチレン F-4」
東ソー株式会社製「TSKgel 標準ポリスチレン F-10」
東ソー株式会社製「TSKgel 標準ポリスチレン F-20」
東ソー株式会社製「TSKgel 標準ポリスチレン F-40」
東ソー株式会社製「TSKgel 標準ポリスチレン F-80」
東ソー株式会社製「TSKgel 標準ポリスチレン F-128」
東ソー株式会社製「TSKgel 標準ポリスチレン F-288」
東ソー株式会社製「TSKgel 標準ポリスチレン F-550」
温度計、撹拌装置、還流冷却管、滴下装置を備えた4ツ口フラスコに、フェノ-ルノボラック型エポキシ樹脂(DIC株式会社製「エピクロンN-740-80M」、固形分エポキシ当量:180g/当量、有効成分80%)620質量部、アクリル酸205質量部、t-ブチルハイドロキノン1質量部、2-メチルイミダゾール10質量部を仕込み、40℃で十分に撹拌溶解した。その後、窒素と空気とを1対1で混合したガス流通下で、75~80℃まで昇温した。更に、75~80℃で10時間反応させると、酸価が1(mgKOH/g)以下になったので、反応を終了し、ビニルエステル樹脂(B-2)を得た。
温度計、撹拌装置、還流冷却管、滴下装置を備えた4ツ口フラスコに、ポリオキシエチレンモノエチルエーテル(日油株式会社製「ユニオックスM-550」、水酸基価:100)124質量部、及びビスフェノールA型エポキシ樹脂(DIC株式会社製「エピクロン1050」、エポキシ当量:477g/当量)99質量部、及びメチルエチルケトン65質量部を加え、40℃で十分に撹拌溶解した。次いで、40℃でトリレンジイソシアネート38質量部を添加し、60~65℃で6時間反応させ赤外線吸収スペクトルによりNCOの2260cm-1の特性ピ-クの消失を確認した。その後、40℃まで冷却しアクリル酸15質量部、t-ブチルハイドロキノン1質量部、2-メチルイミダゾール3質量部を仕込み、窒素と空気とを1対1で混合したガス流通下で、75~80℃まで昇温した。更に、75~80℃で10時間反応させると、酸価が1(mgKOH/g)以下になったので、反応を終了し、ビニルエステル樹脂(A-1)を得た。ビニルエステル樹脂(A-1)の重量平均分子量は、13,000であった。
次いで、40℃まで冷却し、ポリオキシエチレンジスチレン化フェニルエーテル(花王株式会社製「エマルゲンA-500」)27質量部を加え十分に攪拌した。次いで、イオン交換水850質量部を30分かけて滴下し、更に15分間攪拌混合した。この水分散物を減圧蒸留により濃縮して、不揮発分30質量%のビニルエステル樹脂の水分散体である繊維集束剤(1)を得た。
ポリアクリロニトリル系炭素繊維(単糸径7μm、ストランド強度4,400MPa、弾性率235GPa、6000本)のノーサイズ糸を束ね、繊維集束剤(1)をイオン交換水で不揮発分5質量%に希釈したものを浸漬法で含浸し、ローラーで絞ることで有効成分の付着量を1質量%に調整し、次いで、150℃で30分間熱処理することによって、繊維集束剤(1)によって表面処理の施された炭素繊維束(1)を得た。
TM式摩擦抱合力試験機TM-200(大栄科学精機製作所製)を用い、ジグザグに配置した鏡面クロムメッキステンレス針3本を介して50gの張力で、炭素繊維束(1)を1000回擦過させ(往復運動速度300回/分)、炭素繊維束(1)の毛羽立ちの状態を下記の基準で目視判定した。
○:数本の毛羽は見られたものの、実用上問題ないレベルであった。
△:毛羽立ちが確認でき、糸切れも若干見られた。
×:毛羽立ち及び単糸の糸切れが非常に多く確認できた。
室温下、炭素繊維クロス(織物の重さ200g/m2、単糸径7μm、ストランド強度4,400MPa、弾性率235GPa、サイジング処理(表面処理)の施されたポリアクリロニトリル系炭素繊維クロス)を裁断して得た約300mm×300mmの大きさのクロスを、該クロスの質量部に対して約30倍の質量のアセトン中に浸漬し、12時間放置した。浸漬後、クロスを80℃の乾燥機を用いて2時間乾燥することで、炭素繊維の表面に付着した樹脂分等を除去し、サイジング処理(表面処理)のされていない状態の炭素繊維クロスを得た。
上記炭素繊維クロスに、繊維集束剤(1)をイオン交換水で不揮発分5質量%に希釈したものを、固形分の付着量が1質量%となるように含浸させ、乾燥機を用いて、150℃で30分間乾燥処理をして炭素繊維クロス(1)を得た。
ビニルエステル樹脂溶液(DICマテリアル株式会社製「エクスド-マ9102-01NP」)100質量部に、6質量%ナフテン酸コバルト0.5質量部及びメチルエチルケトンパーオキサイド(日本油脂株式会社製「パーメックN」)1.0質量部を混合した混合物を、離型処理の施された350mm×350mmのガラス板上に流し、上記で得た炭素繊維クロス(1)を載せ、ハンドレイアップ成形法(8プライ)によって積層し、常温(25℃)で12時間硬化させた後、更に60℃で3時間硬化させることによって、炭素繊維強化プラスチック(炭素繊維の含有率;50体積%)である成形品(1)を得た。
上記で得た成形品(1)について、幅15mm×長さ100mm×厚さ2mmの試験片を使用し、JIS K 7181に準拠して測定した。
上記で得た成形品(1)について、幅13mm×長さ77mm×厚さ2mmのダンベル試験片を使用しJIS K 7074に準拠して測定した。
上記で得た成形品(1)について、幅10mm×長さ15mm×厚さ2mmの試験片を使用しJIS K 7078に準拠して測定した。
温度計、撹拌装置、還流冷却管、滴下装置を備えた4ツ口フラスコに、ポリエチレングリコール(エチレンオキサイド付加モル数12)81質量部、ポリオキシエチレンモノエチルエーテル(日油株式会社製「ユニオックスM-550」、水酸基価:100)30質量部、メチルエチルケトン64質量部を加えて40℃で十分に撹拌溶解した。次いで、40℃でトリレンジイソシアネート47質量部を添加し、75℃で2時間反応させた。次いで、ビスフェノールA型エポキシ樹脂(DIC株式会社製「エピクロン1050」、エポキシ当量:477g/当量)97質量部、60~65℃で6時間反応させ赤外線吸収スペクトルによりNCOの2260cm-1の特性ピ-クの消失を確認した。その後、40℃まで冷却しアクリル酸15質量部、t-ブチルハイドロキノン1質量部、2-メチルイミダゾール3質量部を仕込み、窒素と空気とを1対1で混合したガス流通下で、75~80℃まで昇温した。更に、75~80℃で10時間反応させると、酸価が1(mgKOH/g)以下になったので、反応を終了し、ビニルエステル樹脂(A-2)を得た。ビニルエステル樹脂(A-2)の重量平均分子量は、13,500であった。
次いで、40℃まで冷却し、ポリオキシエチレンジスチレン化フェニルエーテル(花王株式会社製「エマルゲンA-500」)27質量部を加え十分に攪拌した。次いで、イオン交換水850質量部を30分かけて滴下し、更に15分間攪拌混合した。この水分散物を減圧蒸留により濃縮して、不揮発分30質量%のビニルエステル樹脂の水分散体である繊維集束剤(2)を得た。
温度計、撹拌装置、還流冷却管、滴下装置を備えた4ツ口フラスコに、実施例1で得たビニルエステル樹脂(A-1)274質量部を加え40℃に調整した後、ビスフェノールA型エポキシアクリレ-ト樹脂(DIC株式会社製「ユニディックV-5500」、有効成分99%以上、以下、ビニルエステル樹脂(B-1)と略記する。)115質量部、及びポリオキシエチレンジスチレン化フェニルエーテル(花王株式会社製「エマルゲンA-500」)20質量部を加え十分に攪拌した。次いで、イオン交換水950質量部を30分かけて滴下し、更に15分間攪拌混合した。この水分散物を減圧蒸留により濃縮して、不揮発分30質量%のビニルエステル樹脂の水分散体である繊維集束剤(3)を得た。
温度計、撹拌装置、還流冷却管、滴下装置を備えた4ツ口フラスコに、実施例1で得たビニルエステル樹脂(A-1)300質量部を加え40℃に調整した後、合成例1で得たビニルエステル樹脂(B-2)150質量部、及びポリオキシエチレンジスチレン化フェニルエーテル(花王株式会社製「エマルゲンA-500」)21質量部を加え十分に攪拌した。次いで、イオン交換水1000質量部を30分かけて滴下し、更に15分間攪拌混合した。この水分散物を減圧蒸留により濃縮して、不揮発分30質量%のビニルエステル樹脂の水分散体である繊維集束剤(4)を得た。
温度計、撹拌装置、還流冷却管、滴下装置を備えた4ツ口フラスコに、グリセリンジメタクリレートヘキサメチレンジイソシアネート(共栄社化学製「UA101H」、末端不飽和基数:4個)149重量部、ノニオン系乳化剤(ポリオキシエチレン(70モル)スチレン化(5モル)クミルフェノール(質量比90:10))16.5質量部、及びメチルエチルケトン142質量部を加え50℃で均一に溶解した。その後、乳化槽に内容物を移し、ポリグリセリンポリグリシジルエーテル(ナガセケムテックス株式会社製「デナコール EX-521」、エポキシ当量:183g/当量、エポキシ基数:3以上)166重量部を加え均一に分散攪拌後に、ホモミキサ-により強制攪拌しながら、イオン交換水3000質量部を10分間で加え強制乳化した。その後、この水分散物を減圧蒸留により濃縮して、不揮発分15質量%の樹脂混合物の水分散体である繊維集束剤(R1)を得た。
Claims (6)
- アルコキシポリオキシアルキレン構造及びウレタン結合を有するビニルエステル樹脂(A)と、水性媒体とを含有することを特徴とする繊維集束剤。
- 前記ビニルエステル樹脂(A)が、ビスフェノールA型エポキシ樹脂由来の構造を有するものである請求項1記載の繊維集束剤。
- 前記ビニルエステル樹脂(A)以外のビニルエステル樹脂(B)をさらに含有する請求項1又は2記載の繊維集束剤。
- 請求項1~3のいずれか1項記載の繊維集束剤を有することを特徴とする繊維材料。
- 請求項4記載の繊維材料及び熱硬化性樹脂を含有することを特徴とする成形材料。
- 請求項5記載の成形材料の硬化物であることを特徴とする成形品。
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