WO2022091732A1 - Composition aqueuse de résine époxy, agent d'encollage de fibres, faisceau de fibres, matériau de moulage et article moulé - Google Patents

Composition aqueuse de résine époxy, agent d'encollage de fibres, faisceau de fibres, matériau de moulage et article moulé Download PDF

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WO2022091732A1
WO2022091732A1 PCT/JP2021/037088 JP2021037088W WO2022091732A1 WO 2022091732 A1 WO2022091732 A1 WO 2022091732A1 JP 2021037088 W JP2021037088 W JP 2021037088W WO 2022091732 A1 WO2022091732 A1 WO 2022091732A1
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epoxy resin
mass
resin composition
aqueous
fiber
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PCT/JP2021/037088
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English (en)
Japanese (ja)
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孝史 後藤
定 永浜
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Dic株式会社
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Priority to CN202180063593.4A priority Critical patent/CN116194533A/zh
Priority to JP2022558963A priority patent/JP7276622B2/ja
Publication of WO2022091732A1 publication Critical patent/WO2022091732A1/fr

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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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/02—Polyalkylene oxides
    • 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
    • D06M15/507—Polyesters
    • 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
    • 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
    • D06M15/55—Epoxy resins

Definitions

  • the present invention relates to an aqueous epoxy resin composition, a fiber sizing agent, a fiber bundle, a molding material, and a molded product.
  • matrix resins such as epoxy resin and vinyl ester resin and fiber reinforced plastics containing glass fiber and carbon fiber are used.
  • the glass fiber or carbon fiber used for the fiber reinforced plastic usually, from the viewpoint of imparting high strength, a fiber material that has been focused to about several thousand to tens of thousands by a fiber sizing agent is often used.
  • a fiber sizing agent characterized by containing an epoxy resin, a urethane resin having an alkoxypolyoxyalkylene structure and an epoxy group, a polyester resin having a sulfonic acid base, and an aqueous medium is known. (See, for example, Patent Document 1).
  • this fiber sizing agent may have insufficient adhesiveness to the matrix resin, and the mechanical strength of the obtained molded product may be inferior. Further, since the fiber sizing agent is required to have compounding stability when a silane coupling agent is compounded, a material having excellent compounding stability, long-term storage stability, and adhesiveness to a matrix resin has been required. ..
  • An object to be solved by the present invention is to provide an aqueous resin composition which can be used for producing a fiber bundle capable of imparting excellent strength to a molded product and has excellent long-term storage stability and compounding stability.
  • an aqueous epoxy resin composition containing an epoxy resin, a polyester resin having a sulfonic acid base, an aromatic nonionic surfactant, and an aqueous medium.
  • the present invention was completed by finding that the present invention can be solved.
  • the present invention is an aqueous epoxy resin composition containing an epoxy resin (A), a polyester resin (B) having a sulfonic acid base, an aromatic nonionic surfactant (C), and an aqueous medium.
  • the present invention relates to an aqueous epoxy resin composition, wherein the content of the epoxy resin (A) is 75 to 95% by mass in the total solid content.
  • the aqueous epoxy resin composition of the present invention can be used for producing a fiber bundle capable of imparting excellent strength to a molded product, and is excellent in long-term storage stability and compounding stability. It can be suitably used as a sizing agent.
  • the aqueous epoxy resin composition of the present invention is an aqueous epoxy resin composition containing an epoxy resin (A), a polyester resin having a sulfonic acid base (B), an aromatic nonionic surfactant (C), and an aqueous medium.
  • the content of the epoxy resin (A) is 75 to 95% by mass in the total solid content.
  • the epoxy resin (A) will be described.
  • examples of the epoxy resin (A) include cresol novolak type epoxy resins such as orthocresol novolak type epoxy resin; phenol novolac type epoxy resin, ethylphenol novolak type epoxy resin, butylphenol novolak type epoxy resin, octylphenol novolak type epoxy resin and the like.
  • Phenol novolak type epoxy resin bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AD type epoxy resin, bisphenol S type epoxy resin, naphthalene type epoxy resin, dicyclopentadiene type epoxy resin, bisphenol A novolak type epoxy resin
  • examples thereof include bisphenol F novolak type epoxy resin, bisphenol AD novolak type epoxy resin, bisphenol S novolak type epoxy resin, etc.
  • cresol novolak because the heat resistance and mechanical strength of the obtained molded product are further improved.
  • a type epoxy resin, a phenol novolac type epoxy resin, a bisphenol A type epoxy resin, a bisphenol A novolak type epoxy resin, and a dicyclopentadiene type epoxy resin are preferable. These epoxy resins (A) can be used alone or in combination of two or more.
  • the epoxy equivalent of the epoxy resin (A) is preferably in the range of 100 to 3000 g / equivalent, and more preferably in the range of 100 to 1000 g / equivalent.
  • polyester resin (B) having a sulfonic acid base for example, an aromatic polyester resin, an aliphatic polyester resin, or the like can be used, but since the adhesive strength with the matrix resin and the storage stability are further improved. , It is preferable to use an aromatic polyester resin.
  • polyester resin (B) Since the polyester resin (B) has a sulfonic acid base, it can also function as a dispersant in water.
  • the sulfonic acid base contained in the polyester resin (B) preferably exists in the polyester resin (C) in the range of 0.1 to 1.0 mol / kg because the long-term storage stability is further improved. , 0.2 to 0.6 mol / kg, more preferably present.
  • the polyester resin (B) preferably has a weight average molecular weight of 5,000 to 30,000, preferably 5,000 to 15, because the mechanical strength and storage stability of the obtained molded product are further improved. More preferably, it is in the range of 000.
  • polyester resin (B) it is preferable to use a polyester resin (B) having a glass transition temperature of ⁇ 20 to 80 ° C. because the mechanical strength of the obtained molded product is further improved.
  • polyester resin (B) one obtained by reacting a polyol (b1) with a polycarboxylic acid (b2) can be used.
  • the sulfonic acid base contained in the polyester resin (B) is a part of the polyol (b1) or the polycarboxylic acid (b2), for example, a polyol having a sulfonic acid base or a polycarboxylic acid having a sulfonic acid base.
  • a compound having a sulfonate such as, it can be introduced into the polyester resin (B).
  • polyol (b1) examples include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 2-methyl-1,3-propanediol, and 1,5-pentane.
  • a polyol having a sulfonic acid base can be used as a compound having a sulfonic acid base in a part or all thereof, and for example, 2-butene-1,4-diol and the like can be used.
  • a polyol having a sulfonic acid base obtained by sulfonation of a polyol having a saturated group can be used.
  • polycarboxylic acid (b2) examples include aromatic polycarboxylic acids such as terephthalic acid, isophthalic acid, orthophthalic acid, naphthalenedicarboxylic acid and biphenyldicarboxylic acid; oxalic acid, succinic acid, anhydrous succinic acid, adipic acid and azeline.
  • aromatic polycarboxylic acids such as terephthalic acid, isophthalic acid, orthophthalic acid, naphthalenedicarboxylic acid and biphenyldicarboxylic acid
  • oxalic acid succinic acid, anhydrous succinic acid, adipic acid and azeline.
  • Saturated or unsaturated aliphatic poly such as acid, sebacic acid, dodecanedioic acid, hydrogenated dimeric acid, fumaric acid, maleic acid, maleic anhydride, itaconic acid, itaconic acid anhydride, citraconic acid, citraconic acid an
  • Carboxylic acid fatty acids such as 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 2,5-norbornnedicarboxylic acid and its anhydride, tetrahydrophthalic acid and its anhydride.
  • a polycarboxylic acid having a cyclic structure or the like can be used. Among these, it is preferable to use an aromatic polycarboxylic acid, and it is more preferable to use terephthalic acid or isophthalic acid, because the storage stability is further improved.
  • polycarboxylic acids (b2) trimellitic acid, pyromellitic acid, benzophenone tetracarboxylic acid, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic acid anhydride, trimesic acid, etc.
  • Those having three or more carboxyl groups such as ethylene glycol bis (anhydrotrimeritate), glyceroltris (anhydrotrimeritate), 1,2,3,4-butanetetracarboxylic acid can also be used.
  • polycarboxylic acid (b2) a polycarboxylic acid having a sulfonic acid base in a part or all of the polycarboxylic acid can be used.
  • metal salts such as 4-sulfoisophthalic acid, 5-sulfoisophthalic acid, sulfoterephthalic acid, 4-sulfonaphthalene-2,7-dicarboxylic acid and the like can be mentioned.
  • an esterified product of 5-sodium sulfoisophthalic acid such as 5-sodium sulfoisophthalic acid and dimethyl 5-sodium sulfoisophthalate, because the storage stability is further improved, and 5-sodium is preferable. It is more preferred to use dimethyl sulfoisophthalate.
  • the polyester resin (B) can be produced by subjecting the polyol (b1) and the polycarboxylic acid (b2) to an esterification reaction by a conventionally known method under a solvent-free or organic solvent.
  • the polyol (b1) and the polycarboxylic acid (b2) are heated to 180 to 300 ° C. in the presence or absence of a catalyst in an inert gas atmosphere. It can be carried out by a method of esterification or transesterification reaction, and then polycondensation under reduced pressure.
  • the total of the polyol (b1) and the polycarboxylic acid (b2) is 3 It is preferable to use it in the range of about 30% by mass.
  • aromatic nonionic surfactant (C) examples include polyoxyalkylene alkyl phenyl ethers such as polyoxyethylene nonylphenyl ether; polyoxyethylene monostyrene phenyl ethers, polyoxyethylene distyrene phenyl ethers, and polys.
  • Polyoxyethylene styrene phenyl ether such as oxyethylene tristyrene phenyl ether; Polyoxyalkylene styrene phenyl ether such as polyoxyethylene polyoxypropylene tristyrene phenyl ether; Polyoxyalkylene benzyl such as polyoxyethylene benzyl phenyl ether Phenyl ether; Polyoxyalkylene cumyl phenyl ether such as polyoxyethylene cumyl phenyl ether; Polyoxyalkylene naphthyl phenyl ether such as polyoxyethylene naphthyl phenyl ether; Polyoxyalkylene such as polyoxyethylene styrene (methyl phenyl ether) Examples thereof include styrene formation (alkyl phenyl ether).
  • aromatic nonionic surfactants (C) can be used alone or in combination of two or more.
  • aqueous epoxy resin composition of the present invention may be used in combination with other surfactants other than the aromatic nonionic surfactant (C), but has storage stability and silane coupling agent compounding stability. It is preferable that the amount of other surfactant in the surfactant is less than 10%, because the amount of the surfactant is further improved.
  • Examples of the aqueous medium include water, an organic solvent miscible with water, and a mixture thereof.
  • the organic solvent miscible with water include methanol, ethanol, and n-. And alcohol compounds such as 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; lactam compounds such as N-methyl-2-pyrrolidone, etc. Can be mentioned.
  • 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 environmental load, water alone or a mixture of water and an organic solvent miscible with water is preferable, and water alone is particularly preferable.
  • the aqueous epoxy resin composition of the present invention is prepared, for example, by mixing and stirring the epoxy resin (A), the polyester resin (B), the aromatic nonionic surfactant (C), and a solvent, and then with the mixture thereof. It can be obtained by mixing with an aqueous medium and removing the solvent if necessary.
  • the epoxy resin (A) in the solid content of the aqueous epoxy resin composition of the present invention is 75 to 95% by mass, but 80 to 95% by mass because the interlayer shear strength of the obtained molded product is further improved. Is preferable.
  • the polyester resin (B) in the solid content of the aqueous epoxy resin composition of the present invention is preferably 0.5 to 10% by mass, preferably 0.5 to 5% by mass, because dispersion stability and compounding stability are further improved. More preferably by mass.
  • the aromatic nonionic surfactant (C) in the solid content of the aqueous epoxy resin composition of the present invention is preferably 1 to 25% by mass, because the compounding stability and the mechanical strength of the molded product are further improved. 2 to 20% by mass is more preferable.
  • the mass ratio (B / C) of the polyester resin (B) to the aromatic nonionic surfactant (C) in the solid content of the fiber sizing agent of the present invention is the compounding stability and the molded product. 0.1 to 0.75 is preferable because the durability is further improved.
  • the solid content in the aqueous epoxy resin composition of the present invention is preferably 40 to 70% by mass, more preferably 45 to 65% by mass, from the viewpoint of storage stability and economy.
  • the aqueous medium in the aqueous epoxy resin composition of the present invention is preferably 30 to 60% by mass, more preferably 35 to 55% by mass, from the viewpoint of storage stability and economy.
  • the viscosity of the aqueous epoxy resin composition of the present invention is preferably 1000 mPa ⁇ s or less, and more preferably 500 mPa ⁇ s or less, because it is easy to handle such as taking it out of the container at the time of use.
  • the viscosity is a value when the temperature of the aqueous epoxy resin composition is measured at 25 ° C. using a rotary viscometer.
  • the volume average particle size of the aqueous epoxy resin composition of the present invention is 0. It is preferably 1 to 1.0 ⁇ m, more preferably 0.1 to 0.5 ⁇ m.
  • the volume average particle diameter is a value measured using a laser diffraction type particle size distribution meter.
  • aqueous epoxy resin composition of the present invention can be used as a silane coupling agent, a curing catalyst, a lubricant, a filler, a thixo-imparting agent, a tackifier, a wax, a heat stabilizer, a light-resistant stabilizer, and a fluorescence increase, if necessary.
  • Additives such as whitening agents and foaming agents, pH adjusters, leveling agents, antigelling agents, dispersion stabilizers, antioxidants, radical trapping agents, heat resistance imparting agents, inorganic fillers, organic fillers, plastics, Reinforcing agents, catalysts, antibacterial agents, fungicides, rust preventives, thermoplastic resins, thermosetting resins, pigments, dyes, conductivity-imparting agents, antistatic agents, moisture permeability improvers, water repellents, oil repellents, Hollow foam, crystalline water-containing compound, flame retardant, water absorbent, hygroscopic agent, deodorant, foam stabilizer, antifoaming agent, fungicide, antiseptic, algae-proofing agent, pigment dispersant, blocking inhibitor, water A decomposition inhibitor can be used in combination.
  • aqueous epoxy resin composition of the present invention When used as a sizing agent for glass fibers, 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 fibers.
  • 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 of the solid content of the aqueous epoxy resin composition of the present invention.
  • the aqueous epoxy resin composition of the present invention is, for example, an emulsion such as vinegar-based, ethylene vinegar-based, acrylic-based, epoxy-based, urethane-based, polyester-based, polyamide-based; styrene-butadiene-based, acrylonitrile-butadiene-based. , Acrylic-butadiene-based latex, and further, it can be used in combination with a water-soluble resin such as polyvinyl alcohol and cellulose.
  • an emulsion such as vinegar-based, ethylene vinegar-based, acrylic-based, epoxy-based, urethane-based, polyester-based, polyamide-based; styrene-butadiene-based, acrylonitrile-butadiene-based. , Acrylic-butadiene-based latex, and further, it can be used in combination with a water-soluble resin such as polyvinyl alcohol and cellulose.
  • the fiber sizing agent of the present invention contains the aqueous epoxy resin composition of the present invention, and for the purpose of preventing yarn breakage, fluffing, etc. of glass fibers, carbon fibers, etc., for example, a plurality of fibers. Can be used for focusing and surface treatment.
  • Examples of the fiber material that can be treated using the fiber sizing agent of the present invention include glass fiber, carbon fiber, silicon carbide fiber, pulp, linen, cotton, nylon, polyester, acrylic, polyurethane, polyimide, Kevlar, Nomex and the like.
  • Examples thereof include polyamide fibers made of aramid and the like.
  • glass fiber and carbon fiber are preferably used because of their high strength.
  • the glass fiber that can be treated using the fiber sizing agent for example, those obtained by using alkali-containing glass, low-alkali glass, non-alkali glass or the like as raw materials can be used, but the deterioration with time is particularly small. It is preferable to use non-alkali glass (E glass) having stable mechanical properties.
  • E glass non-alkali glass
  • the carbon fiber that can be treated using the fiber sizing agent generally, a polyacrylonitrile-based carbon fiber, a pitch-based carbon fiber, or the like can be used.
  • a polyacrylonitrile-based carbon fiber it is preferable to use a polyacrylonitrile-based carbon fiber from the viewpoint of imparting excellent strength.
  • the carbon fiber from the viewpoint of imparting even better strength and the like, it is preferable to use one having a single yarn diameter of 0.5 to 20 ⁇ m, and it is more preferable to use one having a single yarn diameter of 2 to 15 ⁇ m. preferable.
  • the carbon fiber for example, twisted yarn, spun, spun processed, and non-woven 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.
  • a fiber sizing agent is used in a kiss coater method or a roller.
  • a method of uniformly applying the fiber sizing agent to the fiber surface by a method, a dipping method, a spray method, a brush, or another known method.
  • the fiber sizing agent contains an aqueous medium or an organic solvent as a solvent, it is preferable to heat and dry the fiber using a heating roller, hot air, a hot plate or the like after the coating.
  • the amount of the film formed on the surface of the fiber material is preferably 0.1 to 5% by mass, preferably 0.3 to 1% by mass, based on the total mass of the bundled and surface-treated fiber bundle. It is more preferably 5.5% by mass.
  • the focused and surface-treated fiber material obtained by the above method is used in combination with the matrix resin (D) described later to produce a high-strength molded product.
  • the fiber material surface-treated with the fiber sizing agent of the present invention is used in combination with the matrix resin (D) to form a molded product or the like, and the interface between the fiber and the matrix resin (D) adheres to each other. Since the properties can be remarkably improved, the strength of the molded product can be improved.
  • thermosetting resin (D1) a thermosetting resin (D1) or a thermoplastic resin (D2) can be used.
  • thermosetting resin (D1) a phenol resin, a polyimide resin, a bismaleimide resin, an unsaturated polyester resin, an epoxy resin, a vinyl ester resin and the like can be used.
  • thermoplastic resin (D2) include saturated polyester resins such as polyethylene terephthalate and polybutylene terephthalate, and polyamide resins such as polypropylene, polystyrene, polycarbonate, polyphenylene sulfide, polyphenylene oxide, 6-nylon and 6,6-nylon. Acrylonitrile-styrene copolymer, acrylonitrile-butadiene-styrene copolymer, polyacetal, polyetherimide, polyether ether ketone and the like can be used.
  • the fibers bundled using the fiber sizing agent of the present invention include epoxy resins, unsaturated polyester resins, polyamide resins such as 6-nylon and 6,6-nylon, polyphenylene sulfide, polybutylene terephthalate, polycarbonate, and polyether. It is more preferable to use it in combination with a matrix resin of ether ketone in order to obtain a high-strength molded product.
  • Examples of the molding material containing the surface-treated fiber material, the matrix resin (D), and if necessary, a polymerizable monomer and the like include prepreg and sheet molding compound (SMC).
  • the prepreg is obtained by, for example, applying the matrix resin (D) on a release paper, placing a surface-treated fiber material on the coated surface, and pressing and impregnating the prepreg with a roller or the like as necessary. Can be manufactured.
  • the prepreg When producing the prepreg, it is preferable to use a bisphenol A type epoxy resin, a glycidylamine type epoxy resin such as tetraglycidylaminodiphenylmethane, or an epoxy resin such as a novolak type epoxy resin as the matrix resin (D). ..
  • the sheet molding compound is processed into a sheet by sufficiently impregnating the surface-treated fiber material with a mixture of, for example, the matrix resin (D1) and a polymerizable unsaturated monomer such as styrene. It can be manufactured by equalizing.
  • the matrix resin (D1) it is preferable to use an unsaturated polyester resin or a vinyl ester resin as the matrix resin (D1).
  • Curing of the molding material proceeds by, for example, radical polymerization under pressure or normal pressure, heating or light irradiation.
  • a known thermosetting agent, photocuring agent, or the like can be used in combination.
  • examples of the molding material include those obtained by kneading the thermoplastic resin (D2) and the surface-treated fiber material under heating. Such a molding material can be used for secondary processing by, for example, an injection molding method.
  • the prepreg made of the thermoplastic resin (D2) can be produced, for example, by placing a surface-treated fiber material on a sheet and impregnating the molten thermoplastic resin (D2).
  • the prepreg made of the thermoplastic resin (D2) 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 by using the molding material has high strength, it can be used for, for example, an automobile member, an aircraft member, an industrial member, or the like.
  • the average molecular weight of the resin was 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 and used. "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 This "TSKgel G2000" (7.8 mm ID x 30 cm) x 1 Detector: RI (Differential Refractometer) Column temperature: 40 ° C Eluent: Tetrahydrofuran (THF) Flow rate: 1.0 mL / min Injection volume: 100 ⁇ L (sample concentration 4 mg / mL tetrahydrofuran solution) Standard sample: A calibration curve was prepared using the following monodisperse polystyrene.
  • Example 1 Production and evaluation of aqueous epoxy resin composition (1)
  • 180 parts by mass of cresol novolac type epoxy resin epoxy equivalent 209 g / equivalent, softening point 75 ° C.; hereinafter abbreviated as "epoxy resin (A-1)”
  • epoxy resin (A-1) cresol novolac type epoxy resin
  • B-1 polyester resin
  • C-1 aromatic nonionic surfactant
  • Example 2 Production and evaluation of aqueous epoxy resin composition (2)
  • aqueous epoxy resin composition (2) 184 parts by mass of phenol novolac type epoxy resin (epoxy equivalent 182 g / equivalent, semi-solid type; hereinafter abbreviated as "epoxy resin (A-2)) in a reaction vessel equipped with a stirrer, a thermometer, and a reflux cooler.
  • epoxy resin (A-2) phenol novolac type epoxy resin
  • B-1 polyester resin
  • C-3 aromatic nonionic surfactant
  • polyoxyethylene polyoxypropylene tristyrene phenyl ether (oxyethylene average addition mole number 21, oxypropylene average addition mole number 4; hereinafter abbreviated as "aromatic nonionic surfactant (C-4)").
  • aromatic nonionic surfactant (C-4) oxyethylene average addition mole number 21, oxypropylene average addition mole number 4; hereinafter abbreviated as "aromatic nonionic surfactant (C-4)").
  • aromatic nonionic surfactant (C-4) oxyethylene polyoxypropylene tristyrene phenyl ether
  • Example 3 Production and evaluation of aqueous epoxy resin composition (3)
  • 188 parts by mass of bisphenol A type epoxy resin epoxy equivalent 475 g / equivalent, softening point 70 ° C; hereinafter abbreviated as "epoxy resin (A-3)"
  • epoxy resin (A-3) bisphenol A type epoxy resin
  • reaction vessel equipped with a stirrer, a thermometer, and a reflux cooler.
  • Polyester resin (B-1) 4 parts by mass, polyoxyethylene tristyrene phenyl ether (oxyethylene average addition molar number 40; hereinafter abbreviated as "aromatic nonionic surfactant (C-5)") 8 81 parts by mass and 81 parts by mass of methyl ethyl ketone were added, dissolved at 75 ° C., and then cooled to 40 ° C. Then, 520 parts by mass of ion-exchanged water was gradually added while stirring with a homomixer to obtain an aqueous dispersion. The solvent was distilled off under reduced pressure from this aqueous dispersion and concentrated to a non-volatile content of 55% by mass to obtain an aqueous epoxy resin composition (3).
  • aromatic nonionic surfactant (C-5)) 8 81 parts by mass and 81 parts by mass of methyl ethyl ketone were added, dissolved at 75 ° C., and then cooled to 40 ° C. Then, 520
  • Example 4 Production and evaluation of aqueous epoxy resin composition (4)
  • 180 mass of bisphenol A novolak type epoxy resin epoxy equivalent 210 g / equivalent, softening point 85 ° C; hereinafter abbreviated as "epoxy resin (A-4)
  • epoxy resin (A-4) bisphenol A novolak type epoxy resin
  • reaction vessel equipped with a stirrer, a thermometer, and a reflux cooler.
  • Non-volatile content [(W 3 -W 1 ) / (W 2 -W 1 )] ⁇ 100 W 1 ; Mass of metal petri dish (g) W 2 ; mass of metal petri dish + mass of weighed sample (g) W 3 ; mass of metal petri dish + mass of sample after drying (g)
  • Bisphenol A type liquid epoxy resin (epoxy equivalent 188 g / equivalent) 50 parts by mass, bisphenol A type solid epoxy resin (epoxy equivalent 475 g / equivalent, softening point 70 ° C) 20 parts by mass, cresol novolac type epoxy resin (epoxy equivalent 209 g / equivalent) , 4 parts by mass of dicyandiamide and 4 parts by mass of N- (3,4-dichlorophenyl) -N', N'-dimethylurea were prepared in 30 parts by mass (softening point 75 ° C.) and applied onto a release paper.
  • the carbon fiber bundles obtained above were arranged and arranged in one direction on the coated resin film at equal intervals, and then heated to impregnate the epoxy resin to prepare a prepreg having a carbon fiber content of 60% by volume.
  • the prepared prepregs were laminated and treated under pressure at 150 ° C. for 1 hour and then at 140 ° C. for 4 hours to obtain a molded product.
  • interlayer shear strength of epoxy molded products The interlayer shear strength of the test plate having a thickness of 2.5 mm and a width of 6.0 mm was measured by a method according to ASTM D-2344. Further, the interlayer shear strength of the same test plate after being boiled in distilled water for 72 hours was also measured in the same manner.
  • the tensile strength was measured for each test piece according to the measurement method of ISO527.
  • a dumbbell type tensile test piece having a total length of 170 mm, a narrow parallel portion length of 80 mm, a narrow parallel portion width of 10 mm, a wide parallel portion distance of 109 mm, a wide parallel portion width of 20 mm, and a thickness of 4 mm was used.
  • Table 1 shows the compositions and evaluation results of Examples 1 to 4 above.
  • Table 2 shows the compositions and evaluation results of Comparative Examples 1 to 4 above.
  • aqueous epoxy resin compositions of the present invention of Examples 1 to 4 are excellent in storage stability and compounding stability, and that the molded product obtained by using the aqueous epoxy resin composition is excellent in interlayer shear strength and tensile strength. rice field.
  • Comparative Example 1 is an example in which the aromatic nonionic surfactant (C), which is an essential component of the present invention, is not contained, but the compounding stability is inferior and the interlayer shear strength of the molded product is insufficient. Was confirmed.
  • Comparative Example 2 is an example in which the content of the epoxy resin (A) is less than the lower limit of the present invention, but it was confirmed that the interlayer shear strength of the molded product and the tensile strength after the moisture resistance heat test were insufficient.
  • Comparative Examples 3 and 4 are examples that do not contain the polyester resin (B) having a sulfonic acid group, which is an essential component of the present invention, but it was confirmed that the storage stability was insufficient.

Abstract

La présente invention concerne une composition aqueuse de résine époxy qui contient (A) une résine époxy, (B) une résine de polyester qui comporte un groupe sulfonate, (C) un tensioactif aromatique non ionique, et un milieu aqueux, et qui est caractérisée en ce que la teneur en résine époxy (A) par rapport à la teneur totale en matières solides varie de 75 à 95 % en masse. Cette composition aqueuse de résine époxy est appropriée pour être utilisée dans un agent d'encollage de fibres, étant donné que cette composition aqueuse de résine époxy peut être utilisée pour la production d'un faisceau de fibres qui est capable de conférer une très grande résistance à un article moulé, tout en présentant une excellente stabilité au stockage à long terme et une excellente stabilité en mélange.
PCT/JP2021/037088 2020-10-27 2021-10-07 Composition aqueuse de résine époxy, agent d'encollage de fibres, faisceau de fibres, matériau de moulage et article moulé WO2022091732A1 (fr)

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JP2022558963A JP7276622B2 (ja) 2020-10-27 2021-10-07 水性エポキシ樹脂組成物、繊維集束剤、繊維束、成形材料、及び成形品

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007107004A (ja) * 2005-10-13 2007-04-26 Xerox Corp エポキシ樹脂を含むエマルションおよびトナー
JP2010194807A (ja) * 2009-02-24 2010-09-09 Ajinomoto Co Inc 金属膜付きシート及び金属膜付き樹脂シート
JP2016117886A (ja) * 2014-12-18 2016-06-30 ゼロックス コーポレイションＸｅｒｏｘ Ｃｏｒｐｏｒａｔｉｏｎ 転相乳化による結晶性ポリエステルラテックスの調製のための単一溶媒調合物
JP2016160567A (ja) * 2015-03-05 2016-09-05 Dic株式会社 繊維集束剤ならびに集束されたガラス繊維及び炭素繊維
JP2016204641A (ja) * 2015-04-24 2016-12-08 ゼロックス コーポレイションＸｅｒｏｘ Ｃｏｒｐｏｒａｔｉｏｎ 転相乳化を介するハイブリッドラテックス

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007107004A (ja) * 2005-10-13 2007-04-26 Xerox Corp エポキシ樹脂を含むエマルションおよびトナー
JP2010194807A (ja) * 2009-02-24 2010-09-09 Ajinomoto Co Inc 金属膜付きシート及び金属膜付き樹脂シート
JP2016117886A (ja) * 2014-12-18 2016-06-30 ゼロックス コーポレイションＸｅｒｏｘ Ｃｏｒｐｏｒａｔｉｏｎ 転相乳化による結晶性ポリエステルラテックスの調製のための単一溶媒調合物
JP2016160567A (ja) * 2015-03-05 2016-09-05 Dic株式会社 繊維集束剤ならびに集束されたガラス繊維及び炭素繊維
JP2016204641A (ja) * 2015-04-24 2016-12-08 ゼロックス コーポレイションＸｅｒｏｘ Ｃｏｒｐｏｒａｔｉｏｎ 転相乳化を介するハイブリッドラテックス

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