CN116194533A - Aqueous epoxy resin composition, fiber bundling agent, fiber bundle, molding material and molded article - Google Patents

Aqueous epoxy resin composition, fiber bundling agent, fiber bundle, molding material and molded article Download PDF

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Publication number
CN116194533A
CN116194533A CN202180063593.4A CN202180063593A CN116194533A CN 116194533 A CN116194533 A CN 116194533A CN 202180063593 A CN202180063593 A CN 202180063593A CN 116194533 A CN116194533 A CN 116194533A
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epoxy resin
mass
resin composition
parts
aqueous
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后藤孝史
永浜定
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DIC Corp
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DIC Corp
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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

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Textile Engineering (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

Disclosed is an aqueous epoxy resin composition which is characterized by containing an epoxy resin (A), a polyester resin (B) having a sulfonate group, an aromatic nonionic surfactant (C) and an aqueous medium, wherein the content of the epoxy resin (A) is 75-95 mass% of the total solid content. The aqueous epoxy resin composition is useful for producing a fiber bundle which can impart excellent strength to a molded article, and is excellent in long-term storage stability and compounding stability, and therefore is suitable for use as a fiber bundling agent.

Description

Aqueous epoxy resin composition, fiber bundling agent, fiber bundle, molding material and molded article
Technical Field
The present invention relates to an aqueous epoxy resin composition, a fiber bundling agent, a fiber bundle, a molding material and a molded article.
Background
As automobile members, aircraft members, and the like, which require high strength and excellent durability, for example, fiber-reinforced plastics including matrix resins such as epoxy resins and vinyl ester resins, glass fibers, carbon fibers, and the like are used.
As glass fibers and carbon fibers used in the fiber-reinforced plastic, generally, fiber materials which are bundled into approximately several thousands to several tens of thousands by a fiber bundling agent are often used from the viewpoint of imparting high strength.
As the above-mentioned fiber bundling agent, a fiber bundling agent is known which is characterized by containing an epoxy resin, a urethane resin having an alkoxypolyoxyalkylene structure and an epoxy group, a polyester resin having a sulfonate group, and an aqueous medium (for example, refer to patent document 1.).
However, the fiber bundling agent may have insufficient adhesion to the matrix resin, and the resulting molded article may have poor mechanical strength. In addition, since the fiber bundling agent is required to have blending stability when a silane coupling agent is blended, a material excellent in blending stability, long-term storage stability, and adhesion to a matrix resin is required.
Prior art literature
Patent literature
Patent document 1: japanese patent laid-open publication 2016-160567
Disclosure of Invention
Problems to be solved by the invention
The present invention aims to provide an aqueous resin composition which can be used for producing a fiber bundle capable of imparting excellent strength to a molded article and which is excellent in long-term storage stability and blending stability.
Means for solving the problems
The present inventors have studied to solve the above problems, and as a result, have found that an aqueous epoxy resin composition containing an epoxy resin, a polyester resin having a sulfonate group, an aromatic nonionic surfactant, and an aqueous medium can solve the above problems, and have completed the present invention.
Specifically, the present invention relates to an aqueous epoxy resin composition comprising an epoxy resin (A), a polyester resin (B) having a sulfonate group, an aromatic nonionic surfactant (C) and an aqueous medium, wherein the content of the epoxy resin (A) is 75 to 95% by mass based on the total solid content.
Effects of the invention
The aqueous epoxy resin composition of the present invention can be used for producing a fiber bundle which can impart excellent strength to a molded article, and is excellent in long-term storage stability and compounding stability, and therefore can be suitably used as a bundling agent for glass fibers and carbon fibers.
Detailed Description
The aqueous epoxy resin composition of the present invention comprises an epoxy resin (A), a polyester resin (B) having a sulfonate group, an aromatic nonionic surfactant (C) and an aqueous medium, wherein the content of the epoxy resin (A) is 75 to 95% by mass based on the total solid content.
The epoxy resin (a) is described. Examples of the epoxy resin (a) include cresol novolac type epoxy resins such as o-cresol novolac type epoxy resin; phenol novolac type epoxy resins such as phenol novolac type epoxy resin, ethylphenol novolac type epoxy resin, butylphenol novolac type epoxy resin, octylphenol novolac type epoxy resin and the like; 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 novolac type epoxy resin, bisphenol F novolac type epoxy resin, bisphenol AD novolac type epoxy resin, bisphenol S novolac type epoxy resin, and the like, and cresol novolac type epoxy resin, phenol novolac type epoxy resin, bisphenol a novolac type epoxy resin, dicyclopentadiene type epoxy resin, and the like are preferable from the viewpoint of further improvement in heat resistance and mechanical strength of the obtained molded article. These epoxy resins (A) may be used alone or in combination of 2 or more.
The epoxy equivalent of the epoxy resin (a) is preferably in the range of 100 to 3000 g/equivalent, more preferably in the range of 100 to 1000 g/equivalent, from the viewpoint of further improving the strength of the obtained molded article.
As the polyester resin (B) having a sulfonate group, for example, an aromatic polyester resin, an aliphatic polyester resin, or the like can be used, and from the viewpoint of further improving the adhesive strength with the base resin and the storage stability, the aromatic polyester resin is preferably used.
Since the polyester resin (B) has a sulfonate group, it can also function as a dispersant in water.
The sulfonate group of the polyester resin (B) is preferably present in the polyester resin (C) in the range of 0.1 to 1.0mol/kg, more preferably in the range of 0.2 to 0.6mol/kg, from the viewpoint of further improvement in long-term storage stability.
The polyester resin (B) is preferably a polyester resin having a weight average molecular weight of 5,000 to 30,000, more preferably in the range of 5,000 to 15,000, from the viewpoint of further improving the mechanical strength and storage stability of the molded article obtained.
As the polyester resin (B), a polyester resin having a glass transition temperature of-20 to 80℃is preferably used in view of further improvement in mechanical strength of the molded article obtained.
As the polyester resin (B), a polyester resin obtained by reacting the polyol (B1) with the polycarboxylic acid (B2) can be used.
The sulfonate group of the polyester resin (B) may be introduced into the polyester resin (B) by using, for example, a sulfonate-group-containing polyol, a sulfonate-group-containing polycarboxylic acid, or the like as a part of the polyol (B1) and the polycarboxylic acid (B2).
Examples of the polyhydric alcohol (b 1) include aliphatic diols such as ethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, 1, 4-butanediol, 2-methyl-1, 3-propanediol, 1, 5-pentanediol, neopentyl glycol, 1, 6-hexanediol, 3-methyl-1, 5-pentanediol, 1, 9-nonanediol, 2-ethyl-2-butylpropanediol, diethylene glycol, triethylene glycol, and dipropylene glycol; diols having an aliphatic ring structure such as 1, 4-cyclohexanedimethanol; polyols having 3 or more hydroxyl groups such as glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, and the like.
In addition, as the polyol (b 1), a polyol having a sulfonate group which is a compound having a sulfonate group may be used in part or all of the above, and for example, a polyol having a sulfonate group obtained by sulfonating a polyol having an unsaturated group such as 2-butene-1, 4-diol may be used.
As the polycarboxylic acid (b 2), for example, aromatic polycarboxylic acids such as terephthalic acid, isophthalic acid, phthalic acid, naphthalene dicarboxylic acid, and biphenyl dicarboxylic acid; saturated or unsaturated aliphatic polycarboxylic acids such as oxalic acid, succinic anhydride, adipic acid, azelaic acid, sebacic acid, dodecanedioic acid, hydrogenated dimer acid, fumaric acid, maleic anhydride, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, and dimer acid; and polycarboxylic acids having an aliphatic ring structure such as 1, 4-cyclohexanedicarboxylic acid, 1, 3-cyclohexanedicarboxylic acid, 1, 2-cyclohexanedicarboxylic acid, 2, 5-norbornene dicarboxylic acid and its anhydride, tetrahydrophthalic acid and its anhydride. Among these, aromatic polycarboxylic acids are preferably used, and terephthalic acid and isophthalic acid are more preferably used, from the viewpoint of further improvement in storage stability.
In addition to the polycarboxylic acid, polycarboxylic acids having 3 or more carboxyl groups such as trimellitic acid, pyromellitic acid, benzophenone tetracarboxylic acid, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride, pyromellitic acid, ethylene glycol bis (dehydrated trimellitate), glycerol tris (dehydrated trimellitate), and 1,2,3, 4-butane tetracarboxylic acid can be used as the polycarboxylic acid (b 2).
As the polycarboxylic acid (b 2), a polycarboxylic acid having a sulfonate group may be used in part or all of them. Examples thereof include metal salts such as 4-sulfoisophthalic acid, 5-sulfoisophthalic acid, sulfoterephthalic acid, and 4-sulfonaphthalene-2, 7-dicarboxylic acid. Among these, from the viewpoint of further improving the storage stability, an esterified product of isophthalic acid-5-sodium sulfonate such as isophthalic acid-5-sodium sulfonate or dimethyl isophthalate-5-sodium sulfonate is preferably used, and dimethyl isophthalate-5-sodium sulfonate is more preferably used.
The polyester resin (B) can be produced by esterifying the polyhydric alcohol (B1) and the polycarboxylic acid (B2) with a conventionally known method in the absence of a solvent or in an organic solvent.
The esterification reaction described above can be specifically carried out by the following method: in an inert gas atmosphere, the polyhydric alcohol (b 1) and the polycarboxylic acid (b 2) are heated to 180 to 300 ℃ in the presence or absence of a catalyst to perform esterification or transesterification, and then polycondensation is performed under reduced pressure.
In addition, from the viewpoint of further improving the storage stability, the sulfonate group-containing compound used in producing the polyester resin (B) is preferably used in the range of 3 to 30 mass% of the total of the polyol (B1) and the polycarboxylic acid (B2).
Examples of the aromatic nonionic surfactant (C) include polyoxyalkylene alkylphenyl ethers such as polyoxyethylene nonylphenyl ether; polyoxyethylene styrenated phenyl ethers such as polyoxyethylene monostyrenated phenyl ether, polyoxyethylene distyrenated phenyl ether, and polyoxyethylene trisstyrenated phenyl ether; polyoxyalkylene styrenated phenyl ethers such as polyoxyethylene polyoxypropylene trisstyrenated phenyl ether; polyoxyalkylene benzyl phenyl ethers such as polyoxyethylene benzyl phenyl ether; polyoxyalkylene cumylphenyl ethers such as polyoxyethylene cumylphenyl ether; polyoxyalkylene naphthylphenyl ethers such as polyoxyethylene naphthylphenyl ether; polyoxyalkylene styrenation (alkylphenyl ether) such as polyoxyethylene styrenation (methylphenyl ether) and the like. Among these, polyoxyethylene styrenated phenyl ethers having 40 or more oxyethylene units are preferable, and polyoxyethylene styrenated phenyl ethers having 40 or more oxyethylene units are more preferable, from the viewpoints of further improvement in storage stability and compounding stability of the silane coupling agent. These aromatic nonionic surfactants (C) may be used alone or in combination of 2 or more.
In the aqueous epoxy resin composition of the present invention, a surfactant other than the above-mentioned aromatic nonionic surfactant (C) may be used in combination, and from the viewpoint of further improvement in storage stability and compounding stability of the silane coupling agent, the other surfactant among the surfactants is preferably less than 10%.
Examples of the aqueous medium include water, an organic solvent mixed with water, and a mixture thereof. Examples of the organic solvent to be mixed with water include alcohol compounds such as methanol, ethanol, n-propanol and isopropanol; ketone compounds such as acetone and methyl ethyl ketone; polyalkylene glycol compounds such as ethylene glycol, diethylene glycol, and propylene glycol; an alkyl ether compound of a polyalkylene glycol; lactam compounds such as N-methyl-2-pyrrolidone, and the like. In the present invention, only water may be used, or a mixture of water and an organic solvent mixed with water may be used, or only an organic solvent mixed with water may be used. From the viewpoints of safety and environmental load, water alone or a mixture of water and an organic solvent mixed with water is preferable, and water alone is particularly preferable.
The aqueous epoxy resin composition of the present invention can be obtained, for example, by: the epoxy resin (a), the polyester resin (B), the aromatic nonionic surfactant (C), and the solvent are mixed and stirred, and then the mixture is mixed with an aqueous medium, and the solvent is removed as needed.
The epoxy resin (a) in the solid content of the aqueous epoxy resin composition of the present invention is preferably from 80 to 95 mass% in terms of further improvement in interlayer shear strength of the obtained molded article.
The polyester resin (B) in the solid content of the aqueous epoxy resin composition of the present invention is preferably 0.5 to 10 mass%, more preferably 0.5 to 5 mass%, from the viewpoint of further improvement in dispersion stability and compounding stability.
The aromatic nonionic surfactant (C) in the solid content of the aqueous epoxy resin composition of the present invention is preferably 1 to 25 mass%, more preferably 2 to 20 mass%, from the viewpoint of further improvement in blending stability and mechanical strength of the molded article.
In addition, from the viewpoint of further improving the blending stability and the durability of the molded article, the mass ratio (B/C) of the polyester resin (B) to the aromatic nonionic surfactant (C) in the solid component of the fiber bundling agent of the present invention is preferably 0.1 to 0.75.
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 viewpoints of storage stability and economy.
The aqueous medium in the aqueous epoxy resin composition of the present invention is preferably 30 to 60 mass%, more preferably 35 to 55 mass%, from the viewpoints of storage stability and economy.
The viscosity of the aqueous epoxy resin composition of the present invention is preferably 1000mpa·s or less, more preferably 500mpa·s or less, from the viewpoint of facilitating handling such as removal from a container at the time of use. The viscosity was measured at 25℃using a rotary viscometer, and the temperature of the aqueous epoxy resin composition was measured.
The volume average particle diameter of the aqueous epoxy resin composition of the present invention is preferably 0.1 to 1.0. Mu.m, more preferably 0.1 to 0.5. Mu.m, from the viewpoints of reducing the sedimentation rate of particles during storage, maintaining long-term uniformity and making adhesion of particles to fibers uniform. The volume average particle diameter is a value measured by a particle size distribution analyzer using laser diffraction.
The aqueous epoxy resin composition of the present invention may optionally contain additives such as silane coupling agents, curing catalysts, lubricants, fillers, thixotropic agents, tackifiers, waxes, heat stabilizers, light stabilizers, fluorescent brighteners, 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, catalysts, antibacterial agents, mold inhibitors, rust inhibitors, thermoplastic resins, thermosetting resins, pigments, dyes, conductivity imparting agents, antistatic agents, moisture permeability improving agents, water repellents, oil repellents, hollow foam bodies, compounds containing crystal water, flame retardants, water absorbents, moisture absorbents, deodorants, foam stabilizers, antifoaming agents, mildew inhibitors, preservatives, anti-algae agents, pigment dispersants, antiblocking agents, and water resolvers.
In the case where the aqueous epoxy resin composition of the present invention is 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 adhesion strength of the sizing agent to the glass fibers.
Examples of the silane coupling agent include gamma- (2-aminoethyl) aminopropyl trimethoxysilane, gamma- (2-hydroxyethyl) aminopropyl trimethoxysilane, gamma- (2-aminoethyl) aminopropyl triethoxysilane, gamma- (2-hydroxyethyl) aminopropyl triethoxysilane, gamma- (2-aminoethyl) aminopropyl methyldimethoxysilane, gamma- (2-aminoethyl) aminopropyl methyldiethoxysilane, gamma- (2-hydroxyethyl) aminopropyl methyldimethoxysilane, gamma- (2-hydroxyethyl) aminopropyl methyldiethoxysilane, and gamma- (2-hydroxyethyl) aminopropyl methyltriethoxysilane, gamma- (N, N-di-2-hydroxyethyl) aminopropyl triethoxysilane, gamma-aminopropyl methyldimethoxysilane, gamma-aminopropyl methyldiethoxysilane, gamma- (N-phenyl) aminopropyl trimethoxysilane, and gamma-mercaptophenyl trimethoxysilane.
The silane coupling agent is preferably used in an amount of 1 to 30 parts by mass based on 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 may be used in combination with, for example, emulsions of vinyl acetate type, ethylene vinyl acetate type, acrylic type, epoxy type, urethane type, polyester type, polyamide type, and the like; the latex of styrene-butadiene, acrylonitrile-butadiene, acrylic acid-butadiene, etc., and the water-soluble resin of polyvinyl alcohol, cellulose, etc. are used in combination.
The fiber bundling agent of the present invention contains the aqueous epoxy resin composition of the present invention, and is useful for bundling and surface treatment of a plurality of fibers for the purpose of preventing breakage, fuzzing, and the like of glass fibers, carbon fibers, and the like, for example.
Examples of the fiber material that can be treated with the fiber bundling agent of the present invention include glass fibers, carbon fibers, silicon carbide fibers, pulp, hemp, cotton, nylon, polyester, acrylic, polyurethane, polyimide, and polyamide fibers made of aromatic polyamide such as Kevlar and Nomex. Among these, glass fibers and carbon fibers are preferably used because they have high strength.
As glass fibers that can be treated with the fiber-bundling agent, for example, glass fibers obtained from alkali-containing glass, low-alkali glass, alkali-free glass, or the like as a raw material can be used, and alkali-free glass (E-glass) that is less degraded with time and has stable mechanical properties is particularly preferably used.
As the carbon fiber that can be treated with the fiber bundling agent, carbon fibers such as polyacrylonitrile-based carbon fiber and pitch-based carbon fiber can be generally used. Among them, polyacrylonitrile-based carbon fibers are preferably used as the carbon fibers from the viewpoint of imparting excellent strength.
Further, as the carbon fiber, a carbon fiber having a monofilament diameter of 0.5 to 20 μm is preferably used, and a carbon fiber of 2 to 15 μm is more preferably used, from the viewpoint of imparting further excellent strength and the like.
As the carbon fiber, for example, a carbon fiber subjected to yarn twisting, spinning, textile processing, and nonwoven processing can be used. As the carbon fiber, a carbon fiber such as a filament, yarn, roving, precursor, chopped strand, felt, needle punched material, woven fabric, roving woven fabric, or milled fiber can be used.
As a method for forming a film on the surfaces of the glass fiber bundles and the carbon fiber bundles by using the fiber bundling agent of the present invention, there is a method for uniformly coating the fiber surface with the fiber bundling agent by other known methods such as a kiss coater method, a roll method, a dipping method, a spraying method, and brush hair. When the fiber bundling agent contains an aqueous medium and an organic solvent as a solvent, it is preferable to heat and dry the fiber bundling agent after the application using a heating roller, hot air, a hot plate, or the like.
The amount of the film formed on the surface of the fiber material is preferably 0.1 to 5 mass%, more preferably 0.3 to 1.5 mass% based on the total mass of the fiber bundle which has been subjected to the surface treatment.
The surface-treated fiber material, particularly glass fiber or carbon fiber, which has been formed into a bundle by the above method can be used in a molding material for producing a high-strength molded article by using the fiber material in combination with a matrix resin (D) or the like described later.
In particular, when a fiber material surface-treated with the fiber bundling agent of the present invention is used in combination with a matrix resin (D) to form a molded article or the like, the adhesion of the interface between the fibers and the matrix resin (D) can be significantly improved, and thus the strength of the molded article can be improved.
As the matrix resin (D), for example, a thermosetting resin (D1) or a thermoplastic resin (D2) can be used. As the thermosetting resin (D1), a phenol resin, a polyimide resin, a bismaleimide resin, an unsaturated polyester resin, an epoxy resin, a vinyl ester resin, or the like can be used. Examples of the thermoplastic resin (D2) include saturated polyester resins such as polyethylene terephthalate and polybutylene terephthalate, polyamide resins such as polypropylene, polystyrene, polycarbonate, polyphenylene sulfide, polyphenylene ether, 6-nylon and 6, 6-nylon, acrylonitrile-styrene copolymer, acrylonitrile-butadiene-styrene copolymer, polyacetal, polyetherimide and polyether ether ketone.
From the viewpoint of obtaining a molded article having high strength, the fibers obtained by bundling or the like using the fiber bundling agent of the present invention are more preferably used in combination with a matrix resin such as an epoxy resin, an unsaturated polyester resin, a polyamide resin such as 6-nylon or 6, 6-nylon, polyphenylene sulfide, polybutylene terephthalate, polycarbonate or polyether ether ketone.
Examples of the molding material including the surface-treated fibrous material, the matrix resin (D), and optionally, the polymerizable monomer include prepregs, sheet Molding Compounds (SMC), and the like.
The prepreg can be produced, for example, by applying the matrix resin (D) to a release paper, placing a surface-treated fiber material on the applied surface, and if necessary, pressing and impregnating the surface with a roller or the like.
In the production of the prepreg, it is preferable to use, as the matrix resin (D), an epoxy resin such as a glycidyl amine type epoxy resin such as bisphenol a type epoxy resin or tetraglycidyl aminodiphenylmethane or an epoxy resin such as novolac type epoxy resin.
The sheet molding material can be produced, for example, by sufficiently impregnating the surface-treated fiber material with a mixture of the matrix resin (D1) and a polymerizable unsaturated monomer such as styrene, and processing the mixture into a sheet. In the production of the sheet molding compound, an unsaturated polyester resin or a vinyl ester resin is preferably used as the matrix resin (D1).
The curing of the molding material is performed, for example, by radical polymerization by application of pressure or normal pressure, heating, or irradiation of light. In this case, a known thermosetting agent, a photo-curing agent, or the like may be used in combination.
Examples of the molding material include a material obtained by kneading the thermoplastic resin (D2) and the surface-treated fibrous material under heating. The molding material can be used for secondary processing by injection molding or the like.
The prepreg using the thermoplastic resin (D2) can be produced, for example, by placing a surface-treated fiber material in a sheet form and impregnating the molten thermoplastic resin (D2).
The prepreg using the thermoplastic resin (D2) can be used for secondary processing such as molding by stacking 1 sheet or more and then heating under pressure or normal pressure.
The molded article obtained by using the molding material has high strength, and therefore, can be used for, for example, automobile members, aircraft members, industrial members, and the like.
Examples
The present invention will be described more specifically with reference to examples. The average molecular weight of the resin was measured under the following GPC measurement conditions.
[ GPC measurement conditions ]
Measurement device: high-speed GPC apparatus (HLC-8220 GPC, manufactured by Tosoh Co., ltd.)
Column: the following columns manufactured by Tosoh corporation were connected in series and used.
"TSKgel G5000" (7.8 mmI.D..times.30 cm). Times.1 root
"TSKgel G4000" (7.8 mmI.D..times.30 cm). Times.1 root
"TSKgel G3000" (7.8 mmI.D..times.30 cm). Times.1 root
"TSKgel G2000" (7.8 mmI.D..times.30 cm). Times.1 root
A detector: RI (differential refractometer)
Column temperature: 40 DEG C
Eluent: tetrahydrofuran (THF)
Flow rate: 1.0 mL/min
Injection amount: 100. Mu.L (tetrahydrofuran solution with sample concentration of 4 mg/mL)
Standard sample: calibration curves were prepared using monodisperse polystyrene as described below.
(monodisperse polystyrene)
TSKgel Standard polystyrene A-500 manufactured by Tosoh Co., ltd "
TSKgel Standard polystyrene A-1000 manufactured by Tosoh Co., ltd "
TSKgel Standard polystyrene A-2500 manufactured by Tosoh Co., ltd "
TSKgel Standard polystyrene A-5000 manufactured by Tosoh Co., ltd "
TSKgel Standard polystyrene F-1 manufactured by Tosoh Co., ltd "
TSKgel Standard polystyrene F-2 manufactured by Tosoh Co., ltd "
TSKgel Standard polystyrene F-4 manufactured by Tosoh Co., ltd "
TSKgel Standard polystyrene F-10 manufactured by Tosoh Co., ltd "
TSKgel Standard polystyrene F-20 manufactured by Tosoh Co., ltd "
TSKgel Standard polystyrene F-40 manufactured by Tosoh Co., ltd "
TSKgel Standard polystyrene F-80 manufactured by Tosoh Co., ltd "
TSKgel Standard polystyrene F-128 manufactured by Tosoh Co., ltd "
TSKgel Standard polystyrene F-288 manufactured by Tosoh Co., ltd "
TSKgel Standard polystyrene F-550 manufactured by Tosoh Co., ltd "
Production example 1 production of polyester resin (B-1)
To a reaction vessel adjusted to 180 ℃, 558 parts by mass of ethylene glycol, 478 parts by mass of diethylene glycol, 896 parts by mass of terephthalic acid, 478 parts by mass of isophthalic acid, and 0.5 parts by mass of butyl tin oxyhydroxide were charged, the temperature was raised to 240 ℃ over 4 hours, the reaction was continued at 240 ℃, and about 260 parts by mass of a distillate was collected. Then, after cooling to 180 ℃, 213 parts by mass of dimethyl isophthalate-5-sodium sulfonate and 0.5 parts by mass of tetraisopropyl titanate were charged, the temperature was further raised to 260 ℃, and polycondensation reaction was carried out under reduced pressure of 2.0mm at a mercury column for 1 hour, whereby a polyester resin (B-1) having a weight average molecular weight of 8900 and a glass transition temperature of 44℃was obtained. The sulfonate group concentration of the polyester (B-1) was 0.31mol/kg, and the carboxyl group concentration was 0.05mmol/g.
Production example 2 production of polyester resin (RB-1)
A polycondensation reaction was carried out in the same manner as in production example 1 except that 53 parts by mass of trimellitic acid was used in place of the total amount of dimethyl isophthalate-5-sodium sulfonate used in production example 1, thereby obtaining a polyester resin (RB-1). The weight average molecular weight of the polyester (RB-1) was 11,000, and the carboxyl group concentration was 0.31mmol/g.
( Example 1: production and evaluation of aqueous epoxy resin composition (1) )
180 parts by mass of a cresol novolac epoxy resin (epoxy equivalent 209 g/equivalent, softening point 75 ℃ C.; hereinafter abbreviated as "epoxy resin (A-1)"), 4 parts by mass of a polyester resin (B-1), 40 parts by mass of a polyoxyethylene styrenated phenyl ether (average addition mole number of ethylene oxide), 8 parts by mass of an aromatic nonionic surfactant (C-1) ", hereinafter abbreviated as" aromatic nonionic surfactant (C-1) "), 8 parts by mass of a polyoxyethylene distyrenated phenyl ether (average addition mole number of ethylene oxide 18; hereinafter abbreviated as" aromatic nonionic surfactant (C-2) ") and 77 parts by mass of methyl ethyl ketone were charged into a reaction vessel equipped with a stirrer, a thermometer and a reflux condenser, dissolved at 75 ℃ and cooled to 40 ℃. Next, 530 parts by mass of ion-exchanged water was slowly added while stirring with a homomixer, to obtain an aqueous dispersion. The solvent was distilled off from the aqueous dispersion under reduced pressure, and concentrated to a nonvolatile content of 60%, whereby an aqueous epoxy resin composition (1) was obtained.
( Example 2: production and evaluation of aqueous epoxy resin composition (2) )
Into a reaction vessel equipped with a stirrer, a thermometer and a reflux condenser, 184 parts by mass of a phenol novolac type epoxy resin (epoxy equivalent 182 g/equivalent, semi-solid type; hereinafter abbreviated as "epoxy resin (A-2)") 2 parts by mass of a polyester resin (B-1), 60 parts by mass of a polyoxyethylene diphenylethylene ether (average addition mole number of ethylene oxide), 10 parts by mass of a polyoxyethylene polyoxypropylene tristyrenated phenyl ether (average addition mole number of ethylene oxide 21, average addition mole number of propylene oxide 4; hereinafter abbreviated as "aromatic nonionic surfactant (C-4)") 4 parts by mass of methyl ethyl ketone 79 parts by mass were charged, and after dissolution at 75 ℃, the mixture was cooled to 40 ℃. Next, 530 parts by mass of ion-exchanged water was slowly added while stirring with a homomixer, to obtain an aqueous dispersion. The solvent was distilled off from the aqueous dispersion under reduced pressure, and concentrated to 50% by mass of a nonvolatile component, whereby an aqueous epoxy resin composition (2) was obtained.
( Example 3: production and evaluation of aqueous epoxy resin composition (3) )
188 parts by mass of bisphenol A epoxy resin (epoxy equivalent 475 g/equivalent; hereinafter abbreviated as "epoxy resin (A-3)") 188 parts by mass, 4 parts by mass of polyester resin (B-1), 8 parts by mass of polyoxyethylene tristyrenated phenyl ether (average molar number of addition of ethylene oxide 40; hereinafter abbreviated as "aromatic nonionic surfactant (C-5)") and 81 parts by mass of methyl ethyl ketone were added to a reaction vessel equipped with a stirrer, a thermometer and a reflux condenser, dissolved at 75℃and cooled to 40 ℃. Next, 520 parts by mass of ion-exchanged water was slowly added while stirring with a homomixer, to obtain an aqueous dispersion. The solvent was distilled off from the aqueous dispersion under reduced pressure, and concentrated to a nonvolatile content of 55 mass%, whereby an aqueous epoxy resin composition (3) was obtained.
( Example 4: production and evaluation of aqueous epoxy resin composition (4) )
180 parts by mass of bisphenol A novolac epoxy resin (epoxy equivalent: 210 g/equivalent, softening point: 85 ℃ C.; hereinafter abbreviated as "epoxy resin (A-4)") 6 parts by mass of polyester resin (B-1), 8 parts by mass of aromatic nonionic surfactant (C-3), 4 parts by mass of aromatic nonionic surfactant (C-4), 2 parts by mass of polyoxyethylene polyoxypropylene block polymer (weight average molecular weight: 17000, oxyethylene component: 80% by mass) and 77 parts by mass of methyl ethyl ketone were added to a reaction vessel equipped with a stirrer, a thermometer and a reflux condenser, and dissolved at 75 ℃ and cooled to 40 ℃. Next, 511 parts by mass of ion-exchanged water was slowly added while stirring with a homomixer, to obtain an aqueous dispersion. The solvent was distilled off from the aqueous dispersion under reduced pressure, and concentrated to 50% by mass of a nonvolatile component, whereby an aqueous epoxy resin composition (4) was obtained.
( Comparative example 1: production and evaluation of aqueous epoxy resin composition (R1) )
200 parts by mass of an epoxy resin (A-1), 200 parts by mass of a polyester resin (B-1), 130 parts by mass of N-methyl-2-pyrrolidone and 50 parts by mass of methyl ethyl ketone were charged into a reaction vessel equipped with a stirrer, a thermometer and a reflux condenser, dissolved at 75℃and cooled to 60 ℃. Next, 1000 parts by mass of ion-exchanged water was slowly added while stirring with a homomixer, to obtain an aqueous dispersion. Methyl ethyl ketone was distilled off from the aqueous dispersion under reduced pressure, and concentrated to a nonvolatile content of 35 mass%, whereby an aqueous epoxy resin composition (R1) was obtained.
( Comparative example 2: production and evaluation of aqueous epoxy resin composition (R2) )
70 parts by mass of an epoxy resin (A-2), 6 parts by mass of a polyester (B-1), 60 parts by mass of an aromatic nonionic surfactant (C-3), 64 parts by mass of an aromatic nonionic surfactant (C-2) and 30 parts by mass of methyl ethyl ketone were charged into a reaction vessel equipped with a stirrer, a thermometer and a reflux condenser, dissolved at 75℃and cooled to 40 ℃. Next, 570 parts by mass of ion-exchanged water was slowly added while stirring with a homomixer, to obtain an aqueous dispersion. The solvent was distilled off from the aqueous dispersion under reduced pressure, and concentrated to a nonvolatile content of 35 mass%, whereby an aqueous epoxy resin composition (R2) was obtained.
( Comparative example 3: production and evaluation of aqueous epoxy resin composition (R3) )
180 parts by mass of an epoxy resin (A-2), 4 parts by mass of a polyester (RB-1), 8 parts by mass of an aromatic nonionic surfactant (C-3), 8 parts by mass of an aromatic nonionic surfactant (C-2) and 77 parts by mass of methyl ethyl ketone were charged into a reaction vessel equipped with a stirrer, a thermometer and a reflux condenser, dissolved at 75℃and cooled to 40 ℃. Then, 6.2 parts by mass of triethylamine was added thereto, followed by stirring and mixing until uniform. Next, 530 parts by mass of ion-exchanged water was slowly added to obtain an aqueous dispersion. The solvent was distilled off from the aqueous dispersion under reduced pressure, and concentrated to a nonvolatile content of 35 mass%, whereby an aqueous epoxy resin composition (R3) was obtained.
( Comparative example 4: production and evaluation of aqueous epoxy resin composition (R4) )
180 parts by mass of an epoxy resin (A-1), 10 parts by mass of an aromatic nonionic surfactant (C-2) and 77 parts by mass of methyl ethyl ketone were added to a reaction vessel equipped with a stirrer, a thermometer and a reflux condenser, and dissolved at 75℃and cooled to 40 ℃. Next, 530 parts by mass of ion-exchanged water was slowly added while stirring with a homomixer, to obtain an aqueous dispersion. The solvent was distilled off from the aqueous dispersion under reduced pressure, and concentrated to 40 mass% of a nonvolatile component, whereby an aqueous epoxy resin composition (R4) was obtained.
[ method for measuring nonvolatile component ]
In a metal petri dish (inner diameter: 65mm, depth: 14 mm) having been precisely weighed in advance to the 4 th position after the decimal point, about 1g of the aqueous epoxy resin composition obtained above was precisely weighed to the 4 th position after the decimal point, 5ml of ion-exchanged water was added, and the nonvolatile components were obtained from the remaining amount of the sample after drying at 107℃for 1.5 hours in a hot air circulation type dryer. The following shows the calculation formula of the nonvolatile component.
Non-volatile component (% by mass) = [ (W) 3 -W 1 )/(W 2 -W 1 )]×100
W 1 : quality of Metal Petri dish (g)
W 2 : mass of metal Petri dish + mass of sample (g) weighed
W 3 : mass of metal dish + mass of dried sample (g)
[ method of measuring viscosity ]
The aqueous epoxy resin composition obtained immediately after production was measured using the following measuring equipment.
Measurement device: VISCOMETER MODEL RB100L (manufactured by DONGMAO Co., ltd.) and measuring temperature: 25 ℃, rotor rotation speed: 60rpm, measurement time: 60 seconds
[ method for measuring average particle diameter ]
The aqueous epoxy resin composition immediately after production obtained as described above was diluted with ion-exchanged water so that the concentration of the epoxy resin became in the range of several tens to several hundreds ppm, and the obtained solution was used as a measurement solution, and the volume average particle diameter was measured using the following measurement equipment.
Measurement device: SALD-2300 (manufactured by Shimadzu corporation), measuring temperature: 23 DEG C
[ evaluation of storage stability (appearance) ]
The aqueous epoxy resin composition obtained above was stored at 40℃for 30 days, and the occurrence of a precipitate and the solidification phenomenon of the liquid were visually confirmed, and the storage stability was evaluated based on the following criteria.
O: no change
Delta: has a plurality of sediments
X: intense generation, or solidification, of the precipitate
[ evaluation of storage stability (epoxy group residual Rate) ]
The aqueous epoxy resin composition obtained above was stored at 40℃for 30 days, and the epoxy equivalent before and after storage was measured by the pyridine hydrochloride method to calculate the residual rate of epoxy groups.
"residual ratio of epoxy group (%)" = "epoxy equivalent before storage (g/equivalent)"/"epoxy equivalent after storage (g/equivalent)") x 100
[ evaluation of compounding stability ]
Ion-exchanged water and γ -aminopropyl triethoxysilane were added to the aqueous epoxy resin composition obtained above to prepare a 20 mass% aqueous dilution of the nonvolatile component of epoxy resin/γ -aminopropyl triethoxysilane=10/1 (solid content ratio). Next, the mixture was allowed to stand at 40 ℃ for 3 days, and whether or not aggregates were generated or not and the solidification phenomenon of the liquid were visually confirmed, and the blending stability was evaluated based on the following criteria.
O: no change
Delta: has a plurality of sediments
X: intense generation, or solidification, of the precipitate
[ treatment of carbon fiber with sizing agent ]
The unsized filaments of polyacrylonitrile-based carbon fibers (diameter: 7 μm/7000) were bundled, impregnated with ion-exchanged water by an impregnation method, the aqueous epoxy resin composition obtained above was diluted to a nonvolatile content of 5 mass%, extruded by a roll to adjust the amount of the active ingredient to be adhered to 1 mass%, and then heat-treated at 150℃for 30 minutes to obtain a carbon fiber bundle surface-treated with the aqueous epoxy resin composition.
[ production of epoxy molded article ]
50 parts by mass of bisphenol A type liquid epoxy resin (epoxy equivalent 188 g/equivalent), 20 parts by mass of bisphenol A type solid epoxy resin (epoxy equivalent 475 g/equivalent, softening point 70 ℃ C.) and 30 parts by mass of cresol novolac type epoxy resin (epoxy equivalent 209 g/equivalent, softening point 75 ℃ C.) were mixed with 4 parts by mass of dicyandiamide and 4 parts by mass of N- (3, 4-dichlorophenyl) -N ', N' -dimethylurea, and the mixture was applied to a release paper. The carbon fiber bundles obtained above were aligned in one direction at equal intervals on the coated resin film, and then heated to impregnate the resin with the resin, thereby producing a prepreg having a carbon fiber content of 60% by volume. The resulting prepregs were laminated, and were subjected to a press treatment at 150℃for 1 hour, followed by a treatment at 140℃for 4 hours, whereby a molded article was obtained.
[ evaluation of interlaminar shear Strength of epoxy molded article ]
For a test plate having a thickness of 2.5mm and a width of 6.0mm, the interlaminar shear strength was measured by the method according to ASTM D-2344. The interlayer shear strength was also measured in the same manner as in the test plate obtained by boiling the same test plate in distilled water for 72 hours.
[ production of carbon fiber chopped strands ]
The non-sized filaments of polyacrylonitrile-based carbon fibers (diameter: 7 μm/6000) were bundled, impregnated with ion-exchanged water by an impregnation method, and the aqueous epoxy resin composition obtained above was diluted to a nonvolatile content of 5 mass%, and extruded by a roll, whereby the amount of the active ingredient deposited was adjusted to 1 mass%. Next, the carbon fiber bundles were cut to a length of about 4mm, and heat-treated at 150 ℃ for 30 minutes, thereby obtaining carbon fiber chopped strands surface-treated with a carbon fiber bundling agent.
[ production of PPS molded article ]
The carbon fiber chopped strands 30 parts by mass or glass fiber chopped strands 30 parts by mass obtained above were uniformly mixed with polyphenylene sulfide (PPS) 70 parts by mass. Next, the above compounding materials were charged into a twin screw extruder with an outlet, and melt-kneaded at a set resin temperature of 330 ℃ to obtain pellets of the resin composition. Using the pellets, molding was performed by an injection molding machine to obtain PPS molded products.
[ measurement of tensile Strength of PPS molded article ]
Tensile strength was measured for each test piece according to the method of ISO 527. The test piece was a dumbbell-shaped tensile test piece having a total length of 170mm, a narrow parallel portion length of 80mm, a narrow parallel portion width of 10mm, a distance of 109mm between wide parallel portions, a wide parallel portion width of 20mm, and a thickness of 4 mm.
[ measurement of moist Heat resistance of PPS molded article ]
After each test piece was immersed in an aqueous ethylene glycol solution (50 mass%) at a high temperature of 140℃for 3000 hours, the tensile strength of each test piece was measured according to the method of ISO 527.
The compositions and evaluation results of examples 1 to 4 are shown in Table 1.
TABLE 1
Figure BDA0004129030730000181
The compositions and evaluation results of the comparative examples 1 to 4 are shown in Table 2.
TABLE 2
Figure BDA0004129030730000191
The aqueous epoxy resin compositions of examples 1 to 4, which were aqueous epoxy resin compositions of the present invention, were confirmed to have excellent storage stability and blending stability, and molded articles obtained using the aqueous epoxy resin compositions were confirmed to have excellent interlayer shear strength and tensile strength.
On the other hand, comparative example 1 was an example in which the aromatic nonionic surfactant (C) as an essential component of the present invention was not contained, and it was confirmed that the blending stability was poor and the interlayer shear strength of the molded article was insufficient.
Comparative example 2 shows that the content of the epoxy resin (a) is less than the lower limit of the present invention, and that the interlayer shear strength and the tensile strength after the wet heat resistance test of the molded article are insufficient.
Comparative examples 3 and 4 are examples in which the polyester resin (B) having a sulfonic acid group as an essential component of the present invention was not contained, and it was confirmed that the storage stability was insufficient.

Claims (7)

1. An aqueous epoxy resin composition comprising an epoxy resin (A), a polyester resin (B) having a sulfonate group, an aromatic nonionic surfactant (C) and an aqueous medium, wherein the content of the epoxy resin (A) is 75 to 95% by mass based on the total solid content.
2. The aqueous epoxy resin composition according to claim 1, wherein the aromatic nonionic surfactant (C) comprises a surfactant having 40 or more oxyethylene units.
3. The aqueous epoxy resin composition according to claim 1 or 2, wherein the sulfonate group concentration of the polyester resin (B) is 0.2mol/kg to 0.6mol/kg.
4. A fiber collecting agent comprising the aqueous epoxy resin composition according to any one of claims 1 to 3.
5. A fiber bundle, which is formed by bundling the fiber bundle agent according to claim 4.
6. A molding material comprising the fiber bundle according to claim 5 and a matrix resin.
7. A molded article comprising the cured product of the molding material according to claim 6.
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