WO2021095628A1 - エポキシ樹脂組成物、プリプレグおよび繊維強化複合材料 - Google Patents

エポキシ樹脂組成物、プリプレグおよび繊維強化複合材料 Download PDF

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WO2021095628A1
WO2021095628A1 PCT/JP2020/041335 JP2020041335W WO2021095628A1 WO 2021095628 A1 WO2021095628 A1 WO 2021095628A1 JP 2020041335 W JP2020041335 W JP 2020041335W WO 2021095628 A1 WO2021095628 A1 WO 2021095628A1
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epoxy resin
component
resin composition
epoxy
fiber
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French (fr)
Japanese (ja)
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古川浩司
佐野健太郎
川崎順子
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Toray Industries Inc
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Toray Industries Inc
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Priority to EP20888658.0A priority Critical patent/EP4059977A4/en
Priority to JP2020570089A priority patent/JP7631807B2/ja
Priority to US17/772,581 priority patent/US12600853B2/en
Priority to CN202080079150.XA priority patent/CN114729107B/zh
Publication of WO2021095628A1 publication Critical patent/WO2021095628A1/ja
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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
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C08J5/249—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs characterised by the additives used in the prepolymer mixture
    • 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
    • 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
    • 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
    • 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
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/32—Epoxy compounds containing three or more epoxy groups
    • C08G59/3227—Compounds containing acyclic nitrogen atoms
    • 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
    • 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
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/50—Amines
    • C08G59/5033—Amines aromatic
    • 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
    • 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
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/50—Amines
    • C08G59/504—Amines containing an atom other than nitrogen belonging to the amine group, carbon and hydrogen
    • 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
    • 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
    • C08J5/10—Reinforcing macromolecular compounds with loose or coherent fibrous material characterised by the additives used in the polymer mixture
    • 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
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C08J5/241—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres
    • C08J5/243—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres using carbon fibres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/06—Elements
    • 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
    • C08L63/10—Epoxy resins modified by unsaturated 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
    • 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
    • C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon

Definitions

  • the present invention relates to an epoxy resin composition preferably used for a fiber-reinforced composite material for aerospace applications, general industrial applications, sports applications, etc., and a prepreg and a fiber-reinforced composite material using the epoxy resin composition. ..
  • Fiber-reinforced composite materials that use carbon fiber or aramid fiber as reinforcing fibers utilize their high specific strength and specific elastic modulus to make structural materials such as aircraft and automobiles, tennis rackets, golf shafts, fishing rods, bicycles, etc. It is widely used for sports such as housings and general industrial applications.
  • a thermosetting resin is mainly used from the viewpoint of heat resistance and productivity, and among them, an epoxy resin is preferable from the viewpoint of mechanical properties such as adhesiveness to the reinforcing fiber. Used.
  • Patent Document 1 a method for improving elastic modulus and strength by combining an epoxy resin having a specific structure and a nanofiller has been studied. Further, a method for improving the resin strength by adding an additive in order to reduce that dicyandiamide used as a curing agent remains undissolved and becomes a defect has been studied (Patent Document 2). Further, a method of using a liquid curing agent which is unlikely to cause defects in a resin composition for an RTM molding method has been studied (Patent Document 3).
  • an object of the present invention to provide an epoxy resin composition having excellent elastic modulus, strength, and pot life, which can be suitably used for prepreg and fiber reinforced composite material applications.
  • the present invention employs the following means in order to solve such a problem. That is, it is an epoxy resin composition containing the following components [A] to [C] and satisfying the following conditions (1) to (3).
  • Compound (1), which has substantially no curability of an epoxy resin At least a part of the component [C] has two or more alcoholic hydroxyl groups in the molecule.
  • the present invention is a prepreg composed of the epoxy resin composition of the present invention and reinforcing fibers.
  • the present invention is a fiber-reinforced composite material composed of a cured product of the epoxy resin composition of the present invention and reinforcing fibers.
  • an epoxy resin composition having excellent elastic modulus, strength and pot life that can be suitably used for prepreg and fiber-reinforced composite material applications can be obtained.
  • the resin composition of the present invention contains the constituent elements [A] to [C] as essential components.
  • the "component” means a compound contained in the composition.
  • the component [A] in the present invention is an epoxy resin.
  • the epoxy resin of the component [A] one containing two or more epoxy groups in one molecule raises the glass transition temperature of the cured product obtained by heating and curing the resin composition and improves heat resistance. It is preferable because it can be used. Further, an epoxy resin containing one epoxy group in one molecule may be blended. These epoxy resins may be used alone or in combination as appropriate.
  • Examples of the epoxy resin of the component [A] include diaminodiphenylmethane type, diaminodiphenylsulfone type, aminophenol type, bisphenol type, metaxylene diamine type, 1,3-bisaminomethylcyclohexane type, isocyanurate type, and hydantin type. , Phenol novolac type, orthocresol novolac type, trishydroxyphenylmethane type, tetraphenylol ethane type and other epoxy resins. Of these, diaminodiphenylmethane-type, aminophenol-type, and bisphenol-type epoxy resins are particularly preferably used because they have a good balance of physical properties.
  • diaminodiphenylmethane type epoxy resin examples include ELM434 (manufactured by Sumitomo Chemical Co., Ltd.), "Araldite (registered trademark)” MY720 (manufactured by Huntsman Advanced Materials Co., Ltd.), and "Araldite (registered trademark)” MY721.
  • Examples of commercially available diaminodiphenyl sulfone type epoxy resins include TG3DAS (manufactured by Mitsui Kagaku Fine Co., Ltd.).
  • aminophenol type epoxy resins include ELM120 (manufactured by Sumitomo Chemical Co., Ltd.), ELM100 (manufactured by Sumitomo Chemical Co., Ltd.), "jER (registered trademark)” 630 (manufactured by Mitsubishi Chemical Co., Ltd.), and "Araldite”.
  • bisphenol A type epoxy resins include "EPON (registered trademark)” 825 (manufactured by Mitsubishi Chemical Corporation), “Epicron (registered trademark)” 850 (manufactured by DIC Corporation), and “Epototo (registered trademark)”. "YD-128 (manufactured by Toto Kasei Co., Ltd.), and DER-331 and DER-332 (manufactured by Dow Chemical Corporation) and the like can be mentioned.
  • bisphenol F-type epoxy resins include "Araldite (registered trademark)” GY282 (manufactured by Huntsman Advanced Materials), “jER (registered trademark)” 806, “jER (registered trademark)” 807, and “jER”. (Registered trademark) “1750 (above, manufactured by Mitsubishi Chemical Corporation),” Epicron (registered trademark) “830 (manufactured by DIC Co., Ltd.) and” Epototo (registered trademark) "YD-170 (manufactured by Toto Kasei Co., Ltd.) ) And so on.
  • an epoxy compound other than the above may be appropriately blended in the epoxy resin composition of the present invention.
  • the component [B] in the present invention is a polyamine curing agent.
  • the polyamine curing agent has a plurality of amino groups (including two aspects of the amino group) capable of reacting with the epoxy group, and functions as a curing agent.
  • the polyamine curing agent undergoes an addition reaction with the epoxy resin, and at that time, a hydroxyl group is generated by ring-opening of the epoxy group.
  • a strong intermolecular interaction occurs between this hydroxyl group generated in the crosslinked structure of the cured epoxy resin and the constituent element [C] described later, so that the constituent element [C] is easily retained in the crosslinked structure. ,
  • the effect of improving elastic modulus, strength, and elongation can be obtained.
  • polyamine curing agent examples include aliphatic polyamines and aromatic polyamines. These polyamine curing agents may be used alone or in combination as appropriate. Aromatic polyamines, especially aromatic diamines, are excellent as curing agents in that they can impart high mechanical properties and heat resistance to the cured epoxy resin.
  • 2,2'-diethyldiaminodiphenylmethane 2,4-diethyl-6-methyl-m-phenylenediamine, 4,6-diethyl-2-methyl-m-phenylenediamine, 4 , Diethyltoluenediamine such as 6-diethyl-m-phenylenediamine, 4,4'-methylenebis (N-methylaniline), 4,4'-methylenebis (N-ethylaniline), 4,4'-methylenebis (N-) sec-butylaniline), N, N'-di-sec-butyl-p-phenylenediamine, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, 3, 3'-diisopropyl-4,4'-diaminodiphenylmethane, 3,
  • 3,3'-diaminodiphenyl sulfone and 4,4'-diaminodiphenyl sulfone are preferably used because the obtained cured product has excellent mechanical properties.
  • a solid curing agent is used as the polyamine curing agent from the viewpoint that the increase in viscosity when the epoxy resin composition of the present invention is held at 70 ° C. can be suppressed and the pot life can be effectively improved.
  • aromatic polyamines include Seika Cure S (manufactured by Wakayama Seika Kogyo Co., Ltd.), MDA-220 (manufactured by Mitsui Chemicals Co., Ltd.), and "jER Cure (registered trademark)" WA (manufactured by Mitsubishi Chemicals Co., Ltd.).
  • the ratio H / E of the number of moles E of the epoxy group of the component [A] to the number of moles H of the active hydrogen of the polyamine curing agent is 0.50 or more and 1.30. It is preferably 0.70 or more and 1.20 or less, and more preferably 0.80 or more and 1.10 or less.
  • the H / E 0.80 or more and 1.10 or less, the amount of hydroxyl groups generated by the reaction between the epoxy resin and the polyamine curing agent becomes appropriate.
  • the component [C] described later is easily held in the crosslinked structure, and the effect of improving the elastic modulus, strength, and elongation can be obtained.
  • the total number of moles E of the epoxy group of the component [A] and at least one of 3,3'-diaminodiphenyl sulfone and 4,4'-diaminodiphenyl sulfone. ((Total number of moles of at least one of 3,3'-diaminodiphenyl sulfone and 4,4'-diaminodiphenyl sulfone) / E) is preferably 0.50 or more and 1.30 or less.
  • the epoxy resin composition of the present invention can be adjusted to 70 ° C. It is possible to suppress the increase in viscosity when holding the pot with, and to effectively improve the pot life.
  • the component [C] is a compound having a boiling point of 130 ° C. or higher and a molecular weight m of 50 or higher and 250 or lower, which does not have an epoxy group in the molecule and substantially has a curable ability of an epoxy resin. It is a compound that does not exist.
  • compounds such as amines and phenols that can undergo an addition reaction with an epoxy resin, acid anhydrides that can copolymerize with an epoxy resin, imidazole that can be a self-polymerization reaction initiator of an epoxy resin, an aromatic urea compound, and a tertiary amine compound are used.
  • It is a compound having an epoxy resin curable ability and does not correspond to a compound having no epoxy resin curable ability.
  • the component [C] exists in the gap portion of the crosslinked structure without being incorporated into the crosslinked structure, and the state is maintained even after curing. As a result, the elastic modulus of the obtained cured epoxy resin product is increased. Further, surprisingly, the inventor has found that by blending the component [C], not only a high elastic modulus but also a high elongation and high strength epoxy resin cured product can be obtained. The reason for this is not clear, but the inventor thinks as follows. The component [C] does not have an epoxy group in the molecule and has substantially no curability of the epoxy resin, so that it does not react with the epoxy resin or polyamine forming the crosslinked structure.
  • the component [C] is not constrained by the crosslinked structure formed by the reaction of the epoxy resin and the polyamine and the covalent bond, and is appropriately held in the voids of the crosslinked structure, so that the cured product is obtained.
  • the inventor believes that the voids inside can be effectively filled and the elastic modulus of the cured product is increased. Further, when the cured product is strained, the component [C] can move freely in the crosslinked structure, so that the strain energy leading to fracture can be relaxed, and the elongation and strength of the cured product are increased. The inventor thinks that.
  • the boiling point of the component [C] is 130 ° C. or higher, more preferably 180 ° C. or higher, volatilization of the component [C] when the epoxy resin composition is cured can be suppressed, and the mechanical properties are excellent.
  • a cured resin product or a fiber-reinforced composite material can be obtained. Further, it is possible to suppress the generation of voids and the deterioration of mechanical properties in the obtained fiber-reinforced composite material.
  • the boiling point is a value at normal pressure (101 kPa). If the boiling point at normal pressure cannot be measured, the converted boiling point converted to 101 kPa in the boiling point conversion chart can be used.
  • the molecular weight m of the component [C] is 50 or more and 250 or less. By setting the molecular weight of the component [C] within such a range, the component [C] is appropriately held in the voids of the crosslinked structure formed by the reaction of the epoxy resin and the polyamine, and has an elastic modulus and strength. , A cured product with excellent elongation can be obtained. Further, by setting the molecular weight m of the component [C] to 50 or more and 150 or less, a cured product having a particularly excellent elastic modulus can be obtained. Further, preferably 70 or more and 110 or less, a cured product having a further excellent elastic modulus can be obtained. Further, preferably, by setting the content to 50 or more and 110 or less, a cured product having particularly excellent strength can be obtained. Further, preferably 50 or more and 90 or less, a cured product having further excellent strength can be obtained.
  • At least a part of the component [C] has two or more alcoholic hydroxyl groups in the molecule (condition (1)).
  • the compound having an alcoholic hydroxyl group is a compound in which hydrogen of an aliphatic hydrocarbon is substituted with a hydroxyl group, and does not include a compound having a phenolic hydroxyl group in which hydrogen in an aromatic ring is substituted with a hydroxyl group. Since the component [C] has an alcoholic hydroxyl group in the molecule, it is strong between the alcoholic hydroxyl group in the crosslinked structure formed from the component [A] and the component [B] and the component [C].
  • the intermolecular interaction works and the component [C] is easily held in the void portion of the crosslinked structure, an excellent effect of improving elongation and strength can be obtained. Further, when the component [C] has two or more alcoholic hydroxyl groups in the molecule, the points where the above-mentioned intermolecular interaction occurs in the crosslinked structure are increased, and a particularly excellent effect of improving elongation and strength is obtained. can get.
  • Examples of the component [C] having two or more alcoholic hydroxyl groups in the molecule include 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, and 1 , 4-butanediol, 2,3-butanediol, 2-methyl-1,2-propanediol, 2-methyl-1,3-propanediol, 1,2-pentanediol, 1,3-pentanediol, 1, , 4-Pentanediol, 1,5-Pentanediol, 2,3-Pentanediol, 2,4-Pentanediol, 2-Methyl-1,2-Butanediol, 2-Methyl-2,3-Butanediol, 2 -Methyl-1,4-butanediol, 3-methyl-1,2-butanediol, 3-methyl-1
  • Examples thereof include alicyclic polyols, polyols having an ether group such as diethylene glycol, triethylene glycol, dipropylene glycol and tripropylene glycol, and aromatic polyols such as benzenedimethanol. These compounds may be used alone or in combination as appropriate.
  • the ratio C / E of the number of moles E of the epoxy group of the component [A] to the number of moles C of the component [C] satisfying the above condition (1) is 0.01. As mentioned above, it is important that it is 0.20 or less (condition (2)).
  • condition (2) By setting the C / E within such a range, the component [C] is appropriately retained in the voids of the crosslinked structure formed by the reaction of the epoxy resin and the polyamine, and the elastic modulus, strength, and elongation are adjusted. An excellent cured product can be obtained.
  • a cured product having a particularly excellent elastic modulus can be obtained. ..
  • a cured product having particularly excellent strength can be obtained.
  • a cured product having particularly excellent strength can be obtained.
  • both the elastic modulus and the strength are particularly excellent. You get things.
  • the viscosity of the resin composition of the present invention when held at 70 ° C. for 2 hours is 5.0 times or less the initial viscosity at 70 ° C. (condition (3)).
  • a ratio also referred to as “viscosity increase ratio”
  • the step of kneading the resin composition and the resin composition In the step of impregnating the reinforcing fiber with the material, the change in viscosity of the resin composition becomes small, and the pot life can be lengthened. Further, it is possible to reduce the variation in the flow amount of the resin composition during molding, suppress the variation in the resin content contained in the fiber-reinforced composite material, and obtain a fiber-reinforced composite material having stable dimensions and mechanical properties. ..
  • the viscosity increase ratio is determined by using at least one of 3,3'-diaminodiphenyl sulfone and 4,4'-diaminodiphenyl sulfone in which the polyamine curing agent of the component [B] is solid as an aromatic diamine. It can be effectively suppressed.
  • the epoxy resin composition of the present invention is excellent in elastic modulus, strength, and elongation, and is suitably used as a matrix resin of a fiber-reinforced composite material. That is, the fiber-reinforced composite material of the present invention comprises a cured product of the epoxy resin composition of the present invention and reinforcing fibers.
  • Methods for obtaining a fiber-reinforced composite material include a method of impregnating a reinforcing fiber with a resin composition in a molding process such as a hand lay-up method, an RTM method, a filament winding method, and a drawing molding method, or a method of preliminarily converting a resin composition into a reinforcing fiber.
  • a method of molding the impregnated prepreg by an autoclave method or a press molding method.
  • the prepreg of the present invention comprises the epoxy resin composition of the present invention and reinforcing fibers.
  • the reinforcing fiber used for the prepreg and the fiber-reinforced composite material of the present invention carbon fiber, graphite fiber, aramid fiber, glass fiber and the like can be preferably mentioned, but carbon fiber is particularly preferable.
  • the form and arrangement of the reinforcing fibers are not limited, and for example, fibrous structures such as long fibers aligned in one direction, a single tow, a woven fabric, a knit, and a braid are used.
  • the reinforcing fibers two or more types of carbon fibers, glass fibers, aramid fibers, boron fibers, PBO fibers, high-strength polyethylene fibers, alumina fibers, silicon carbide fibers and the like may be used in combination.
  • carbon fibers include acrylic, pitch and rayon carbon fibers, and acrylic carbon fibers having particularly high tensile strength are preferably used.
  • the form of the carbon fiber twisted yarn, untwisted yarn, untwisted yarn and the like can be used, but in the case of twisted yarn, the orientation of the filaments constituting the carbon fiber is not parallel, so that the obtained carbon fiber reinforced composite material can be used. Since it causes deterioration of the mechanical properties of the carbon fiber reinforced composite material, untwisted or untwisted yarn having a good balance between formability and strength characteristics of the carbon fiber reinforced composite material is preferably used.
  • the carbon fiber preferably has a tensile elastic modulus of 200 GPa or more and 440 GPa or less.
  • the tensile elastic modulus of the carbon fiber is affected by the crystallinity of the graphite structure constituting the carbon fiber, and the higher the crystallinity, the higher the elastic modulus. Within this range, the rigidity and strength of the carbon fiber reinforced composite material are all balanced at a high level, which is preferable.
  • a more preferable elastic modulus is 230 GPa or more and 400 GPa or less, and more preferably 260 GPa or more and 370 GPa or less.
  • the tensile elastic modulus of the carbon fiber is a value measured according to JIS R7608 (2008).
  • the prepreg of the present invention can be produced by various known methods.
  • a prepreg can be produced by a hot melt method in which the resin composition is reduced in viscosity by heating and impregnated into reinforcing fibers without using an organic solvent.
  • a method of directly impregnating the reinforcing fibers with a resin composition whose viscosity has been reduced by heating or a method of first producing a release paper sheet with a resin film in which the resin composition is once coated on a release paper or the like. Then, a method can be used in which a resin film is laminated on the reinforcing fiber side from both sides or one side of the reinforcing fiber, and the reinforcing fiber is impregnated with the resin composition by heating and pressurizing.
  • the content of the reinforcing fibers in the prepreg is preferably 30% by mass or more and 90% by mass or less.
  • the content is preferably 30% by mass or more, more preferably 35% by mass or more, still more preferably 65% by mass or more.
  • the advantages of the fiber-reinforced composite material having excellent specific strength and specific elastic modulus can be easily obtained. Further, when molding the fiber-reinforced composite material, it is possible to prevent the amount of heat generated during curing from becoming too high.
  • the content to 90% by mass or less, more preferably 85% by mass or less, it is possible to suppress the generation of voids in the composite material due to poor resin impregnation. Moreover, the tackiness of the prepreg can be maintained.
  • the fiber-reinforced composite material of the present invention can be produced, for example, by laminating the above-mentioned prepreg of the present invention in a predetermined form and pressurizing and heating to cure the resin.
  • a method of applying heat and pressure a press molding method, an autoclave molding method, a bagging molding method, a lapping tape method, an internal pressure molding method and the like are adopted.
  • the fiber-reinforced composite material of the present invention can be widely used for aerospace applications, general industrial applications and sports applications. More specifically, in general industrial applications, it is suitably used for structures such as automobiles, ships, and railroad vehicles. In sports applications, it is suitably used for golf shafts, fishing rods, tennis and badminton rackets.
  • the unit "part" of the composition ratio means a mass part unless otherwise specified.
  • the various characteristics (physical properties) were measured in an environment with a temperature of 23 ° C. and a relative humidity of 50% unless otherwise specified.
  • Component [C] A compound having a boiling point of 130 ° C. or higher and a molecular weight m of 50 to 250 g / mol, having no epoxy group in the molecule, and substantially curing the epoxy resin. A compound that has no ability.
  • 1,2-ethanediol (boiling point: 197 ° C, molecular weight m: 62 g / mol, manufactured by Tokyo Chemical Industry Co., Ltd.) 1,2-Propanediol (boiling point: 188 ° C., molecular weight m: 76 g / mol, manufactured by Tokyo Chemical Industry Co., Ltd.) -1,2-Hexanediol (boiling point: 245 ° C., molecular weight m: 118 g / mol, manufactured by Tokyo Chemical Industry Co., Ltd.) -Trans-1,2-cyclopentanediol (boiling point: 250 ° C., molecular weight m: 102 g / mol, manufactured by Sigma-Aldrich Japan GK).
  • the ratio H / E of the number of moles H of active hydrogen of the component [B] to the number E of moles of the epoxy group of the component [A] was 1.00.
  • the ratio C / E of the number of moles C of the component [C] to the number of moles E of the epoxy group of the component [A] was 0.10.
  • the molecular weight m of the component [C] was 62.
  • Examples 2 to 12 The respective components [A], [B] and [C] were blended in the same procedure as in Example 1 above according to the blending ratios in Tables 1 and 2, to obtain a resin composition.
  • Comparative Example 1 the component [C] was not mixed. Comparing Comparative Example 1 and Example 1, the elastic modulus, strength, and elongation of the cured resin product are improved by blending the component [C], and the strength and elongation are particularly dramatic. It can be seen that it has improved.
  • Comparative Example 2 also does not contain the component [C]. Comparing Comparative Example 2 and Example 12, it can be seen that the elastic modulus and strength of the cured resin product are dramatically improved by blending the component [C] in the same manner.
  • Comparative Example 5 ethanol was blended instead of the component [C]. Ethanol does not satisfy the condition that the boiling point of the component [C] is 130 ° C. or higher and that the molecular weight m is 50 or more and 250 or less. Comparing Comparative Example 5 and Example 1, the elasticity of the cured resin product obtained by blending the component [C] satisfying the requirements of a boiling point of 130 ° C. or higher and a molecular weight m of 50 or higher and 250 or lower. It can be seen that the rate, strength, and elongation improve.
  • Comparative Example 6 the 1,2-hexadecanediol containing 1,2-hexadecanediol instead of the component [C] does not satisfy the condition that the molecular weight m of the component [C] is 50 or more and 250 or less. .. Comparing Comparative Example 6 and Example 1, it can be seen that the elastic modulus, strength, and elongation of the obtained cured resin product are improved when the component [C] satisfies the above conditions.
  • Comparative Example 7 glycidol was blended instead of the component [C]. Glycidol has an epoxy group in the molecule. Comparing Comparative Example 7 and Example 1, it can be seen that the elastic modulus, strength, and elongation of the obtained cured resin product are improved because the component [C] does not have an epoxy group in the molecule.
  • Comparative Example 8 the conditions that the number of moles E of the epoxy group of the component [A] and the number of moles C of the component [C] are 0.01 or more and 0.20 or less are not satisfied. Comparing Comparative Example 8 and Example 1, it can be seen that the elastic modulus, strength, and elongation of the obtained cured resin product are improved by satisfying the above conditions.
  • Comparative Example 9 does not satisfy the condition that the viscosity of the epoxy resin composition when held at 70 ° C. for 2 hours is 5.0 times or less of the initial viscosity at 70 ° C. Therefore, the composition has a large increase in viscosity in the step of mixing the epoxy resin and has a short pot life. Comparing Comparative Example 9 and Example 1, it can be seen that the pot life of the obtained resin composition is long and the handleability is excellent by satisfying the above conditions.
  • Example 2 when Example 3, Example 4, Example 5, Comparative Example 1, and Comparative Example 8 are compared, they are the same component [A], component [B], and component [C]. It is an epoxy resin composition containing, and only the blending amount of the component [C] is different.
  • the relationship between the ratio C / E of the number of moles C of the component [C] to the number of moles E of the epoxy group of the component [A] and the elastic modulus is shown in FIG. 1, and the relationship with the strength is shown in FIG. From FIGS. 1 and 2, it can be seen that in the epoxy resin composition of the present invention, when the C / E is 0.01 or more and 0.20 or less, a cured product having excellent elastic modulus, strength, and elongation can be obtained. ..
  • Example 1 comparing Example 1, Example 4, Example 6, Example 7, Comparative Example 1, and Comparative Example 6, these are epoxies containing the same component [A] and component [B] in the same compounding ratio.
  • the type or presence or absence of the resin composition which is a component [C] or a compound compounded in place of the component [C] is different.
  • the relationship between the molecular weight m of the component [C] and the elastic modulus is shown in FIG. 3, and the relationship with the strength is shown in FIG. From FIGS. 3 and 4, it can be seen that in the resin composition of the present invention, when the molecular weight m of the component [C] is 50 to 150, a cured product having a particularly excellent elastic modulus can be obtained. Further, it can be seen that when the molecular weight m of the component [C] is 50 to 110, a cured product having particularly excellent strength can be obtained.

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  • Polymers & Plastics (AREA)
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  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
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PCT/JP2020/041335 2019-11-15 2020-11-05 エポキシ樹脂組成物、プリプレグおよび繊維強化複合材料 Ceased WO2021095628A1 (ja)

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EP20888658.0A EP4059977A4 (en) 2019-11-15 2020-11-05 EPOXY RESIN COMPOSITION, PREPREG AND FIBER REINFORCED COMPOSITE MATERIAL
JP2020570089A JP7631807B2 (ja) 2019-11-15 2020-11-05 エポキシ樹脂組成物、プリプレグおよび繊維強化複合材料
US17/772,581 US12600853B2 (en) 2019-11-15 2020-11-05 Epoxy resin composition, prepreg, and fiber reinforced composite material
CN202080079150.XA CN114729107B (zh) 2019-11-15 2020-11-05 环氧树脂组合物、预浸料及纤维增强复合材料

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN118715270A (zh) * 2022-02-16 2024-09-27 东丽株式会社 预浸料坯、纤维增强复合材料、纤维增强复合材料制管状体、高尔夫球杆杆身及钓竿

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008095013A (ja) * 2006-10-13 2008-04-24 Fujikura Ltd エポキシ系接着剤、カバーレイ、プリプレグ、金属張積層板、プリント配線基板
JP2010077176A (ja) * 2008-09-24 2010-04-08 Fuji Kasei Kogyo Co Ltd 氷点下で硬化可能な水性エマルションエポキシド組成物
JP2014227473A (ja) 2013-05-23 2014-12-08 東レ株式会社 複合材料用エポキシ樹脂組成物、繊維強化複合材料およびそれらの製造方法
JP2017535652A (ja) * 2014-11-20 2017-11-30 ダウ グローバル テクノロジーズ エルエルシー 促進剤組成物
JP2018095675A (ja) 2016-12-08 2018-06-21 三菱ケミカル株式会社 エポキシ樹脂組成物、並びにこれを用いた成形品、プリプレグ及び繊維強化プラスチック
US20190134926A1 (en) * 2017-11-08 2019-05-09 Cytec Industries Inc. Composites with interlaminar toughening particles and method of making the same
WO2019181402A1 (ja) 2018-03-20 2019-09-26 東レ株式会社 プリプレグおよび繊維強化複合材料

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4352720B2 (ja) * 2003-02-24 2009-10-28 東レ株式会社 繊維強化複合材料用エポキシ樹脂組成物、繊維強化複合材料およびその製造方法
JP2009155431A (ja) 2007-12-26 2009-07-16 Sumitomo Bakelite Co Ltd 液状封止樹脂組成物、半導体装置および半導体装置の製造方法
JP5886629B2 (ja) * 2009-01-06 2016-03-16 ブルー キューブ アイピー エルエルシー 非臭素化難燃性エポキシ樹脂における金属化合物
US9132611B2 (en) * 2009-09-30 2015-09-15 Hitachi Chemical Co., Ltd. Resin composition, prepreg using same, metal foil with resin, adhesive film, and metal-clad laminate
WO2012043453A1 (ja) * 2010-09-28 2012-04-05 東レ株式会社 エポキシ樹脂組成物、プリプレグおよび繊維強化複合材料
CN109265655B (zh) 2018-09-04 2020-12-25 北京化工大学 一种快速固化树脂体系及制备方法

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008095013A (ja) * 2006-10-13 2008-04-24 Fujikura Ltd エポキシ系接着剤、カバーレイ、プリプレグ、金属張積層板、プリント配線基板
JP2010077176A (ja) * 2008-09-24 2010-04-08 Fuji Kasei Kogyo Co Ltd 氷点下で硬化可能な水性エマルションエポキシド組成物
JP2014227473A (ja) 2013-05-23 2014-12-08 東レ株式会社 複合材料用エポキシ樹脂組成物、繊維強化複合材料およびそれらの製造方法
JP2017535652A (ja) * 2014-11-20 2017-11-30 ダウ グローバル テクノロジーズ エルエルシー 促進剤組成物
JP2018095675A (ja) 2016-12-08 2018-06-21 三菱ケミカル株式会社 エポキシ樹脂組成物、並びにこれを用いた成形品、プリプレグ及び繊維強化プラスチック
US20190134926A1 (en) * 2017-11-08 2019-05-09 Cytec Industries Inc. Composites with interlaminar toughening particles and method of making the same
WO2019181402A1 (ja) 2018-03-20 2019-09-26 東レ株式会社 プリプレグおよび繊維強化複合材料

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP4059977A4

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN118715270A (zh) * 2022-02-16 2024-09-27 东丽株式会社 预浸料坯、纤维增强复合材料、纤维增强复合材料制管状体、高尔夫球杆杆身及钓竿

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TWI858183B (zh) 2024-10-11
CN114729107B (zh) 2024-08-02
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