WO2023176935A1 - Ｒｔｍ用エポキシ樹脂組成物、樹脂硬化物、繊維強化複合材料およびその製造方法 - Google Patents

Ｒｔｍ用エポキシ樹脂組成物、樹脂硬化物、繊維強化複合材料およびその製造方法 Download PDF

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WO2023176935A1
WO2023176935A1 PCT/JP2023/010373 JP2023010373W WO2023176935A1 WO 2023176935 A1 WO2023176935 A1 WO 2023176935A1 JP 2023010373 W JP2023010373 W JP 2023010373W WO 2023176935 A1 WO2023176935 A1 WO 2023176935A1
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Prior art keywords
epoxy resin
resin composition
mass
rtm
component
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English (en)
French (fr)
Japanese (ja)
Inventor
大典 小西
啓之 平野
紘也 土田
伸之 富岡
遼平 渡
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Toray Industries Inc
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Toray Industries Inc
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Priority to AU2023235727A priority Critical patent/AU2023235727A1/en
Priority to EP23770888.8A priority patent/EP4495156A4/en
Priority to CN202380022413.7A priority patent/CN118742585A/zh
Priority to US18/846,013 priority patent/US20260015455A1/en
Priority to JP2023518784A priority patent/JPWO2023176935A1/ja
Publication of WO2023176935A1 publication Critical patent/WO2023176935A1/ja
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • 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
    • C08G59/20—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
    • C08G59/22—Di-epoxy compounds
    • C08G59/24—Di-epoxy compounds carbocyclic
    • C08G59/245—Di-epoxy compounds carbocyclic 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
    • C08G59/20—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
    • C08G59/3209—Epoxy compounds containing three or more epoxy groups obtained by polymerisation of unsaturated mono-epoxy compounds
    • 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
    • C08G59/3218—Carbocyclic compounds
    • 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
    • C08G59/38—Epoxy compounds containing three or more epoxy groups together with di-epoxy compounds
    • 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
    • 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
    • C08J5/24—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
    • 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
    • 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
    • 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
    • C08J2363/08—Epoxidised polymerised polyenes
    • 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
    • C08J2463/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins

Definitions

  • the present invention relates to an epoxy resin composition for RTM, a cured resin material, a fiber-reinforced composite material using the same, and a method for producing the same, which is preferably used for aerospace components and general industrial applications.
  • Epoxy resin compositions are widely used as matrix resins for fiber-reinforced composite materials, taking advantage of their excellent heat resistance, adhesive properties, and mechanical strength.
  • Fiber-reinforced composite materials are manufactured by integrating reinforcing fibers and matrix resin, and manufacturing methods include laminating and molding prepregs impregnated with reinforcing fibers and matrix resin in advance, and forming reinforced fiber base materials. There is a method of injecting a low-viscosity matrix resin into the resin and curing it.
  • methods using prepreg have been widely used in industry and the aircraft field because they exhibit high mechanical properties, but they have the disadvantage that the manufacturing process, such as preparing and shaping the prepreg, takes time.
  • a two-component epoxy resin composition is often used from the viewpoint of moldability.
  • a two-part epoxy resin composition is composed of an epoxy base liquid containing an epoxy resin as a main component and a hardening agent liquid containing a hardening agent as a main component. It refers to an epoxy resin composition obtained by mixing.
  • an epoxy resin composition in which all components including the base agent and curing agent are mixed into one is called a one-component epoxy resin composition.
  • the matrix resin In the injection molding method, in order to obtain a large-sized fiber-reinforced composite material, the matrix resin needs to have a low viscosity in the injection process. In addition, in order to use fiber-reinforced composite materials as primary structural materials for aircraft applications, etc., it is desired that the fiber-reinforced composite materials have a well-balanced modulus of elasticity under moist heat, heat resistance, and fracture toughness. In order to make the matrix resin low in viscosity while achieving both elastic modulus and heat resistance under moist heat, there is a method of blending a large amount of polyfunctional and low molecular weight epoxy resin, but this increases the crosslinking density of the cured resin.
  • Patent Document 1 describes a technique for obtaining a cured epoxy resin with high fracture toughness by using a thermoplastic resin and core-shell rubber particles in a specific ratio.
  • Patent Document 2 discloses that by containing a low-viscosity epoxy resin and core-shell type rubber particles, a cured resin product with high fracture toughness can be obtained, and that the epoxy resin composition can be applied to a reinforcing fiber base material in a resin injection process. A technique has been disclosed that achieves both the property of having good impregnating properties.
  • Patent Document 3 discloses that by using 4,4-methylenebis(isopropyl-6-methylaniline) and core-shell type rubber particles together as a curing agent for epoxy resin, the fracture toughness of the cured resin is improved compared to that without using the combination. Techniques for increasing this have been disclosed.
  • Patent Document 4 discloses an epoxy resin composition containing N,N-diglycidyl-4-phenoxyaniline with low volatility, which provides a prepreg from which molded products with few voids can be obtained, and is suitable for resin transfer molding. There is also a general example that the law can also be used.
  • the epoxy resin composition described in Patent Document 1 has excellent fracture toughness of the cured resin obtained by curing the epoxy resin composition, but since M-CDEA is used as a curing agent, the curing reaction is slow, and fiber reinforcement is required. The problem was that the manufacturing cycle for composite materials was long. In addition, the elastic modulus under moist heat was insufficient.
  • the epoxy resin composition described in Patent Document 2 has a low viscosity in the resin injection process and can yield a resin cured product with high heat resistance, but the elastic modulus under moist heat is significantly insufficient.
  • the epoxy resin composition described in Patent Document 3 has a low viscosity in the resin injection process and has excellent impregnating properties into the reinforcing fiber base material, but the elastic modulus of the cured resin obtained by curing the epoxy resin composition is low.
  • the fracture toughness was extremely low, and although the fracture toughness was improved, it did not reach the required level.
  • the epoxy resin composition described in Patent Document 4 has a high water absorption rate, a resin cured product obtained by curing the epoxy resin composition, and a significant decrease in the elastic modulus and glass transition temperature under moist heat, and also has a high water absorption rate in the resin injection process. has a high viscosity and poor impregnation into reinforcing fiber base materials, making it difficult to apply to the RTM method.
  • An object of the present invention is to provide an epoxy resin composition for RTM, a cured resin product, and a fiber-reinforced composite material using the same, which improves the drawbacks of the prior art.
  • the inventors of the present invention discovered an epoxy resin composition for RTM having the following structure, and completed the present invention. That is, the epoxy resin composition for RTM of the present invention has the following configuration.
  • An epoxy resin composition for RTM that contains the following components [A], [B], and [C] and satisfies all conditions 1 to 4 below.
  • [A] Tetrafunctional glycidylamine type epoxy resin [B] At least one aromatic amine curing agent selected from the group consisting of alkylbenzenediamine and methylenebisaniline
  • R 1 and R 2 each represent at least one selected from aliphatic hydrocarbon groups having 1 to 4 carbon atoms. If R 1 and R 2 are plural, they are the same. n is an integer of 0 to 4, and m is an integer of 0 to 5. X represents -O- or -S-.)
  • Condition 1 Viscosity at 110°C is 1 mPa ⁇ s or more and 200 mPa ⁇ s or less
  • Condition 2 Mass reduction rate after heating at 110°C for 30 minutes is 0.3% by mass or less
  • Condition 3 Curing at 180°C for 2 hours
  • Condition 4 The rubber state elastic modulus of the cured resin obtained by curing at 180° C.
  • component [E] is at least selected from the group consisting of dicyclopentadiene type epoxy resin, biphenyl type epoxy resin, phenol aralkyl type epoxy resin, and naphthalene type epoxy resin.
  • component [B] is an alkylbenzenediamine.
  • the epoxy resin composition for RTM according to any one of [1] to [6] which contains dimethylthiotoluenediamine as the alkylbenzenediamine.
  • a fiber-reinforced composite material comprising the cured resin according to [10] and a reinforcing fiber base material.
  • the epoxy resin composition for RTM according to any one of [1] to [9] is injected into a reinforcing fiber base material placed in a mold heated to 70 ° C. or more and 190 ° C. or less, and impregnated.
  • a method for producing a fiber-reinforced composite material that is cured within the mold.
  • an epoxy resin composition for RTM from which a cured resin product having an excellent balance of elastic modulus, heat resistance, and fracture toughness in a moist heat environment can be obtained.
  • the epoxy resin composition for RTM of the present invention maintains the above characteristics in the resin cured product, and has low viscosity and low volatility in the resin injection process, so it can be used to create large-sized and high Vf fiber reinforced composites by injection molding. It can be suitably used as an epoxy resin composition for RTM suitable for manufacturing.
  • the epoxy resin composition for RTM of the present invention includes at least one aromatic amine curing agent selected from the group consisting of [A] a tetrafunctional glycidylamine type epoxy resin, [B] an alkylbenzenediamine, and methylenebisaniline; C] Contains an aniline type epoxy resin represented by formula (I) as an essential component.
  • component [D] core-shell type rubber particles are selected from the group consisting of a dicyclopentadiene type epoxy resin, a biphenyl type epoxy resin, a phenol aralkyl type epoxy resin, and a naphthalene type epoxy resin as the component [E]. , preferably includes at least one solid epoxy resin.
  • component [A] The epoxy resin composition for RTM of the present invention needs to contain a tetrafunctional glycidylamine type epoxy resin as component [A].
  • component [A] the resin cured product obtained by curing the RTM epoxy resin composition of the present invention exhibits high heat resistance and has an excellent moist heat elastic modulus.
  • component [A] preferably contains 20 parts by mass or more and 80 parts by mass or less, more preferably 40 parts by mass or more and 60 parts by mass or less, and 40 parts by mass or more and 50 parts by mass, based on 100 parts by mass of the total epoxy resin.
  • containing 20 parts by mass or more and 80 parts by mass or less out of 100 parts by mass of the total epoxy resin means 20 parts by mass when the total epoxy resin contained in the epoxy resin composition for RTM of the present invention is 100 parts by mass. 80 parts by mass or less (the same expressions hereinafter also apply).
  • the total epoxy resin refers to all of the epoxy resin components contained in the epoxy resin composition for RTM of the present invention.
  • component [A] examples include tetraglycidyldiaminodiphenylmethane, tetraglycidyldiaminodiphenyl sulfone, and the like.
  • TG3DAS manufactured by Konishi Chemical Industry Co., Ltd.
  • the epoxy resin composition for RTM of the present invention needs to contain an aniline type epoxy resin represented by formula (I) as component [C].
  • component [C] the elastic modulus of the cured resin obtained by curing the RTM epoxy resin composition of the present invention can be maintained, while the rubber state elastic modulus can be made low. If component [C] is not included, the cured resin product obtained by curing the epoxy resin composition will have a low elastic modulus.
  • component [C] is contained in 10 parts by mass or more and 50 parts by mass or less, and more preferably 20 parts by mass or more and 40 parts by mass or less, based on 100 parts by mass of the total epoxy resin.
  • Examples of such component [C] include diglycidyl-p-phenoxyaniline, diglycidyl-4-(4-methylphenoxy)aniline, diglycidyl-4-(4-tert-butylphenoxy)aniline, and diglycidyl-4-(4- Examples include phenoxyphenoxy)aniline and the like.
  • the epoxy resin composition for RTM of the present invention preferably contains core-shell type rubber particles as component [D] from 1 part by mass to 10 parts by mass, and preferably from 3 parts by mass to 6 parts by mass, based on 100 parts by mass of the total epoxy resin. It is more preferable to include the following:
  • component [D] in the above range, the fracture toughness can be made higher without impairing the elastic modulus of the cured resin obtained when the epoxy resin composition for RTM of the present invention is cured. Therefore, by using the epoxy resin composition for RTM of the present invention as a matrix resin, a fiber-reinforced composite material with better compression properties and impact resistance can be obtained.
  • the resulting cured resin may not have a sufficient effect of improving toughness. If the amount of component [D] exceeds 10 parts by mass, the viscosity of the RTM epoxy resin composition may become high in the resin injection process, and the resulting cured resin may have a low elastic modulus. In some cases,
  • the resin toughness value of the cured epoxy resin product in the present invention can be evaluated, for example, from the K1c value obtained from the SENB test described in ASTM D5045-99.
  • Component [B] in the present invention is at least one aromatic amine curing agent selected from the group consisting of alkylbenzenediamine and methylenebisaniline.
  • Such alkylbenzenediamine is an aromatic amine compound having one or more alkyl groups and two amino groups on the benzene ring, and toluenediamines such as diethyltoluenediamine and dimethylthiotoluenediamine are preferably used.
  • an alkylbenzenediamine as a curing agent for an epoxy resin, it is possible to suppress the viscosity of the RTM epoxy resin composition in the resin injection process and obtain a cured resin product with excellent elastic modulus.
  • dimethylthiotoluenediamine is particularly preferred since it allows a cured resin product with an excellent balance between elastic modulus and toughness to be obtained.
  • alkylbenzenediamine Commercial products of such alkylbenzenediamine include "jER Cure (registered trademark)” WA (manufactured by Mitsubishi Chemical Corporation), “Ethacure (registered trademark)” 100 (manufactured by Albemarle), and “Heart Cure (registered trademark)" 10.
  • Such methylenebisaniline is an aromatic amine compound in which two aniline compounds are connected by a methylene bridge, and various substituents may be present on each benzene ring.
  • methylenebisaniline as a curing agent for epoxy resins, it is possible to obtain cured resins with low water absorption and excellent toughness.
  • methylenebisanilines examples include 4,4-methylenebis(isopropyl-6-methylaniline) (M-MIPA), methylenebis(diethylaniline) (M-DEA), methylenebis(chlorodiethylaniline) (M-CDEA). , methylene (methylethylaniline)-(chlorodiethylaniline) (M-MEACDEA), and the like.
  • M-MIPA 4,4-methylenebis(isopropyl-6-methylaniline)
  • M-DEA methylenebis(diethylaniline)
  • M-CDEA methylenebis(chlorodiethylaniline)
  • M-MEACDEA methylene (methylethylaniline)-(chlorodiethylaniline)
  • 4,4-methylenebis(isopropyl-6-methylaniline) is particularly preferred since it allows a cured resin product to be obtained with an excellent balance between elastic modulus and toughness.
  • MDA-220 manufactured by Mitsui Chemicals, Inc.
  • Lonzacure (registered trademark)” M-MIPA "Lonzacure (registered trademark)” M-DEA
  • Lonzacure (registered trademark) examples include “M-CDEA”, “Lonzacure (registered trademark)” M-DIPA (manufactured by Lonza), “Kayahard (registered trademark)” AA (PT) (manufactured by Nippon Kayaku Co., Ltd.), and the like.
  • component [B] in the present invention is an alkylbenzenediamine, and it is also preferable that component [B] contains both an alkylbenzenediamine and methylenebisaniline.
  • component [B] in the present invention is an alkylbenzenediamine
  • a cured resin product with excellent elastic modulus can be obtained while sufficiently suppressing the viscosity of the RTM epoxy resin composition in the resin injection step.
  • the viscosity of the epoxy resin composition for RTM can be suppressed in the resin injection process, while achieving a balance between elastic modulus, low water absorption, and toughness. This is preferable in that an excellent cured resin product can be obtained.
  • component [B] is preferably liquid at 23°C. Since the component [B] is liquid, the viscosity of the epoxy resin composition for RTM of the present invention can be lowered, and it can be suitably used for injection molding of fiber-reinforced composite materials.
  • component [E] At least one solid epoxy resin selected from the group consisting of dicyclopentadiene-type epoxy resin, biphenyl-type epoxy resin, phenol aralkyl-type epoxy resin, and naphthalene-type epoxy resin is used as component [E].
  • the content is preferably 50 parts by mass or more, and more preferably 20 parts by mass or more and 40 parts by mass or less.
  • dicyclopentadiene type epoxy resins and naphthalene type epoxy resins are preferably used because they have an excellent balance between elastic modulus and toughness.
  • Particularly preferably used is a dicyclopentadiene type epoxy resin.
  • a dicyclopentadiene type epoxy resin In addition to the effect of lowering the water absorption rate of the cured epoxy resin product, it is possible to increase the fracture toughness of the cured resin product.
  • dicyclopentadiene type epoxy resins that can be used as component [E] include “EPICLON (registered trademark)” HP-7200L, “EPICLON (registered trademark)” HP-7200, “EPICLON (registered trademark)” HP- 7200H, “EPICLON (registered trademark)” HP-7200HH (manufactured by DIC Corporation), and the like.
  • biphenyl-type epoxy resins that can be used as component [E] include "jER (registered trademark)" YX-4000 (manufactured by Mitsubishi Chemical Corporation).
  • phenolic aralkyl epoxy resins that can be used as component [E] include NC-3000H, NC-3000, NC-3000L, NC-7000, NC-7300, NC-2000, and NC-2000L (including Nipponka Co., Ltd. (manufactured by Yakuhin Co., Ltd.).
  • naphthalene-type epoxy resins that can be used as component [E] include "EPICLON (registered trademark)” HP-4770, “EPICLON (registered trademark)” HP-4700 (manufactured by DIC Corporation), etc. It will be done.
  • the epoxy resin composition for RTM of the present invention must satisfy all of the following conditions 1 to 4.
  • Condition 1 Viscosity at 110°C is 1 mPa ⁇ s or more and 200 mPa ⁇ s or less
  • Condition 2 Mass reduction rate after heating at 110°C for 30 minutes is 0.3% by mass or less
  • Condition 3 Curing at 180°C for 2 hours
  • Condition 4 The rubber state elastic modulus of the cured resin obtained by curing is 2 MPa or more and 8 MPa or less: The water absorption rate of the cured resin obtained by curing at 180° C. for 2 hours is 1% or more and 3% or less.
  • the epoxy resin composition for RTM of the present invention needs to have a viscosity at 110°C of 1 mPa ⁇ s or more and 200 mPa ⁇ s or less, preferably 2 mPa ⁇ s or more and 100 mPa ⁇ s or less, It is more preferably 5 mPa ⁇ s or more and 45 mPa ⁇ s or less, and even more preferably 5 mPa ⁇ s or more and 40 mPa ⁇ s or less.
  • the epoxy resin composition for RTM of the present invention has excellent impregnating properties into the reinforcing fiber base material in the resin injection process, so the epoxy resin composition for RTM of the present invention can be applied to large structural materials. It can be suitably used.
  • the viscosity of such an epoxy resin composition for RTM is measured using a dynamic viscoelasticity device under the following conditions: measurement mode: parallel plate (25 mm ⁇ , gap 1.0 mm), shear rate: 100 s ⁇ 1 , and set temperature 110° C. .
  • measurement mode parallel plate (25 mm ⁇ , gap 1.0 mm)
  • shear rate 100 s ⁇ 1
  • set temperature 110° C. the epoxy resin composition was set on a parallel plate heated to 110° C. within 5 minutes after preparation, with a gap of 1.0 mm, and the measurement was started.
  • the complex viscosity at the time when the sample temperature rises to 110° C. is defined as ⁇ 0 .
  • the epoxy resin composition for RTM of the present invention must have a mass reduction rate of 0.3% by mass or less after heating at 110°C for 30 minutes, and preferably 0.2% by mass or less. It is preferably 0.15% by mass or less, and more preferably 0.15% by mass or less. Within this range, volatilization of the resin component during the molding process is suppressed, resulting in a fiber-reinforced composite material with a high Vf and exhibiting excellent mechanical properties.
  • the mass reduction rate of such an epoxy resin composition for RTM is determined by putting about 2 g of the epoxy resin composition into an aluminum cup with an inner diameter of 50 mm, weighing it with an electronic balance, and then heating it in a blower oven set at 110 ° C. The sample was taken out after 30 minutes, cooled to room temperature, weighed again, and the mass reduction rate of the resin was calculated.
  • the epoxy resin composition for RTM of the present invention must have a rubber state modulus of the cured resin obtained by curing the epoxy resin composition at 180°C for 2 hours in the range of 2 MPa or more and 8 MPa or less. It is preferably in the range of 2 MPa or more and 6 MPa or less, and more preferably in the range of 2 MPa or more and 5 MPa or less. Within this range, the cured resin obtained by curing the epoxy resin composition for RTM of the present invention exhibits excellent fracture toughness while maintaining elastic modulus and heat resistance.
  • the fiber-reinforced composite material obtained as the matrix resin has excellent impact resistance. If the rubber state elastic modulus is greater than 8 MPa, the above effects cannot be obtained. When the rubber state elastic modulus is less than 2 MPa, the fracture toughness is improved, but the elastic modulus and heat resistance of the cured epoxy resin are reduced, so that the compressive strength under wet heat of the fiber reinforced composite material is reduced.
  • the rubber state elastic modulus of such a cured resin is determined using a dynamic viscoelasticity measuring device.
  • a test piece with a thickness of 2.0 mm, a width of 12.7 mm, and a length of 45 mm is set in a solid twisting jig, and the temperature is increased at a heating rate of 5°C. /min, a frequency of 1 Hz, and a strain amount of 0.08% in a temperature range of 40° C. or higher and 260° C. or lower.
  • the rubber state elastic modulus is the storage elastic modulus at a temperature 50° C. higher than the glass transition temperature in the obtained storage elastic modulus vs. temperature graph.
  • the glass transition temperature is the temperature at the intersection of the tangent line drawn to the glass state and the tangent line drawn to the glass transition temperature region in the obtained storage modulus versus temperature graph.
  • the epoxy resin composition for RTM of the present invention must have a water absorption rate of 1% to 3% of the cured resin obtained by curing the epoxy resin composition at 180°C for 2 hours. It is preferably in the range of 1% or more and 2.5% or less, more preferably in the range of 1.5% or more and 2.2% or less, and in the range of 1.5% or more and 1.9% or less. It is more preferable that Within this range, the cured resin obtained by curing the epoxy resin composition for RTM of the present invention has a high elastic modulus under moist heat. The composite material has excellent compressive strength under wet heat conditions. If the water absorption rate is greater than 3%, the above effects cannot be obtained.
  • the adhesion between the cured epoxy resin and the reinforcing fibers in the fiber-reinforced composite material decreases, resulting in a decrease in the impact resistance of the fiber-reinforced composite material.
  • the water absorption rate of the cured resin product is calculated from the difference in mass before and after immersing a test piece with a thickness of 2.0 mm, width of 10 mm, and length of 60 mm in boiling water for 48 hours.
  • the value obtained by dividing the total number of moles of active hydrogen (Mh) of component [B] contained in the epoxy resin composition for RTM of the present invention by the total number of moles of active epoxy groups (Me) contained in all epoxy resins (Mh /Me) is preferably in the range of 0.8 or more and 1.1 or less, more preferably 0.9 or more and 1.0 or less.
  • the total epoxy resin refers to all of the epoxy resin components contained in the epoxy resin composition for RTM of the present invention.
  • the modulus of elasticity is high, and when this is used as a matrix resin, a fiber-reinforced composite material exhibiting higher compression properties under wet heat can be obtained. In addition, it has excellent heat resistance after wetting, so it is suitably used as a fiber-reinforced composite material for structural materials.
  • the total number of moles of active epoxy groups contained in all epoxy resins is the sum of the number of moles of each epoxy resin active group contained in the epoxy resin composition for RTM, and is expressed by the following formula.
  • Ru. Me (mass of epoxy resin A/epoxy equivalent of epoxy resin A)+(mass of epoxy resin B/epoxy equivalent of epoxy resin B)+...+(mass of epoxy resin W/epoxy equivalent of epoxy resin W) ).
  • the heat resistance when wet (wet Tg) of the cured resin obtained by curing the epoxy resin composition at 180°C for 120 minutes is higher than the heat resistance when dry (wet Tg). It has the characteristic that the degree of decrease is small compared to dry Tg).
  • the reduction rate can be expressed from the ratio of wet Tg to dry Tg (wet Tg/dry Tg), and wet Tg/dry Tg is preferably in the range of 0.9 or more and 1.0 or less. , more preferably 0.93 or more and 1.0 or less.
  • Wet Tg can be evaluated, for example, from the following DMA measurement using a test piece obtained by immersing a cured resin product in boiling water for 48 hours.
  • the glass transition temperature (Tg) of the cured resin material of the present invention can be calculated from a scatter diagram of storage modulus and temperature obtained by temperature increase measurement of DMA measurement (dynamic viscoelasticity measurement).
  • the glass transition temperature is the temperature at the intersection of the tangent line drawn to the glass region and the tangent line drawn to the glass transition region in the above scatter diagram.
  • the storage elastic modulus in a rubber state is the storage elastic modulus at a temperature 50° C. higher than the glass transition temperature.
  • the epoxy resin composition for RTM of the present invention has a flexural modulus (E 82 ) of the cured resin obtained by curing the epoxy resin composition at 180°C for 120 minutes at a wet heat of 82°C of 50% at 23°C. It also has the characteristic that the degree of decrease is small compared to the bending elastic modulus (E 23 ) of RH.
  • the reduction rate can be expressed from the ratio of E 82 and E 23 (E 82 /E 23 ), and E 82 /E 23 is preferably 0.75 or more, more preferably 0.80 or more. Yes, and more preferably 0.85 or more.
  • the epoxy resin composition for RTM used in the present invention uses an epoxy resin different from components [A], [C], and [E] as component [F] to the extent that the effects of the present invention are not lost. Good too.
  • epoxy resins examples include bisphenol A epoxy resins, bisphenol F epoxy resins, phenol novolak epoxy resins, triglycidylaminophenol epoxy resins, and the like. These may be used alone or in combination.
  • Examples of commercially available bisphenol A epoxy resins include “jER (registered trademark)” 828 and “jER (registered trademark)” 825 (all manufactured by Mitsubishi Chemical Corporation).
  • the epoxy resin composition for RTM of the present invention may be kneaded using a machine such as a kneader, a planetary mixer, a three-roll extruder, or a twin-screw extruder, or, if uniform kneading is possible, You can also mix by hand using a beaker and spatula.
  • a machine such as a kneader, a planetary mixer, a three-roll extruder, or a twin-screw extruder, or, if uniform kneading is possible, You can also mix by hand using a beaker and spatula.
  • the epoxy resin composition for RTM of the present invention exhibits viscosity stability for a long time at relatively high temperatures and has excellent impregnating properties into reinforcing fiber base materials, so it is particularly suitable for use in the RTM method.
  • a reinforcing fiber base material or preform is placed in a mold, a liquid matrix resin is injected into the mold to impregnate the reinforcing fibers, and the epoxy resin composition is then heated. This is a method of curing to obtain a fiber-reinforced composite material that is a molded article.
  • the temperature at the time of injecting the matrix resin in the method for producing a fiber-reinforced composite material using the epoxy resin composition for RTM of the present invention is not particularly limited, but the reinforcing fiber base is placed in a mold preheated to 70°C to 190°C. It is preferable to install the material and inject the RTM epoxy resin composition of the present invention.
  • the epoxy resin composition has a lower viscosity and the injection time is shortened, making it excellent in mass production.
  • the thermosetting temperature does not need to be the same as the temperature at the time of injection, and the time required for thermosetting may be shortened by increasing the temperature as appropriate.
  • the mold used in the RTM method may be a closed mold made of a rigid material, or an open mold made of a rigid material and a flexible film (bag).
  • the reinforcing fiber substrate can be placed between an open mold of rigid material and a flexible film.
  • the rigid material various existing materials such as metal such as steel and aluminum, fiber reinforced plastic (FRP), wood, and plaster are used.
  • FRP fiber reinforced plastic
  • Polyamide, polyimide, polyester, fluororesin, silicone resin, etc. are used as the material for the flexible film.
  • the reinforcing fibers used in the reinforcing fiber base material used in the fiber-reinforced composite material of the present invention are not particularly limited; , boron fiber, alumina fiber, silicon carbide fiber, etc. can be used. Two or more of these fibers may be used in combination. From the viewpoint of obtaining a lightweight and highly rigid fiber-reinforced composite material, it is preferable to use carbon fiber.
  • the fiber-reinforced composite material of the present invention has excellent mechanical properties, compressive strength under wet heat, and impact resistance, so it can be used in aircraft parts such as fuselages, main wings, tails, rotor blades, fairings, cowls, doors, seats, interior materials, etc.
  • Spacecraft parts such as motor cases and main wings, artificial satellite parts such as structures and antennas, automobile parts such as outer panels, chassis, aerodynamic parts, and seats, railway vehicle parts such as structures and seats, ship parts such as hulls and seats, etc. It can be preferably used for many structural materials.
  • the materials used in this example, the preparation method of samples, etc., and the evaluation method are as follows.
  • Component [B] At least one aromatic amine curing agent selected from the group consisting of alkylbenzenediamine and methylenebisaniline (2-1) Alkylbenzenediamine [B]-1: “jER Cure (registered trademark) )” WA (manufactured by Mitsubishi Chemical Corporation, active hydrogen equivalent: 45 g/eq), [B]-2: “Ethacure (registered trademark)” 300 (manufactured by Albemarle, active hydrogen equivalent: 54 g/eq), (2-2) Methylenebisaniline [B]-3: “Lonzacure (registered trademark)” M-MIPA (manufactured by Lonza, active hydrogen equivalent: 78 g/eq), [B]-4: “Lonzacure (registered trademark)” M-CDEA (manufactured by Lonza, active hydrogen equivalent: 95 g/eq).
  • aromatic amine curing agent selected from the group consisting of alkylbenzenediamine and methylenebisani
  • Component [D] Mixture of core-shell type rubber particles and component [A] or component [F] [D]-1 “Kane Ace (registered trademark)” MX-416 (glycidylamine type epoxy resin (component [ Corresponding to A]) 75% by mass, and 25% by mass of butadiene-based core-shell type rubber particles, epoxy equivalent: 148g/eq), [D]-2 "Kane Ace (registered trademark)” MX-267 (bisphenol F type epoxy resin (corresponding to component [F]) 63% by mass, and butadiene core-shell type rubber particles 37% by mass, epoxy equivalent: 270g/ eq), (manufactured by Kaneka Corporation).
  • Component [E] at least one solid epoxy resin selected from the group consisting of dicyclopentadiene type epoxy resin, biphenyl type epoxy resin, phenol aralkyl type epoxy resin, and naphthalene type epoxy resin
  • ⁇ Method for preparing epoxy resin composition for RTM> A predetermined amount of components other than component [B] and other curing agent components were placed in a stainless steel beaker, the temperature was raised to 60 to 150° C., and the components were appropriately kneaded until they were mutually dissolved to obtain an epoxy base liquid.
  • Component [B] and other curing agent components were added to a separate container, and if necessary, they were heated to make them compatible, thereby obtaining a curing agent liquid.
  • An epoxy resin composition for RTM was obtained by mixing a predetermined amount of epoxy base liquid and curing agent liquid at about 60°C and kneading for 3 minutes with a planetary mixer.
  • the composition is as shown in Tables 1-4.
  • Flexural modulus of cured resin product (humid heat 82°C): E 82 and water absorption evaluation method (3) Flexural modulus of cured resin product (23°C, 50% RH): Evaluation method of E 23 A cured resin product was obtained in the same manner, and a test piece with a width of 10 mm and a length of 60 mm was cut out, and then immersed in boiling water for 48 hours. The taken out test piece was tested using an Instron universal testing machine (manufactured by Instron) with a span of 32 mm and a crosshead speed of 10 mm/min in a high temperature environment (82°C) according to JIS K7171 (1994).
  • Instron universal testing machine manufactured by Instron
  • Point bending was performed and the bending elastic modulus (moist heat 82°C) was measured.
  • a test piece with a width of 12.7 mm and a length of 45 mm was cut from this cured resin product, and using a dynamic viscoelasticity measuring device (ARES-G2, manufactured by TA Instruments), a solid torsion jig was placed with a distance between chunks of 30 mm.
  • the test piece was set in a solid twisting jig, and measurements were taken over a temperature range of 40 to 260°C at a heating rate of 5°C/min, a frequency of 1Hz, and a strain of 0.08%. .
  • the glass transition temperature (dry Tg) was defined as the temperature at the intersection of the tangent line drawn to the glass state and the tangent line drawn to the glass transition temperature region in the obtained storage modulus versus temperature graph.
  • the rubber state elastic modulus was defined as the storage elastic modulus at a temperature 50° C. higher than the glass transition temperature in the obtained storage elastic modulus vs. temperature graph.
  • Example 1 As epoxy resins, 25 parts by mass of "Sumi Epoxy (registered trademark)” ELM-434VL (component [A]), 30 parts by mass of “TOREP (registered trademark)” A-204E (component [C]), and "EPICLON (registered trademark)” were used as epoxy resins.
  • ⁇ 0 was evaluated according to the method for evaluating the viscosity ( ⁇ 0 ) at 110° C. of the epoxy resin composition for RTM (1) above, and it was found to be 40 mPa ⁇ s. Furthermore, the mass reduction rate was evaluated according to the method for evaluating the mass loss rate at 110° C. of the epoxy resin composition for RTM (2) above, and it was found to be 0.12% by mass.
  • Example 2 to 21 An epoxy resin composition for RTM and a cured resin were produced in the same manner as in Example 1, except that the resin compositions were changed as shown in Tables 1 to 3, respectively.
  • ⁇ 0 of each example is 18 mPa ⁇ s or more and 50 mPa ⁇ s or less
  • the mass reduction rate is 0.07 mass% or more and 0.20 mass% or less
  • the rubber state elastic modulus is in the range of 3.5 MPa or more and 8.0 MPa or less. It was within.
  • the epoxy resin composition was evaluated in the same manner as in Example 1 for E 82 and E 23 , wet and dry Tg, water absorption, fracture toughness, rubber state modulus, ⁇ 0 , and mass loss rate.
  • the epoxy resin composition contains component [A] and component [B], but does not contain component [C], and instead contains bisphenol F type epoxy resin and TGpAP, which are other epoxy resins.
  • E 82 was low at 2.40 GPa, and E 82 /E 23 was 0.71, which showed a large decrease in the elastic modulus after wetting.
  • the dry Tg was 184°C
  • the wet Tg was 160°C
  • the wet Tg/dry Tg was 0.87, which was a large decrease in heat resistance after wetting, and the water absorption rate was also high, at 2.8%.
  • the fracture toughness value was 0.8 MPa ⁇ m 0.5 , which was insufficient.
  • the rubber state elastic modulus was 12.0 MPa, which was outside the range.
  • the epoxy resin composition was evaluated in the same manner as in Example 1 for E 82 and E 23 , wet and dry Tg, water absorption, fracture toughness, rubber state modulus, ⁇ 0 , and mass loss rate.
  • the epoxy resin composition contains component [A] and component [B], but does not contain component [C].
  • E 82 was as low as 2.40 GPa, and E 82 /E 23 was 0.73, indicating a large decrease in the elastic modulus after wetting.
  • the dry Tg was 182°C
  • the wet Tg was 158°C
  • the wet Tg/dry Tg was 0.87, which was a large decrease in heat resistance after wetting
  • the water absorption rate was also high at 2.7%.
  • the fracture toughness value was 0.9 MPa ⁇ m 0.5 , which was insufficient.
  • the rubber state elastic modulus was 10.1 MPa, which was outside the range.
  • the mass reduction rate was 0.41% by mass, which was outside the range.
  • the epoxy resin composition was evaluated in the same manner as in Example 1 for E 82 and E 23 , wet and dry Tg, water absorption, fracture toughness, rubber state modulus, ⁇ 0 , and mass loss rate.
  • ⁇ 0 is 230 mPa ⁇ s, which is outside the range, and the water absorption rate of the cured resin product is also 3. It was outside the range at .5%.
  • the rubber state elastic modulus was 10.0 MPa, which was outside the range.
  • the epoxy resin composition had a low elastic modulus under moist heat and a low heat resistance under wet conditions, and a high water absorption rate of 2.7%. Further, the fracture toughness value was 0.8 MPa ⁇ m 0.5 , which was insufficient.
  • the rubber state elastic modulus was 9.8 MPa, which was outside the range.
  • the fracture toughness value was 0.8 MPa ⁇ m 0.5 , which was insufficient.
  • the elastic modulus under moist heat was 2.40 GPa, which was insufficient.
  • the fiber reinforced composite material properties of each example are as follows.
  • Example 1' A fiber-reinforced composite material was produced using the resin composition shown in Table 5 according to ⁇ Preparation of fiber-reinforced composite material> above.
  • Example 6', 12', 16', 18' Fiber-reinforced composite materials were produced and evaluated in the same manner as in Example 1, except that the resin compositions were changed as shown in Table 5.
  • OHC 23 was 311 MPa
  • OHC 82 was 200 MPa
  • OHC 82 /OHC 23 was as low as 0.64.
  • CAI was 269 MPa
  • the impact resistance was also insufficient.
  • This fiber-reinforced composite material had an OHC 23 of 264 MPa, showing low compressive strength at room temperature, and an OHC 82 of 191 MPa, showing low compressive properties under wet heat conditions. Further, the CAI was 255 MPa, and the impact resistance was also insufficient.
  • the epoxy resin composition for RTM of the present invention can provide a cured epoxy resin product that has low viscosity, low volatility, and high elastic modulus and fracture toughness under moist heat.
  • the fiber-reinforced composite material made of the epoxy resin composition has excellent compressive properties and impact resistance under wet heat, so it can be suitably used for aerospace parts and structural members for general industry.

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PCT/JP2023/010373 2022-03-17 2023-03-16 Ｒｔｍ用エポキシ樹脂組成物、樹脂硬化物、繊維強化複合材料およびその製造方法 Ceased WO2023176935A1 (ja)

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