WO2022202086A1 - 熱硬化性樹脂組成物、プリプレグ、繊維強化複合材及び高圧ガス容器 - Google Patents

熱硬化性樹脂組成物、プリプレグ、繊維強化複合材及び高圧ガス容器 Download PDF

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WO2022202086A1
WO2022202086A1 PCT/JP2022/007767 JP2022007767W WO2022202086A1 WO 2022202086 A1 WO2022202086 A1 WO 2022202086A1 JP 2022007767 W JP2022007767 W JP 2022007767W WO 2022202086 A1 WO2022202086 A1 WO 2022202086A1
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resin composition
thermosetting resin
prepreg
epoxy
mass
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PCT/JP2022/007767
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English (en)
French (fr)
Japanese (ja)
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孝介 池内
信彦 松本
展義 大西
大暉 若原
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三菱瓦斯化学株式会社
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Application filed by 三菱瓦斯化学株式会社 filed Critical 三菱瓦斯化学株式会社
Priority to EP22774884.5A priority Critical patent/EP4317238A4/en
Priority to JP2023508836A priority patent/JPWO2022202086A1/ja
Priority to US18/283,701 priority patent/US20240166816A1/en
Priority to CN202280022833.0A priority patent/CN117043222A/zh
Publication of WO2022202086A1 publication Critical patent/WO2022202086A1/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
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/02—Polyamines
    • C08G73/0273—Polyamines containing heterocyclic moieties in the main chain
    • 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
    • C08G59/182—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 using pre-adducts of epoxy compounds with curing agents
    • C08G59/184—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 using pre-adducts of epoxy compounds with curing agents with amines
    • 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
    • C08G59/02—Polycondensates containing more than one epoxy group per molecule
    • C08G59/04—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof
    • C08G59/06—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols
    • C08G59/066—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols with chain extension or advancing agents
    • 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
    • C08G59/28—Di-epoxy 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
    • C08G59/32—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
    • C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
    • C08G59/4014—Nitrogen containing compounds
    • C08G59/4021—Ureas; Thioureas; Guanidines; Dicyandiamides
    • 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
    • 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
    • C08J5/244—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres using glass 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
    • 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
    • C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
    • C08J2379/02—Polyamines

Definitions

  • the present invention relates to a thermosetting resin composition, a prepreg using the thermosetting resin composition, a fiber-reinforced composite material using the prepreg, and a high-pressure gas container using the fiber-reinforced composite material.
  • CNG vehicles environment-friendly natural gas vehicles
  • FCV fuel cell vehicles
  • a fuel cell vehicle uses a fuel cell as a power source, and it is essential to develop a hydrogen station that compresses the fuel hydrogen to a high pressure and fills the vehicle.
  • Steel tanks have hitherto been used as hydrogen stations for fuel cell vehicles, or high-pressure gas storage tanks used as fuel tanks for vehicles such as CNG vehicles and fuel cell vehicles.
  • the development of lighter weight high-pressure gas storage tanks using resin materials has been progressing. By reducing the weight of the on-board fuel tank, there are merits such as improving the fuel efficiency of the vehicle equipped with the fuel tank.
  • Patent Document 1 a resin liner having a resin such as nylon as a main material having gas barrier properties and an elastomer containing an additive having hydrogen adsorption performance, and an FRP layer laminated on the outer peripheral surface A high pressure hydrogen tank is disclosed.
  • a structure that is a coating of a high-pressure hydrogen storage tank has a mesogenic group in the molecule, and a thermosetting resin such as an epoxy monomer capable of forming a smectic structure by a curing reaction
  • a structure which has a cured layer containing a cured product of a resin composition containing mica and a carbon fiber-containing layer on one or both sides of the cured layer.
  • the coating of the high-pressure hydrogen storage tank disclosed in Patent Document 2 includes a cured product of a resin composition containing a thermosetting resin such as an epoxy monomer and mica, and carbon fibers. By reinforcing the resin with carbon fiber, a high-strength material can be obtained that can also be applied to high-pressure hydrogen storage tanks.
  • a thermosetting resin disclosed in Patent Document 2 the hydrogen gas barrier property is not sufficient, and further improvement is required.
  • a fast-curing thermosetting resin (composition) there is a problem that shelf life and pot life are short and workability is lowered.
  • a tow prepreg is produced using such a thermosetting resin (composition)
  • there is a tendency for the moldability to deteriorate during filament winding molding when a tow prepreg is produced using such a thermosetting resin (composition), there is a tendency for the moldability to deteriorate during filament winding molding.
  • An object of the present invention is to provide a thermosetting resin composition capable of forming a tow prepreg having a high barrier property against hydrogen gas and the like, a long shelf life and a long pot life, good workability, and excellent moldability, and the thermosetting property.
  • An object of the present invention is to provide a fiber-reinforced composite material and a high-pressure gas container using a resin composition.
  • the present inventors have proposed an adduct resin (X) which is a reaction product of an amine-epoxy resin (A) and a given epoxy modifier (B), and an epoxy resin curing agent (C), wherein the adduct resin (X ) is a reaction product obtained by reacting 1 to 20 parts by mass of the epoxy modifier (B) with 100 parts by mass of the amine-epoxy resin (A).
  • adduct resin (X ) is a reaction product obtained by reacting 1 to 20 parts by mass of the epoxy modifier (B) with 100 parts by mass of the amine-epoxy resin (A).
  • the present invention relates to the following [1] to [4].
  • [1] including an adduct resin (X) which is a reaction product of an amine epoxy resin (A) and an epoxy modifier (B) below, and an epoxy resin curing agent (C),
  • the adduct resin (X) is a thermosetting reaction product obtained by reacting 100 parts by mass of the amine-epoxy resin (A) with 1 to 20 parts by mass of the epoxy modifier (B). Resin composition.
  • thermosetting resin composition capable of forming a tow prepreg having high barrier properties against hydrogen gas and the like, long shelf life and pot life, good workability, and excellent moldability.
  • a fiber-reinforced composite material using the thermosetting resin composition of the present invention has a high gas barrier property and is suitable as a material for composing a high-pressure gas container such as a high-pressure gas storage tank.
  • thermosetting resin composition comprises an adduct resin (X) which is a reaction product of an amine-epoxy resin (A) and an epoxy modifier (B) described below, and an epoxy resin curing agent (C).
  • the adduct resin (X) is a reaction product obtained by reacting 1 to 20 parts by mass of the epoxy modifier (B) with 100 parts by mass of the amine-epoxy resin (A).
  • thermosetting resin composition of the present invention having the above structure can form a tow prepreg having a long shelf life and pot life, good workability, and excellent moldability.
  • gas barrier properties such as hydrogen gas can be improved.
  • the amine-epoxy resin (A) is modified in advance with a predetermined epoxy modifier (B) at a predetermined ratio to form an adduct resin (X), thereby improving the gas barrier properties derived from the amine-epoxy resin (A). It is possible to adjust the curing speed when curing with the epoxy resin curing agent (C) to an appropriate range without lowering it, improve the shelf life and pot life, and improve the moldability when forming the tow prepreg. guessed. In particular, it is believed that the prescribed epoxy modifier (B) is less likely to inhibit the gas barrier properties of the amine-epoxy resin (A).
  • the thermosetting resin composition, prepreg and fiber-reinforced composite material of the present invention are described below.
  • the thermosetting resin composition of the present invention comprises an adduct resin (X) which is a reaction product of an amine-epoxy resin (A) and an epoxy modifier (B) described below, and an epoxy resin curing agent (C).
  • the adduct resin (X) is a reaction product obtained by reacting 1 to 20 parts by mass of the epoxy modifier (B) with 100 parts by mass of the amine-epoxy resin (A).
  • the amine-epoxy resin (A) (hereinafter also simply referred to as “component (A)”) is not particularly limited as long as it is a polyfunctional epoxy resin having an amino group. Polyfunctional epoxy resins containing ring or alicyclic structures in the molecule are preferred.
  • the amine-epoxy resin (A) include an epoxy resin having a glycidylamino group derived from metaxylylenediamine, an epoxy resin having a glycidylamino group derived from paraxylylenediamine, 1,3-bis Epoxy resins having glycidylamino groups derived from (aminomethyl)cyclohexane, epoxy resins having glycidylamino groups derived from 1,4-bis(aminomethyl)cyclohexane, and glycidylamino groups derived from diaminodiphenylmethane Examples include epoxy resins and epoxy resins having a glycidylamino group derived from para-aminophenol. In order to improve various performances such as flexibility, impact resistance, and resistance to moist heat, two or more of the above epoxy resins may be mixed in an appropriate ratio and used.
  • the amine-epoxy resin (A) preferably has a skeleton represented by the following general formula (1). Furthermore, from the viewpoint of gas barrier properties, the amine-epoxy resin (A) consists of an epoxy resin having a glycidylamino group derived from meta-xylylenediamine and an epoxy resin having a glycidylamino group derived from para-xylylenediamine. Those containing at least one selected from the group as a main component are preferred, and those containing an epoxy resin having a glycidylamino group derived from metaxylylenediamine as a main component are more preferred.
  • the term "main component" as used herein means that other components may be included within the scope of the present invention, preferably 50 to 100% by mass, more preferably 70 to 100% by mass of the total. , more preferably 90 to 100% by mass.
  • Epoxy modifier (B) The epoxy modifier (B) (hereinafter also simply referred to as “component (B)") used in the present invention is used to obtain a tow prepreg with excellent moldability without deteriorating the gas barrier properties of the amine-epoxy resin (A).
  • At least one selected from the group consisting of Component (B) is preferably at least one selected from the group consisting of meta-xylylenediamine and 4,4′-diaminodiphenylmethane, from the viewpoint of achieving both gas barrier properties and flexibility, and has gas barrier properties, flexibility, and shelf life.
  • 4,4′-Diaminodiphenylmethane is more preferable from the viewpoint of life and pot life and low viscosity.
  • Adduct resin (X) is the reaction product of component (A) and component (B) above.
  • Adduct resin (X) is the reaction product of component (A) and component (B) above.
  • the curing speed when curing with the epoxy resin curing agent (C) described later can be adjusted to an appropriate range. As a result, the shelf life and pot life can be improved, the amount of heat generated in the curing reaction can be moderately suppressed, and the safety of the work can be easily ensured.
  • the reaction of component (A) and component (B) is preferably carried out by mixing component (A) and component (B) under conditions of preferably 0 to 100°C, more preferably 0 to 70°C, and then preferably is under an inert gas atmosphere, more preferably under a nitrogen atmosphere, preferably at 30 to 180 ° C., more preferably 30 to 150 ° C., preferably for 1 to 24 hours, more preferably 1 to 15 hours, component ( It is carried out by carrying out the addition reaction while stirring A) and component (B).
  • the adduct resin (X) is 1 to 20 parts by mass, more preferably 1 to 15 parts by mass, more preferably 1 to 12 parts by mass, more preferably 1 to 12 parts by mass, based on 100 parts by mass of the component (A). More preferably 1 to 8 parts by mass, more preferably 1 to 5 parts by mass of the reaction product obtained by the reaction.
  • the amount of the component (B) blended per 100 parts by mass of the component (A) is 1 part by mass or more, the shelf life and pot life are long, the workability is good, and a tow prepreg with excellent moldability can be formed. A flexible resin composition is obtained.
  • the amount is within a range of 20 parts by mass or less, a thermosetting resin composition that can form a tow prepreg having high barrier properties against hydrogen gas and the like and excellent moldability can be obtained.
  • epoxy resin curing agent (C) Specific examples of the epoxy resin curing agent (C) (hereinafter also simply referred to as “component (C)”) used in the present invention include polyphenol compounds, amine compounds, imidazole derivatives, dicyandiamide, urea compounds, and the like. Among them, from the viewpoint of the potential to work favorably on pot life, it is preferably at least one selected from the group consisting of imidazole, tertiary amine, dicyandiamide and dichlorophenyldimethylurea (DCMU), more preferably tertiary amine and dicyandiamide. and dichlorophenyldimethylurea, more preferably dicyandiamide. In addition, as a tertiary amine, an epoxy adduct amine is preferable.
  • the blending ratio of the adduct resin (X) and the epoxy resin curing agent (C) in the thermosetting resin composition is generally the standard when preparing an epoxy resin reaction product by reacting the epoxy resin and the epoxy resin curing agent. It may be within a reasonable blending range.
  • the component (C) is preferably 2 to 30 parts by mass, more preferably 2 to 25 parts by mass with respect to 100 parts by mass of the amine-epoxy resin (A) when forming the adduct resin (X). , more preferably 3 to 20 parts by mass, still more preferably 3 to 15 parts by mass, still more preferably 3 to 12 parts by mass, and even more preferably 5 to 10 parts by mass.
  • thermosetting resin composition capable of forming a tow prepreg which is also excellent in
  • the total content of the adduct resin (X) and the epoxy resin curing agent (C) in the thermosetting resin composition is preferably 10% by mass or more, more preferably 20% by mass, from the viewpoint of obtaining the effects of the present invention. Above, more preferably 30% by mass or more and 100% by mass or less.
  • thermosetting resin composition used in the present invention preferably further contains a solvent from the viewpoint of lowering the viscosity of the composition and enhancing the impregnating properties of the reinforcing fibers described below.
  • a non-reactive solvent is preferred as the solvent, and specific examples thereof include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methoxyethanol, 2-ethoxyethanol and 2-propoxyethanol.
  • the solvent has 8 or less carbon atoms, such as an alcohol solvent, an ester solvent, and a carbonization solvent.
  • At least one selected from the group consisting of hydrogen-based solvents is preferable, and at least one selected from the group consisting of methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, ethyl acetate, and toluene. More preferably, at least one selected from the group consisting of methanol and ethyl acetate.
  • the content is not particularly limited, but from the viewpoint of enhancing the impregnation of the reinforcing fibers of the thermosetting resin composition, preferably is 5% by mass or more, more preferably 10% by mass or more, still more preferably 15% by mass or more, still more preferably 20% by mass or more, still more preferably 30% by mass or more, and even more preferably 40% by mass or more. , from the viewpoint of ease of removal of the solvent, it is preferably 90% by mass or less, more preferably 80% by mass or less, and still more preferably 70% by mass or less.
  • the thermosetting resin composition further contains an unsaturated fatty acid amide having 14 to 24 carbon atoms (hereinafter also simply referred to as "unsaturated fatty acid amide”) from the viewpoint of improving the interfacial adhesion between the cured product and the reinforcing fiber obtained.
  • unsaturated fatty acid amide may be a fatty acid having 14 to 24 carbon atoms and having at least one unsaturated bond.
  • the number of unsaturated bonds in the unsaturated fatty acid is preferably 1-6, more preferably 1-4, still more preferably 1-2.
  • the unsaturated fatty acid amide preferably includes at least one selected from the group consisting of palmitoleamide, oleic acid amide, eicosenoic acid amide, and erucic acid amide.
  • the content of the unsaturated fatty acid amide in the thermosetting resin composition is preferably 0.1 to 20 parts by mass, more than It is preferably 0.2 to 15 parts by mass.
  • the thermosetting resin composition may further contain a thermoplastic resin, a reactive diluent, a non-reactive diluent other than the above solvent, a curing accelerator, a wetting agent, and Additives such as tackifiers, antifoaming agents, antirust agents, lubricants, pigments, oxygen scavengers, ultraviolet absorbers and antioxidants may be added.
  • the total content of the above additives in the composition is based on the total amount of 100 parts by mass of the adduct resin (X) and the epoxy resin curing agent (C). It is preferably 15.0 parts by mass or less, more preferably 10.0 parts by mass or less, and still more preferably 0.001 to 5.0 parts by mass.
  • the total content of the adduct resin (X) and the epoxy resin curing agent (C) in the solid content of the thermosetting resin composition is preferably 85% by mass or more, more preferably It is 90% by mass or more, more preferably 95% by mass or more, and the upper limit is 100% by mass.
  • the solid content of the thermosetting resin composition means the components excluding water and solvent in the thermosetting resin composition.
  • thermosetting resin composition is prepared by, for example, blending predetermined amounts of adduct resin (X), epoxy resin curing agent (C), solvent, and optional additives, and then using a known method and apparatus. It can be prepared by stirring and mixing.
  • the thermosetting resin composition of the present invention has high workability.
  • the solid content viscosity of the thermosetting resin composition when heated at 100° C. is preferably 1 Pa s or less, more preferably 0.8 Pa s or less, and still more preferably 0.5 Pa s or less. be.
  • the lower limit of the solid content viscosity is not particularly limited, it is usually 0.01 Pa ⁇ s or more.
  • the solid content viscosity of the thermosetting resin composition when heated at 100 ° C. is the component (solid content) excluding water and solvent in the thermoplastic resin composition, using a rheometer at a frequency of 1 Hz.
  • the storage elastic modulus G' and the loss elastic modulus G'' are measured while increasing the temperature from 60°C to 180°C at a temperature rate of 5°C/min.
  • the solid content viscosity of the thermosetting resin composition when heated at 100° C. can be measured by the method described in Examples.
  • the thermosetting resin composition of the present invention has a long shelf life and pot life.
  • the shelf life (-10°C) of the thermosetting resin composition is preferably 14 days or longer, more preferably 20 days or longer, and still more preferably 30 days or longer.
  • the pot life (23° C.) of the thermosetting resin composition is preferably 8 hours or longer, more preferably 12 hours or longer, and still more preferably 24 hours or longer.
  • the shelf life (-10°C) and pot life (23°C) of the thermosetting resin composition can be measured by the method described in Examples.
  • a cured product of the thermosetting resin composition of the present invention has high gas barrier properties.
  • the hydrogen gas permeability coefficient of the cured product is preferably 50 [ cc.mm/(m2.day.atm )] or less, more preferably 30 [ cc.mm/(m2.day.atm )] or less. and more preferably 20 [cc ⁇ mm/(m 2 ⁇ day ⁇ atm)] or less.
  • the hydrogen gas permeability coefficient of the cured product of the thermosetting resin composition can be measured under dry conditions at 23° C. by the method described in Examples.
  • the prepreg of the present invention is obtained by impregnating reinforcing fibers with the thermosetting resin composition.
  • the forms of reinforcing fibers used in the present invention include short fibers, long fibers, and continuous fibers.
  • long fibers or continuous fibers are preferable, and continuous fibers are more preferable, from the viewpoint of using prepregs and composite materials as materials constituting a high-pressure gas container.
  • short fibers have a fiber length of 0.1 mm or more and less than 10 mm
  • long fibers have a fiber length of 10 mm or more and 100 mm or less.
  • a continuous fiber refers to a fiber bundle having a fiber length exceeding 100 mm.
  • Shapes of continuous fibers include tows, sheets, tapes, and the like, and continuous fibers forming sheets or tapes include unidirectional (UD) materials, woven fabrics, non-woven fabrics, and the like.
  • the shape of the continuous fibers is preferably tow or tape, more preferably tow.
  • the number of continuous fiber bundles (number of filaments) constituting the tow is preferably 3K to 50K, more preferably 6K to 40K, from the viewpoint of easily obtaining high strength and high elastic modulus.
  • the average fiber length of the continuous fiber bundle is not particularly limited, but is preferably 1 to 10,000 m, more preferably 100 to 10,000 m, from the viewpoint of moldability.
  • the average fineness of the continuous fiber bundle is preferably 50 to 2000 tex (g/1000 m), more preferably 200 to 2000 tex, further preferably 200 to 2000 tex, more preferably 500 to 2000 tex.
  • the average tensile elastic modulus of the continuous fiber bundle is preferably 50-1000 GPa.
  • Materials for reinforcing fibers include inorganic fibers such as glass fiber, carbon fiber, basalt fiber, metal fiber, boron fiber, and ceramic fiber; aramid fiber, polyoxymethylene fiber, aromatic polyamide fiber, polyparaphenylene benzobisoxazole fiber, Organic fibers such as ultra-high molecular weight polyethylene fibers are included.
  • inorganic fibers are preferable from the viewpoint of obtaining high strength, and at least one selected from the group consisting of glass fiber, carbon fiber and basalt fiber is more preferable because it is lightweight and has high strength and high elastic modulus.
  • Carbon fiber is more preferred.
  • Examples of carbon fibers include polyacrylonitrile-based carbon fibers and pitch-based carbon fibers. Carbon fibers made from plant-derived raw materials such as lignin and cellulose can also be used.
  • the reinforcing fibers used in the present invention may be treated with a treating agent.
  • treatment agents include surface treatment agents and sizing agents.
  • Examples of the surface treatment agent include silane coupling agents.
  • Examples of the silane coupling agent include a silane coupling agent having a vinyl group, a silane coupling agent having an amino group, a silane coupling agent having an epoxy group, a silane coupling agent having a (meth)acrylic group, and a mercapto group.
  • a silane coupling agent etc. are mentioned.
  • the sizing agent examples include urethane sizing agents, epoxy sizing agents, acrylic sizing agents, polyester sizing agents, vinyl ester sizing agents, polyolefin sizing agents, polyether sizing agents, and carboxylic acid sizing agents. and the like, and one or more of these can be used in combination.
  • sizing agents in combination of two or more include urethane/epoxy sizing agents, urethane/acrylic sizing agents, urethane/carboxylic acid sizing agents, and the like.
  • the amount of the treatment agent is preferably less than that of the reinforcing fiber from the viewpoint of improving the interfacial adhesion between the thermosetting resin composition and the cured product, and further improving the strength and impact resistance of the resulting prepreg and composite material. is 0.001 to 5% by mass, more preferably 0.1 to 3% by mass, and still more preferably 0.5 to 2% by mass.
  • commercially available products can also be used as reinforcing fibers.
  • Examples of commercially available carbon fibers that are continuous fibers include trading card yarns “T300”, “T300B”, “T400HB”, “T700SC”, “T800SC”, “T800HB”, “T830HB”, “T830HB” manufactured by Toray Industries, Inc.
  • the content of the reinforcing fibers in the prepreg of the present invention is not particularly limited, but from the viewpoint of obtaining high strength and high elastic modulus, the volume fraction of the reinforcing fibers in the prepreg is preferably 0.10 or more, more preferably 0. 0.20 or more, more preferably 0.30 or more, and even more preferably 0.40 or more. From the viewpoint of gas barrier properties, impact resistance and moldability, it is preferably 0.98 or less, more preferably 0.95 or less, even more preferably 0.80 or less, and even more preferably 0.70 or less. Range.
  • the volume fraction Vf of reinforcing fibers in the prepreg can be calculated from the following formula.
  • Vf ⁇ mass of reinforcing fiber (g) / specific gravity of reinforcing fiber ⁇ ⁇ [ ⁇ mass of reinforcing fiber (g) / specific gravity of reinforcing fiber ⁇ + ⁇ mass of solid content of impregnated thermosetting resin composition (g ) / specific gravity of the solid content of the thermosetting resin composition ⁇ ]
  • the total content of solids and reinforcing fibers in the thermosetting resin composition constituting the prepreg of the present invention is preferably 70% by mass or more, more preferably 80% by mass or more, from the viewpoint of obtaining the effects of the present invention. , more preferably 90% by mass or more, and the upper limit is 100% by mass.
  • the shape of the prepreg of the present invention can be appropriately selected according to the form of the reinforcing fiber to be used and the application, and examples thereof include tow, sheet, tape and the like.
  • the types of prepregs that make up the sheets or tapes include unidirectional (UD) materials, woven fabrics, non-woven fabrics, and the like.
  • UD unidirectional
  • the shape of the prepreg is preferably tow prepreg or tape-like prepreg from the viewpoint of forming the outer layer by the method described later. , tow prepreg.
  • the method for producing the prepreg of the present invention is not particularly limited, and the prepreg can be produced according to a conventional method. For example, reinforcing a thermosetting resin composition containing the above adduct resin (X) which is a reaction product of an amine epoxy resin (A) and a predetermined epoxy modifier (B), an epoxy resin curing agent (C) and a solvent After the fibers are impregnated, they can be subjected to a drying step to remove the solvent and obtain a prepreg.
  • adduct resin containing the above adduct resin (X) which is a reaction product of an amine epoxy resin (A) and a predetermined epoxy modifier (B), an epoxy resin curing agent (C) and a solvent
  • the method for impregnating the reinforcing fibers with the thermosetting resin composition is not particularly limited, and a known method can be appropriately used depending on the form of the reinforcing fibers.
  • a continuous fiber bundle unwound from a roll is immersed in a resin bath filled with the thermosetting resin composition described above, impregnated with the composition, and then pulled out of the resin bath. mentioned. After that, a step of removing excess thermosetting resin composition using a squeezing roll or the like may be performed.
  • the impregnation of the thermosetting resin composition can also be carried out under pressurized conditions or reduced pressure conditions, if necessary.
  • the reinforcing fibers impregnated with the thermosetting resin composition are subjected to a drying process to remove the solvent.
  • the drying conditions in the drying step are not particularly limited, but are preferably conditions under which the solvent can be removed and curing of the thermosetting resin composition does not proceed excessively.
  • the drying temperature can be selected in the range of 30 to 120° C.
  • the drying time can be selected in the range of 10 seconds to 5 minutes.
  • the prepreg obtained through the above-mentioned drying process may be wound up once to form a prepreg product, or it may be continuously subjected to composite material production after the drying process without winding up.
  • the fiber-reinforced composite material of the present invention is a cured product of the prepreg, and contains a cured product of the thermosetting resin composition as a matrix resin and reinforcing fibers.
  • the thermosetting resin composition, reinforcing fibers, and preferred embodiments thereof are the same as those described for the prepreg.
  • the composite material is produced by preforming the prepreg of the present invention into a desired shape and then curing the prepreg.
  • the above-described tow prepreg is wound around the outer surface of a mandrel or liner, and then cured to produce a composite material having a desired shape.
  • the method of curing the prepreg in manufacturing the composite material is also not particularly limited, and the curing is performed by a known method at a temperature and time sufficient to cure the thermosetting resin composition contained in the prepreg.
  • the curing conditions of the prepreg depend on the thickness of the prepreg and the composite material to be formed. From the viewpoint of properties, the curing temperature is preferably in the range of 80 to 140° C. and the curing time is in the range of 10 minutes to 5 hours.
  • the composite material of the present invention is suitable for use in, for example, pipes, shafts, cylinders, tanks, etc., and is excellent in gas barrier properties such as hydrogen gas and impact resistance. , is suitable as a material for forming a high-pressure gas storage tank, which will be described later.
  • the high-pressure gas container of the present invention uses the fiber-reinforced composite material.
  • the high-pressure gas container of the present invention has good gas barrier properties against hydrogen gas and the like by using the composite material.
  • the high-pressure gas container of the present invention may be composed only of the above composite material, or may be partially composed of the above composite material.
  • a specific example of the high-pressure gas container of the present invention is a high-pressure gas storage tank.
  • the high-pressure gas storage tank preferably has a liner and an outer layer containing the fiber-reinforced composite material.
  • FIG. 1 is a schematic sectional view showing one embodiment of a high-pressure gas storage tank, which is a high-pressure gas container of the present invention.
  • the high-pressure gas storage tank 10 has a liner 1 and an outer layer 2.
  • the liner 1 is a pressure-resistant member having a space filled with gas, and is generally hollow.
  • the outer layer 2 contains the fiber-reinforced composite material of the present invention and is formed to cover the outer surface of the liner 1 .
  • the mouthpiece 3 has, for example, a substantially cylindrical shape, and is fitted and fixed between the liner 1 and the outer layer 2 .
  • a substantially cylindrical opening of the mouthpiece 3 functions as an opening of the high-pressure gas storage tank 10 .
  • the base 3 may be made of other metal such as stainless steel or aluminum, or may be made of resin.
  • the boss 4 is made of, for example, aluminum, is assembled with a part thereof exposed to the outside, and serves to guide heat generation and heat absorption inside the tank to the outside.
  • the valve 5 has, for example, a shape in which a male screw is formed in a cylindrical portion, and is screwed into a female screw formed on the inner surface of the mouthpiece 3 so that the opening of the mouthpiece 3 is closed by the valve 5. Closed.
  • the mouthpiece 3, boss 4 and valve 5 can be replaced by other means.
  • the material of the liner 1 constituting the high-pressure gas storage tank 10 includes a liner mainly composed of resin (hereinafter also referred to as “resin liner”) and a liner mainly composed of metal (hereinafter also referred to as “metal liner”). ) are exemplified. It is preferable to use a resin liner for vehicle tanks and the like that require weight reduction.
  • the resin used for the resin liner is not particularly limited as long as it has excellent gas barrier properties such as hydrogen gas and pressure resistance. be done.
  • thermoplastic resins are preferable from the viewpoint that the liner can be easily molded.
  • the thermoplastic resin include polyamide resins, polyester resins, polyolefin resins, polyimide resins, polycarbonate resins, polyetherimide resins, polyamideimide resins, polyphenylene etherimide resins, polyphenylene sulfide resins, polysulfone resins, polyethersulfone resins, poly arylate resins, liquid crystal polymers, polyetheretherketone resins, polyetherketone resins, polyetherketoneketone resins, polyetheretherketoneketone resins, polybenzimidazole resins, etc., and one or more of these may be used in combination.
  • At least one selected from the group consisting of polyamide resins and polyolefin resins is preferred among thermoplastic resins, and polyamide resins are
  • the polyamide resin contains a diamine-derived structural unit and a dicarboxylic acid-derived structural unit, and 50 mol% or more of the diamine-derived structural units are derived from xylylenediamine.
  • Polyamide resins are preferred. Specific examples include the polyamide resins described in International Publication No. 2016/084475.
  • Polyolefin resins include polyethylene resins such as low-density polyethylene, medium-density polyethylene, high-density polyethylene, and linear low-density polyethylene.
  • the resin liner may contain reinforcing fibers from the viewpoint of obtaining high strength and high elastic modulus.
  • the reinforcing fibers the same ones as those exemplified for the prepreg can be used, and carbon fibers are preferable from the viewpoint of obtaining light weight, high strength and high elastic modulus.
  • the content thereof is such that the volume fraction in the resin liner is preferably 0.10 or more, more preferably 0.20 or more, from the viewpoint of obtaining high strength and high elastic modulus. It is more preferably 0.30 or more, and still more preferably 0.40 or more. From the viewpoint of gas barrier properties and moldability, it is preferably 0.98 or less, more preferably 0.95 or less, still more preferably 0.80 or less, and even more preferably 0.70 or less.
  • the resin liner may contain an elastomer component.
  • the elastomer component include polyolefin elastomers, diene elastomers, polystyrene elastomers, polyamide elastomers, polyester elastomers, polyurethane elastomers, fluorine elastomers, silicone elastomers, etc., other than the above thermoplastic resins. Modified elastomers obtained by modifying these elastomers with ⁇ , ⁇ -unsaturated carboxylic acids and their acid anhydrides, acrylamide and derivatives thereof in the presence or absence of a radical initiator may also be used.
  • the resin liner contains an elastomer component
  • its content is preferably 5 to 20% by mass, more preferably 10 to 15% by mass, in the resin liner from the viewpoint of improving impact resistance while maintaining gas barrier properties. Range.
  • metals used for the metal liner include light alloys such as aluminum alloys and magnesium alloys.
  • the thickness of the liner can be appropriately selected according to the capacity, shape, etc. of the high-pressure gas storage tank. It is more preferably 400 ⁇ m or more, and preferably 60 mm or less, more preferably 40 mm or less, from the viewpoint of miniaturization and weight reduction of the high-pressure gas storage tank.
  • the outer layer 2 constituting the high-pressure gas storage tank 10 is not particularly limited as long as it contains the fiber-reinforced composite material.
  • the content of the fiber-reinforced composite material in the material constituting the outer layer is preferably 50% by mass or more, more preferably 70% by mass or more, and still more preferably 80% by mass. % or more, more preferably 90% by mass or more, and the upper limit is 100% by mass.
  • the outer layer is preferably composed only of the fiber-reinforced composite material of the present invention.
  • the reinforcing fibers in the fiber-reinforced composite material are preferably arranged regularly.
  • the regularly arranged means that 50% by mass or more, preferably 70% by mass or more, of the reinforcing fibers contained in the outer layer are arranged with a certain directionality.
  • the constant directionality is exemplified by spiral, vertical, horizontal, or a combination thereof.
  • the terms helical, vertical, and horizontal are meant to include errors generally interpreted by those skilled in the art, in addition to strict helical arrangements.
  • the thickness of the outer layer can be appropriately selected according to the capacity, shape, etc. of the high-pressure gas storage tank. It is more preferably 400 ⁇ m or more, and preferably 80 mm or less, more preferably 60 mm or less, from the viewpoint of downsizing and weight reduction of the high-pressure gas storage tank.
  • the outer layer 2 As a mode of the outer layer 2, for example, as shown in FIG. 1, there is a mode in which the outer surface of the main body portion of the liner 1 is formed so as to cover the fiber-reinforced composite material without gaps.
  • the outer layer may be applied directly to the outer surface of the liner.
  • one or more other layers may be provided on the outer surface of the liner, and may be provided on the surface of the other layers.
  • an adhesive layer may be provided between the liner and the outer layer in order to improve the adhesion between the liner and the outer layer. Any layer such as a protective layer, a paint layer, and a rust-preventive layer may be formed on the surface of the outer layer.
  • the gas to be stored in the high-pressure gas container of the present invention may be gaseous at 25° C. and 1 atm, and includes hydrogen, oxygen, carbon dioxide, nitrogen, argon, LPG, CFC alternatives, methane, and the like. .
  • hydrogen is preferable from the viewpoint of effectiveness of the present invention.
  • the method for manufacturing the high-pressure gas container of the present invention is not particularly limited.
  • a prepreg containing continuous fibers such as tow prepreg is wound around the outer surface of a mold such as a balloon or ceramic, heat-cured, and then the mold is removed. method; molding by a 3D printer using the prepreg; and the like.
  • the method for manufacturing a high-pressure gas storage tank having a liner and an outer layer containing a fiber-reinforced composite material preferably includes the following steps (I) to (III) in this order.
  • a thermosetting resin composition which is a reaction product obtained by reacting 1 to 20 parts by mass of the epoxy modifier (B) with 100 parts by mass of the amine epoxy resin (A), is used as a continuous fiber.
  • Step of impregnating the bundle Epoxy modifier (B): At least one selected from the group consisting of metaxylylenediamine, paraxylylenediamine, 4,4′-diaminodiphenylmethane and 4,4′-diaminodiphenylsulfone Step (II ): Drying the continuous fiber bundle impregnated with the thermosetting resin composition to remove the solvent to obtain a tow prepreg Step (III): Winding the tow prepreg around the outer surface of a liner, then heating forming an outer layer made of a fiber-reinforced composite material
  • thermosetting resin composition containing an adduct resin (X) which is a reaction product of an amine epoxy resin (A) and an epoxy modifier (B), an epoxy resin curing agent (C) and a solvent is prepared.
  • a continuous fiber bundle is impregnated. This gives an undried tow prepreg.
  • the thermosetting resin composition and its preferred embodiments are the same as above.
  • the reinforcing fibers constituting the continuous fiber bundle and preferred aspects thereof are also the same as above, and at least one selected from the group consisting of glass fiber, carbon fiber and basalt fiber is preferred, and carbon fiber is more preferred.
  • the method for impregnating the continuous fiber bundle with the thermosetting resin composition is not particularly limited, and a known method can be used.
  • step (II) the continuous fiber bundle impregnated with the thermosetting resin composition is dried to remove the solvent to obtain a tow prepreg.
  • the drying conditions are not particularly limited, it is preferable that the conditions are such that the solvent can be removed and the curing of the thermosetting resin composition does not proceed excessively.
  • the drying temperature can be selected in the range of 30 to 120° C.
  • the drying time can be selected in the range of 10 seconds to 5 minutes.
  • the drying can be performed by a known method using a hot air dryer, a heater, a heating roll, a hot plate, or the like.
  • the method using a hot air dryer is preferable.
  • the tow prepreg obtained in step (II) may be wound once, or may be continuously subjected to step (III) without winding.
  • step (III) the tow prepreg obtained in step (II) is wrapped around the outer surface of a liner and then heated to form an outer layer of fiber reinforced composite. This makes it possible to produce a high-pressure gas storage tank with a liner and an outer layer of fibre-reinforced composite material.
  • a step of providing one or more layers in advance on the outer surface of the liner may be performed.
  • the method of winding the tow prepreg around the outer surface of the liner is not particularly limited.
  • known filament winding techniques can be used to spirally and tightly wrap the outer surface of the liner.
  • an adhesive or the like may be used as necessary.
  • the heating is performed by a known method at a temperature and for a time sufficient to cure the thermosetting resin composition contained in the tow prepreg. From the viewpoint of improving productivity, it is preferable that the heating temperature is in the range of 80 to 140° C. and the heating time is in the range of 10 minutes to 5 hours.
  • any layer such as a protective layer, a paint layer, a rust-preventive layer, etc. can be formed on the surface of the outer layer.
  • thermosetting resin composition is heated at 100 ° C., poured into a mold (100 mm ⁇ 100 mm ⁇ 2 mm) coated with a release agent (“Daifree” manufactured by Daikin Co., Ltd.), cured and plate-shaped test piece ( 2 mm thick) was obtained.
  • a vapor permeability measuring device (“G2700T F” manufactured by GTR Tech)
  • the hydrogen gas permeability coefficient [cc mm / (m 2 day atm)] was measured in a dry state at 23 ° C. It was measured.
  • thermosetting resin composition Place 10 g of the thermosetting resin composition in a plastic cup (diameter 60 mm) and check the fluidity of the thermosetting resin composition at 23 ° C. and 50% humidity. The time [h] until it stopped flowing was measured.
  • stops flowing means that even if you try to mix the thermosetting resin composition in the plastic cup with a wooden spatula, it will not move at all. It refers to the state of not being stabbed (same below).
  • thermosetting resin composition Place 10 g of the thermosetting resin composition in a plastic cup (caliber 60 mm), store at -10 ° C., return to room temperature (23 ° C.) every other day, heat at 23 ° C., humidity 50%. The fluidity of the curable resin composition was confirmed, and the number of days [day] until the thermosetting resin composition stopped flowing was measured.
  • thermosetting resin composition ⁇ Solid content viscosity (100°C)>
  • the solid content viscosity of the thermosetting resin composition was measured by the following method using a rheometer "ARES-G2" manufactured by TA Instruments.
  • a composition for solid content viscosity measurement was prepared in the same manner, except that no solvent was used in the preparation of the thermosetting resin composition described later.
  • the composition is filled between aluminum plates at 60 ° C., the frequency is 1 Hz, the distance between the plates is 0.5 mm, and the heating rate is 5 ° C./min.
  • the elastic modulus G′′ was measured to obtain the solid content viscosity [Pa ⁇ s] at 100°C.
  • thermosetting resin composition was evaluated according to the following evaluation criteria by producing a tow prepreg under the following conditions and using it to produce a pipe-type CFRP under the following conditions.
  • the thermosetting resin composition is impregnated into a 24K CF tow (manufactured by Toray Industries, Inc., Torayca yarn “T700SC-24000”, number of filaments: 24K, tensile modulus: 230GPa, weave: 1650tex), and undried tow prepreg. was made. The undried tow prepreg was then dried by heating in a hot air dryer at 120° C. for 60 seconds to produce a tow prepreg.
  • the content of continuous carbon fibers in the tow prepreg was 0.55 in volume fraction.
  • ⁇ Fabrication of pipe-type CFRP> The tow prepreg produced above was wound around an aluminum bar with a diameter of 30 mm for a length of 300 mm while traversing at a circumference of 5 mm. , and held in a hot air dryer at 140° C. for 2 hours for heat curing to obtain a pipe-shaped fiber reinforced resin (pipe-shaped CFRP). (Evaluation criteria) A: It is possible to wind the tow prepreg around the aluminum bar, and the pipe-type CFRP can be molded by curing the resin.
  • thermosetting resin composition is too low and the thermosetting resin composition flows out of the tow prepreg, making it impossible to form a pipe-type CFRP.
  • C The viscosity of the thermosetting resin composition is too high to impregnate the CF tow with the thermosetting resin composition, or even if the CF tow can be impregnated with the thermosetting resin composition, the tow prepreg is hardened. Too much to wrap around the aluminum bar.
  • Example 1 (Preparation and Evaluation of Thermosetting Resin Composition)
  • an epoxy resin amine epoxy resin 1; "TETRAD-X” manufactured by Mitsubishi Gas Chemical Co., Ltd.
  • amine epoxy resin 1 "TETRAD-X” manufactured by Mitsubishi Gas Chemical Co., Ltd.
  • A amine epoxy resin
  • B 4,4′-diaminodiphenylmethane
  • 4,4′-DDM 4,4′-diaminodiphenylmethane
  • thermosetting resin composition 10 g was taken out into a polypropylene container, and a mixed solution of methanol and ethyl acetate as solvents (mass ratio of methanol:ethyl acetate: 1:4) was placed therein at room temperature (23°C). 18.6 g and 0.5 g of dicyandiamide (“DICY7” manufactured by Mitsubishi Chemical Corporation) as an epoxy resin curing agent (C) were added and stirred manually with a wooden spatula to obtain a uniform thermosetting resin composition. rice field. Using this thermosetting resin composition, various evaluations were performed by the above methods. Table 1 shows the results.
  • Example 1 the same method as in Example 1 was used except that the type and amount of the epoxy modifier (B) and the type and amount of the epoxy resin curing agent (C) were changed as shown in Table 1.
  • a thermosetting resin composition was prepared in and various evaluations were performed by the above methods. Table 1 shows the results.
  • Example 1 Comparative Examples 1-5 In Example 1, the same method as in Example 1 was used, except that the type and amount of the epoxy modifier (B) and the type and amount of the epoxy resin curing agent (C) were changed as shown in Table 2. A thermosetting resin composition was prepared in and various evaluations were performed by the above methods. Table 2 shows the results.
  • Example 6 Comparative example 6 In Example 1, the adduct resin (X) was not prepared, and dicyandiamide was added as the epoxy resin curing agent (C) to the amine epoxy resin (A) in the amount shown in Table 2.
  • a thermosetting resin composition was prepared by the method, and various evaluations were performed by the above method. Table 2 shows the results.
  • Comparative example 7 In Example 1, the adduct resin (X) was not prepared, and 10 g of isophorone diamine (IPDA, manufactured by Tokyo Chemical Industry Co., Ltd.) was added as the epoxy resin curing agent (C) to 100 g of the amine-epoxy resin (A).
  • IPDA isophorone diamine
  • a thermosetting resin composition was prepared in the same manner as in Example 1, and various evaluations were performed by the above methods. Table 2 shows the results.
  • Comparative example 8 Instead of the amine epoxy resin (A), a bisphenol A type epoxy resin ("jER828" manufactured by Mitsubishi Chemical Corporation) was used as a comparative epoxy resin, and the amount of the epoxy modifier (B) was changed as shown in Table 2.
  • a thermosetting resin composition was prepared in the same manner as in Example 1 except that the composition was prepared, and various evaluations were performed by the above methods. Table 2 shows the results. Tables 1 and 2 show the blending amounts of components other than the solvent.
  • thermosetting resin composition of the present invention has a low hydrogen gas permeability coefficient, that is, good hydrogen gas barrier properties.
  • thermosetting resin composition of the present invention can form a tow prepreg which has a long shelf life and a long pot life and is excellent in moldability when winding a fiber-reinforced composite material.
  • thermosetting resin composition capable of forming a tow prepreg having high barrier properties against hydrogen gas and the like, long shelf life and pot life, good workability, and excellent moldability.
  • a fiber-reinforced composite material using the thermosetting resin composition of the present invention has a high gas barrier property and is suitable as a material for composing a high-pressure gas container such as a high-pressure gas storage tank.

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