Thermosetting resin composition, cured product thereof, prepreg, fiber-reinforced composite material, and high-pressure gas container

Abstract

A thermosetting resin composition containing component (A): a polyfunctional epoxy resin, component (B): a (meth)acrylate compound having no glycidyl group, component (C): a compound having a (meth)acryloxy group and a glycidyl group, component (D): an epoxy resin curing agent containing a boron amine complex, and component (E): a thermal radical polymerization initiator, a cured product thereof, a prepreg containing the thermosetting resin composition, a fiber-reinforced composite material, and a high-pressure gas container.

Description

Technical Field

[0001] This invention relates to thermosetting resin compositions and their cured products, prepregs, fiber-reinforced composites, and high-pressure gas containers. Background Technology

[0002] In recent years, environmentally friendly natural gas vehicles (CNG vehicles) and fuel cell vehicles (FCVs) have become increasingly popular. Fuel cell vehicles use fuel cells as their power source and must be equipped with hydrogen stations that compress hydrogen to high pressure and fill the vehicle.

[0003] High-pressure gas storage tanks used in hydrogen stations for fuel cell vehicles, or as onboard fuel tanks for CNG vehicles and fuel cell vehicles, have traditionally been made of steel. However, the development of lighter high-pressure gas storage tanks with resin linings or outer layers is underway. Lightening the onboard fuel tank offers advantages such as improved fuel efficiency for the vehicle.

[0004] Pressure vessels such as high-pressure gas storage tanks typically have a metal liner and an outer layer that covers the outer surface of the liner. However, in recent years, in order to produce lighter pressure vessels, the fabrication of pressure vessels with plastic liners and pressure vessels without liners has also been studied.

[0005] As a method for manufacturing pressure vessels, there is a known method of manufacturing pressure vessels by winding fibers using a tow prepreg (also known as tow sheet) that is pre-impregnated with an epoxy resin composition in reinforcing fibers.

[0006] Prepregs and curable resin compositions suitable for prepregs were also studied. For example, Patent Document 1 discloses a prepreg comprising carbon fibers and a matrix resin as a useful prepreg for molding high-strength and high-toughness fiber-reinforced plastics. The matrix resin is a curable resin composition comprising a bisphenol-type epoxy resin, a (meth)acrylate compound with two or more functional groups, and a curing agent containing dicyandiamide and a free radical polymerizer. The cured product of this curable resin composition has a specified flexural modulus and elongation at break. Furthermore, a method for producing a tubular body by winding the prepreg onto a mandrel is also described.

[0007] Patent Document 2 discloses a curable resin composition comprising two epoxy resins that meet specified requirements, a (meth)acrylate compound with two or more functions, and a curing agent, as a useful prepreg for molding high-strength and high-toughness fiber-reinforced plastics.

[0008] Existing technical documents

[0009] Patent documents

[0010] Patent Document 1: Japanese Patent No. 6993549

[0011] Patent Document 2: Japanese Patent Application Publication No. 2022-27815 Summary of the Invention

[0012] The problem the invention aims to solve

[0013] In thermosetting resin compositions used in the matrix resin of prepregs, a long pot life is required to ensure the long-term shelf life of the prepreg. Furthermore, to ensure heat resistance and high toughness in the fiber-reinforced composite material obtained by curing the prepreg, the thermosetting resin composition used in the matrix resin of the prepreg requires both a high glass transition temperature and high elongation of the cured product. However, the technologies disclosed in Patent Documents 1 and 2 do not fully meet all these requirements.

[0014] On the other hand, if one wants to increase the elongation of the cured thermosetting resin composition, there is usually a tendency for the tensile stress and tensile modulus of the cured product to decrease.

[0015] Therefore, the objective of this invention is to provide a cured product with high glass transition temperature, elongation, tensile stress and tensile modulus, a thermosetting resin composition having a long pot life, the cured product thereof, a prepreg containing the thermosetting resin composition, a fiber-reinforced composite material, and a high-pressure gas container.

[0016] Solution for solving the problem

[0017] The inventors have discovered that the above-mentioned problems can be solved by a thermosetting resin composition containing a multifunctional epoxy resin, a (meth)acrylate compound without glycidyl groups, a compound having (meth)acryloyloxy and glycidyl groups, a specified epoxy resin curing agent, and a thermal free radical polymerization initiator.

[0018] That is, the present invention relates to the following.

[0019] [1] A thermosetting resin composition comprising:

[0020] Component (A): Multifunctional epoxy resin,

[0021] Ingredient (B): (meth)acrylate compounds without glycidyl groups.

[0022] Ingredient (C): A compound containing (meth)acryloyloxy and glycidyl groups.

[0023] Component (D): Epoxy resin curing agent containing boronamine complex, and

[0024] Component (E): Thermal free radical polymerization initiator.

[0025] [2] The thermosetting resin composition according to [1], wherein the aforementioned component (B) comprises component (B1): poly(butadiene-CO-acrylonitrile) with (meth)acryloyloxy groups at both ends.

[0026] [3] The thermosetting resin composition according to [1] or [2], wherein the aforementioned component (B) comprises component (B2): a polyfunctional (meth)acrylate having an aromatic ring.

[0027] [4] The thermosetting resin composition according to any one of [1] to [3], wherein the aforementioned component (C) comprises a compound represented by the following general formula (1).

[0028]

[0029] In equation (1), R 11 Represents a hydrogen atom or a methyl group. Z represents a single bond, -(CH2). m -O- (m is a number from 2 to 8) or a divalent group as shown in the following general formula (2).

[0030]

[0031] In equation (2), R 12 and R 13 Each atom can be represented independently as a hydrogen atom or a methyl group. n is a number from 1 to 5. * indicates a connecting bond.

[0032] [5] The thermosetting resin composition according to any one of [1] to [4], wherein the amine component in the aforementioned boronamine complex is a trialkylamine.

[0033] [6] A cured product, which is a cured product of any one of the thermosetting resin compositions described in [1] to [5].

[0034] [7] A prepreg comprising any one of [1] to [5] a thermosetting resin composition and reinforcing fibers.

[0035] [8] According to the prepreg described in [7], wherein the aforementioned reinforcing fiber is at least one selected from the group consisting of carbon fiber, glass fiber and basalt fiber.

[0036] [9] The prepreg according to [7] or [8], wherein the aforementioned prepreg is a tow prepreg or a strip prepreg.

[0037]

[10] A fiber-reinforced composite material, which is the cured product of the prepreg described in any one of [7] to [9].

[0038]

[11] A high-pressure gas container comprising the fiber-reinforced composite material described in

[10] .

[0039] The effects of the invention

[0040] According to the present invention, it is possible to provide cured products with high glass transition temperature, elongation, tensile stress and tensile modulus, thermosetting resin compositions with long pot life, cured products thereof, prepregs containing the thermosetting resin compositions, fiber-reinforced composite materials and high-pressure gas containers. Detailed Implementation

[0041] [definition]

[0042] In this specification, "(meth)acryloyloxy" includes both acryloyloxy and methacryloyloxy. The same applies to "(meth)acrylate", "(meth)acrylic acid", etc.

[0043] Unless otherwise specified, "room temperature" in this instruction manual refers to 23°C.

[0044] [Thermosetting resin composition]

[0045] The thermosetting resin composition of the present invention (hereinafter also simply referred to as "the composition of the present invention") contains:

[0046] Component (A): Multifunctional epoxy resin,

[0047] Ingredient (B): (meth)acrylate compounds without glycidyl groups.

[0048] Ingredient (C): A compound containing (meth)acryloyloxy and glycidyl groups.

[0049] Component (D): Epoxy resin curing agent containing boronamine complex, and

[0050] Component (E): Thermal free radical polymerization initiator.

[0051] The composition of the present invention, having the above-described structure, yields a cured product with high glass transition temperature (Tg), elongation, tensile stress, and tensile modulus, and thus has a long pot life.

[0052] The reasons for achieving the above-mentioned effects in this invention are not yet certain, but are believed to be as follows.

[0053] The thermosetting resin composition of the present invention comprises: a multifunctional epoxy resin (A) as a thermosetting resin, a (meth)acrylate compound (B) without glycidyl groups, and a compound (C) having (meth)acryloyloxy and glycidyl groups. An epoxy resin curing agent (D) serves as a curing agent for components (A) and (C), and a thermal free radical polymerization initiator (E) functions as a thermal free radical polymerization initiator for curing components (B) and (C).

[0054] Thermosetting (epoxy) resin compositions containing epoxy resin and epoxy resin curing agents generally exhibit excellent curability and heat resistance, but low elongation of the cured product is a concern for applications requiring high toughness. Furthermore, epoxy resin compositions typically cure quickly, therefore, improvements in pot life are needed, particularly for prepregs intended for room-temperature storage.

[0055] By including a boronamine complex in component (D) of the thermosetting resin composition of the present invention, the pot life can be improved. Furthermore, it is believed that by making the thermosetting resin composition of the present invention a composite of an epoxy resin curing system of components (A) and (D) and a (meth)acrylate curing system of components (B) and (E), the elongation of the cured product is increased compared to the case where the epoxy resin curing system is used alone, thereby suppressing the reduction in the pot life of the composition caused by the high reactivity of component (A) with the epoxy resin curing agent.

[0056] Furthermore, component (C) used in this invention has (meth)acryloyloxy and glycidyl groups, which can react with both components (A) and (B), thus acting as a crosslinking agent between components (A) and (B). Therefore, it is believed that the tensile stress and tensile modulus of the obtained cured product are further improved.

[0057] <Ingredient (A): Multifunctional epoxy resin>

[0058] The multifunctional epoxy resin (A) used in this invention is not particularly limited as long as it does not have (meth)acryloyloxy group and has two or more epoxy groups. From the viewpoint of improving the Tg, tensile stress and tensile modulus of the cured product, it is preferred to be a multifunctional epoxy resin containing an aromatic ring or alicyclic structure in the molecule.

[0059] As a specific example of a multifunctional epoxy resin (A), at least one selected from the group consisting of: a multifunctional epoxy resin having a glycidyl amino group derived from m-phenylenediamine, a multifunctional epoxy resin having a glycidyl amino group derived from p-phenylenediamine, a multifunctional epoxy resin having a glycidyl amino group derived from 1,3-bis(aminomethyl)cyclohexane, a multifunctional epoxy resin having a glycidyl amino group derived from 1,4-bis(aminomethyl)cyclohexane, and a multifunctional epoxy resin having a glycidyl amino group derived from diaminodiphenyl... The polyfunctional epoxy resins include methane-derived polyfunctional epoxy resins containing glycidyl amino groups, polyfunctional epoxy resins derived from p-aminophenol containing glycidyl amino groups and / or glycidyloxy groups, polyfunctional epoxy resins derived from resorcinol containing glycidyloxy groups, polyfunctional epoxy resins derived from bisphenol A containing glycidyloxy groups or their hydrides, polyfunctional epoxy resins derived from bisphenol F containing glycidyloxy groups or their hydrides, and polyfunctional epoxy resins derived from phenolic varnish containing glycidyloxy groups. One or more of the above-mentioned polyfunctional epoxy resins may be used.

[0060] From the viewpoint of improving the Tg, tensile stress, and tensile modulus of the cured product, the multifunctional epoxy resin (A) preferably has at least one component selected from the group consisting of a multifunctional epoxy resin with glycidyl amino groups derived from m-phenylenediamine, a multifunctional epoxy resin with glycidyl amino groups derived from p-phenylenediamine, a multifunctional epoxy resin with glycidyl oxygen groups derived from bisphenol A, and a multifunctional epoxy resin with glycidyl oxygen groups derived from bisphenol F. More preferably, it has at least one component selected from the group consisting of an epoxy resin with glycidyl oxygen groups derived from bisphenol A and an epoxy resin with glycidyl oxygen groups derived from bisphenol F.

[0061] It should be noted that the term "main component" as used here refers to other components that may be included without departing from the spirit of the present invention, preferably 50 to 100% by mass of the total, more preferably 70 to 100% by mass, and even more preferably 90 to 100% by mass.

[0062] The multifunctional epoxy resin derived from bisphenol A and having glycidyl group is bisphenol A diglycidyl ether or its oligomer, preferably a multifunctional epoxy resin with the following structural formula.

[0063]

[0064] (In the above formula, s represents the average number of repeating units, which is a number between 0 and 20.)

[0065] From the viewpoint of improving the Tg, tensile stress and tensile modulus of the cured product, s in the above formula is preferably 0~15, more preferably 0~10, further preferably 0.05~10, and even more preferably 0.10~8.0.

[0066] In addition, the multifunctional epoxy resin derived from bisphenol F and having glycidyl group is bisphenol F diglycidyl ether or its oligomer, preferably the multifunctional epoxy resin shown in the following structural formula.

[0067]

[0068] (In the above formula, t represents the average number of repeating units, which is a number between 0 and 20.)

[0069] From the viewpoint of increasing the Tg of the cured product, t in the above formula is preferably 0~15, more preferably 0~10, and even more preferably 0~8.0.

[0070] The multifunctional epoxy resin (A) can be any type of solid epoxy resin or liquid epoxy resin, but from the viewpoint that it is easy to impregnate the reinforcing fibers when applied to prepregs, the multifunctional epoxy resin (A) preferably includes a liquid epoxy resin. "Solid epoxy resin" refers to an epoxy resin that does not have flowability at 25°C, and "liquid epoxy resin" refers to an epoxy resin that has flowability at 25°C.

[0071] From the viewpoint of improving the permeability to reinforcing fibers, the content of liquid epoxy resin in the multifunctional epoxy resin (A) is preferably 30% by mass or more, more preferably 50% by mass or more, further preferably 60% by mass or more, even more preferably 70% by mass or more, even more preferably 80% by mass or more, even more preferably 85% by mass or more, even more preferably 90% by mass or more, and is 100% by mass or less.

[0072] The epoxy equivalent (functional group equivalent) of the multifunctional epoxy resin (A) is not particularly limited. From the viewpoint that it is easy to impregnate the reinforcing fiber when applied to prepreg, it is preferably 1,500 g / equivalent or less, more preferably 1,200 g / equivalent or less, even more preferably 1,000 g / equivalent or less, even more preferably 800 g / equivalent or less, even more preferably 500 g / equivalent or less, even more preferably 350 g / equivalent or less, even more preferably 250 g / equivalent or less. From the viewpoint of improving curability, it is preferably 120 g / equivalent or more.

[0073] When a mixture of two or more epoxy resins is used as a multifunctional epoxy resin (A), the epoxy equivalent of the multifunctional epoxy resin (A) refers to the epoxy equivalent of the mixture.

[0074] As component (A), a multifunctional epoxy resin with glycidyl group derived from bisphenol A can be "jER825", "jER827", "jER828", "jER834", "jER1001", "jER1004" etc. manufactured by Mitsubishi Chemical Corporation. As component (A), a multifunctional epoxy resin with glycidyl group derived from bisphenol F can be commercially available products such as "jER806", "jER806H", "jER807", "jER4005P", "jER4007P", "jER4010P" manufactured by Mitsubishi Chemical Corporation.

[0075] <Ingredient (B): (Meth)acrylate compound without glycidyl groups>

[0076] The component (B) used in this invention is a (meth)acrylate compound that does not have a glycidyl group.

[0077] Component (B) can be any compound that does not contain a glycidyl group and has at least one (meth)acryloyloxy group. From the viewpoint of improving the Tg, elongation, tensile stress, and tensile modulus of the cured product, it is preferable to include a polyfunctional (meth)acrylate compound having two or more (meth)acryloyloxy groups. The polyfunctional (meth)acrylate compound preferably has 2 to 6 (meth)acryloyloxy groups, more preferably 2 to 4, further preferably 2 to 3, and even more preferably 2. If the polyfunctional (meth)acrylate compound has 2 or more (meth)acryloyloxy groups, it is easier to improve the Tg, tensile stress, and tensile modulus of the cured product; if it has 6 or less (meth)acryloyloxy groups, it can suppress the decrease in elongation of the cured product.

[0078] From the viewpoint of improving the Tg, elongation, tensile stress and tensile modulus of the cured product, the content of the polyfunctional (meth)acrylate compound in component (B) is preferably 50% by mass or more, more preferably 60% by mass or more, further preferably 70% by mass or more, even more preferably 80% by mass or more, even more preferably 90% by mass or more, even more preferably 95% by mass or more, even more preferably 98% by mass or more, and is 100% by mass or less.

[0079] From the viewpoint of improving the Tg, elongation, tensile stress and tensile modulus of the cured product, component (B) preferably includes at least one of the following as a polyfunctional (meth)acrylate compound: component (B1): poly(butadiene-CO-acrylonitrile) with (meth)acryloyloxy groups at both ends and component (B2): a polyfunctional (meth)acrylate having an aromatic ring. More preferably, it includes both component (B1) and component (B2).

[0080] (Component (B1): Poly(butadiene-CO-acrylonitrile) with (meth)acryloyloxy groups at both ends)

[0081] From the viewpoint of improving the elongation of the cured product, component (B) preferably includes component (B1): a poly(butadiene-CO-acrylonitrile) compound with (meth)acryloyloxy groups at both ends as a multifunctional (meth)acrylate compound. Component (B1) has a highly flexible structure, and therefore it is believed that it can suppress the decrease in elongation even in cured products with high crosslinking density.

[0082] The component (B1) used in this invention is a di(meth)acrylate with (meth)acryloyloxy groups at both ends of the main chain of a copolymer structure containing butadiene and acrylonitrile.

[0083] From the viewpoint of improving the Tg, elongation, tensile stress and tensile modulus of the cured product, the content of acrylonitrile-derived structural units in component (B1) is preferably 5 to 50% by mass, more preferably 10 to 30% by mass, and even more preferably 10 to 25% by mass.

[0084] The weight-average molecular weight (Mw) of component (B1) is preferably 1,000 to 30,000, more preferably 2,000 to 10,000, and even more preferably 3,000 to 8,000. If Mw is 1,000 or more, it is easier to increase the elongation of the cured product, and if it is 30,000 or less, it is easier to suppress the decrease in Tg, tensile stress and tensile modulus of the cured product.

[0085] Commercially available products containing component (B1) include, for example, the Cherry GLEX "Hypro1300X33LC".

[0086] The content of component (B1) in component (B) is preferably 1-70% by mass, more preferably 5-70% by mass, even more preferably 10-70% by mass, even more preferably 15-70% by mass, even more preferably 15-60% by mass, even more preferably 15-50% by mass, even more preferably 15-35% by mass, even more preferably 15-25% by mass, and even more preferably 15-20% by mass. If the content of component (B1) in component (B) is 1% by mass or more, it is easy to help improve the elongation of the cured product; if it is 70% by mass or less, it can suppress the decrease in Tg, tensile stress and tensile modulus of the cured product.

[0087] (Component (B2): Polyfunctional (meth)acrylates with aromatic rings)

[0088] From the viewpoint of improving the Tg, elongation, tensile stress and tensile modulus of the cured product, component (B) preferably includes component (B2): a polyfunctional (meth)acrylate with an aromatic ring as a polyfunctional (meth)acrylate compound.

[0089] The number of (meth)acryloyloxy groups in component (B2) is preferably 2 to 6, more preferably 2 to 4, further preferably 2 to 3, and even more preferably 2. When the number of (meth)acryloyloxy groups in component (B2) is 2 or more, it is conducive to improving the Tg, tensile stress, and tensile modulus of the cured product; when it is 6 or less, it can suppress the decrease in elongation of the cured product.

[0090] The aromatic ring of component (B2) can be a monocyclic or fused ring, and examples include benzene rings, naphthalene rings, anthracene rings, and tetraphenylene rings, but it is not limited to these. Among these, it is preferably selected from at least one of the group consisting of benzene rings and naphthalene rings, and more preferably a benzene ring.

[0091] The aromatic ring number of component (B2) is 1 or more, and from the viewpoint of improving the Tg, elongation, tensile stress and tensile modulus of the cured product, it is preferred to be 2 or more.

[0092] Specific examples of polyfunctional (meth)acrylates having an aromatic ring as used as component (B2) include polyfunctional (meth)acrylates having a structure derived from biphenol, polyfunctional (meth)acrylates having a structure derived from bisphenol A, polyfunctional (meth)acrylates having a structure derived from bisphenol F, polyfunctional (meth)acrylates having a fluorene structure, polyfunctional (meth)acrylates having a structure derived from aromatic hydrocarbon formaldehyde resin, etc., and one or more of them may be used.

[0093] From the viewpoint of improving the Tg, elongation, tensile stress and tensile modulus of the cured product, component (B2) preferably includes at least one selected from the group consisting of a polyfunctional (meth)acrylate having a structure derived from bisphenol A, a polyfunctional (meth)acrylate having a structure derived from bisphenol F and a polyfunctional (meth)acrylate having a structure derived from an aromatic hydrocarbon formaldehyde resin, more preferably including at least one selected from the group consisting of a polyfunctional (meth)acrylate having a structure derived from bisphenol A and a polyfunctional (meth)acrylate having a structure derived from an aromatic hydrocarbon formaldehyde resin, and even more preferably including a polyfunctional (meth)acrylate having a structure derived from bisphenol A.

[0094] The aforementioned polyfunctional (meth)acrylates may be any of the following: polyester (meth)acrylates having a main skeleton derived from polyols, epoxy (meth)acrylates having a main skeleton derived from epoxy compounds, and urethane (meth)acrylates having a main skeleton derived from polyisocyanates, preferably at least one selected from the group consisting of polyester (meth)acrylates and epoxy (meth)acrylates.

[0095] The aforementioned aromatic hydrocarbon formaldehyde resin is a resin obtained by reacting an aromatic hydrocarbon with formaldehyde. Examples of the aromatic hydrocarbon include at least one selected from the group consisting of benzene, xylene, toluene, mesitylene, pseudocumene, ethylbenzene, propenzene, decylbenzene, cyclohexylbenzene, biphenyl, methylbiphenyl, naphthalene, methylnaphthalene, dimethylnaphthalene, ethylnaphthalene, anthracene, methylanthracene, dimethylanthracene, ethylanthracene, and binaphthalene, preferably at least one selected from the group consisting of xylene, toluene, and mesitylene, and more preferably xylene. It should be noted that xylene formaldehyde resin is also called "xylene resin," toluene formaldehyde resin is also called "toluene resin," and mesitylene formaldehyde resin is also called "mesitylene resin."

[0096] The polyfunctional (meth)acrylate with aromatic rings used as component (B2) is further preferably composed of at least one of the following groups: compounds of general formula (B2-1), general formula (B2-2), general formula (B2-3), and polyfunctional (meth)acrylates having a structure derived from aromatic hydrocarbon formaldehyde resins. It is even more preferred that the polyfunctional (meth)acrylate with aromatic rings used as component (B2-1) contains at least one of the following groups: compounds of general formula (B2-1) and general formula (B2-2). It is even more preferred that the polyfunctional (meth)acrylate with aromatic rings used as component (B2-1) contains at least one of the following groups: compounds of general formula (B2-1) and general formula (B2-2).

[0097]

[0098] In the formula, R 1 and R 2 Each can independently represent a hydrogen atom or a methyl group, R 3 and R 4 Each can independently represent a hydrogen atom or a methyl group. k and l represent the number of repeating units, each independently representing a number from 0 to 20.

[0099]

[0100] In the formula, R 1 ~R 4 Same as above.

[0101]

[0102] In the formula, R 1 and R 2 As mentioned above, R 5 It is an alkylene group with 2 to 6 carbon atoms. X is a diisocyanate residue, and Y is a diol residue. Either X or Y contains an aromatic ring. r represents the number of repeating units, which is 1 or more. r+1 X's and r Y's can be all the same or different from each other.

[0103] In the aforementioned general formula (B2-1), R 1 and R 2 Preferably methyl, R 3 and R 4 Methyl is preferred.

[0104] From the viewpoint of improving the Tg, elongation, tensile stress, and tensile modulus of the cured product, in the aforementioned general formula (B2-1), k and l are each preferably 1 to 15, more preferably 1 to 10, and even more preferably 2 to 6. Furthermore, k+l is a number from 0 to 40, and from the viewpoint of improving the Tg, elongation, tensile stress, and tensile modulus of the cured product, it is preferably 2 to 30, more preferably 2 to 20, even more preferably 4 to 20, and even more preferably 8 to 20.

[0105] As the compound represented by the aforementioned general formula (B2-1), commercially available products such as "BPE-500" and "BPE-900" manufactured by Shin-Nakamura Chemical Industry Co., Ltd. can be used.

[0106] In the aforementioned general formula (B2-2), R 1 and R 2 Preferably methyl, R 3 and R 4 Methyl is preferred. Specific examples of compounds represented by general formula (B2-2) include (meth)acrylate adducts of bisphenol A diglycidyl ether [bisphenol A type epoxy di(meth)acrylate] and (meth)acrylate adducts of bisphenol F diglycidyl ether [bisphenol F type epoxy di(meth)acrylate], preferably bisphenol A type epoxy di(meth)acrylate, more preferably bisphenol A type epoxy dimethacrylate.

[0107] In the aforementioned general formula (B2-3), R 1 and R 2 Methyl is preferred. R 5 It is an alkylene group having 2 to 6 carbon atoms, and the alkylene group can be any type of straight-chain or branched chain. R 5 Preferably, it is an alkylene group having 2 to 4 carbon atoms, more preferably having 2 to 3 carbon atoms.

[0108] In the aforementioned general formula (B2-3), X is a divalent group, representing a residue of the diisocyanate shown as OCN-X-NCO. Examples of such diisocyanates include trimethylene diisocyanate, tetramethylene diisocyanate, 1,3-pentamethylene diisocyanate, 1,5-pentamethylene diisocyanate, hexamethylene diisocyanate, 1,2-propylidene diisocyanate, 1,2-butylidene diisocyanate, 2,3-butylidene diisocyanate, 1,3-butylidene diisocyanate, 2-methyl-1,5-pentamethylene diisocyanate, and 3-methyl-1,5-pentamethylene diisocyanate, as well as chain-like aliphatic diisocyanates; 1,3-cyclopentane diisocyanate, 1,4-cyclohexane diisocyanate, and 1,3-cyclohexane... Aliphatic diisocyanates containing alicyclic structures, such as diisocyanates, methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 1,2-bis(isocyanate methyl)cyclohexane, 1,3-bis(isocyanate methyl)cyclohexane, isophorone diisocyanate, and norbornene diisocyanate; and diisocyanates containing aromatic rings, such as m-phenylene diisocyanate, terephthalene diisocyanate, m-xylene diisocyanate, p-xylene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, naphthalene-1,4-diisocyanate, and naphthalene-1,5-diisocyanate. One or more of these diisocyanates may be used.

[0109] When Y in the aforementioned general formula (B2-3) does not contain an aromatic ring, the aforementioned diisocyanate is a diisocyanate containing an aromatic ring. When Y in the aforementioned general formula (B2-3) contains an aromatic ring, from the viewpoint of improving the elongation of the cured product, the aforementioned diisocyanate is preferably at least one selected from the group consisting of chain-like aliphatic diisocyanates and aliphatic diisocyanates containing alicyclic structures, more preferably at least one selected from the group consisting of hexamethylene diisocyanate, 1,2-bis(isocyanate methyl)cyclohexane, 1,3-bis(isocyanate methyl)cyclohexane and isophorone diisocyanate, and even more preferably hexamethylene diisocyanate.

[0110] In the aforementioned general formula (B2-3), Y is a divalent group, representing a residue of the diol represented by HO-Y-OH. Examples of such diols include chain aliphatic diols such as ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 2-ethyl-1,3-hexanediol, diethylene glycol, triethylene glycol, polyethylene glycol, polypropylene glycol, and polytetramethylene glycol; diols containing alicyclic structures such as cyclohexanediethanol and tricyclodecanediethanol; and diols containing aromatic rings such as biphenol, bisphenol A, bisphenol F, bisphenoxyfluoreneethanol, and diols obtained by adding ethylene oxide, propylene oxide, or caprolactone to these diols. One or more of these diols may be used.

[0111] From the viewpoint of improving the Tg, elongation, tensile stress and tensile modulus of the cured product, the aforementioned diol is preferably at least one selected from the group consisting of chain aliphatic diols and diols containing aromatic rings, more preferably a diol containing aromatic rings, and even more preferably at least one selected from the group consisting of bisphenol A, bisphenol F and diols obtained by adding them to ethylene oxide or propylene oxide.

[0112] In the aforementioned general formula (B2-3), Y is more preferably a divalent group as shown in the following general formula (Y1).

[0113]

[0114] In the formula, R 6 and R 7 Each atom can be independently represented by a hydrogen atom or a methyl group, preferably a methyl group. p and q represent the number of repeating units, each independently representing a number from 0 to 20. * indicates a connecting bond.

[0115] In the aforementioned general formula (B2-3), r is a number greater than or equal to 1, preferably a number greater than or equal to 1 and less than or equal to 200.

[0116] In addition, commercially available products that use polyfunctional (meth)acrylates with a structure derived from aromatic hydrocarbon formaldehyde resins as component (B2) include "NIKANOL XUAT" (carbamate acrylate xylene resin) manufactured by Fudow Co., Ltd.

[0117] The content of component (B2) in component (B) is preferably 30-99% by mass, more preferably 30-95% by mass, even more preferably 30-90% by mass, even more preferably 30-85% by mass, even more preferably 40-85% by mass, even more preferably 50-85% by mass, even more preferably 65-85% by mass, even more preferably 75-85% by mass, and even more preferably 80-85% by mass. If the content of component (B2) in component (B) is 30% by mass or more, it is easy to help improve the Tg, tensile stress and tensile modulus of the cured product; if it is 99% by mass or less, the elongation of the cured product can be maintained.

[0118] In addition to components (B1) and (B2), component (B) may also include monofunctional (meth)acrylates and polyfunctional (meth)acrylates other than components (B1) and (B2) for the purpose of reducing the viscosity of the composition.

[0119] From the viewpoint of improving the Tg, elongation, tensile stress and tensile modulus of the cured product, the total content of components (B1) and (B2) in component (B) is preferably 70% by mass or more, more preferably 80% by mass or more, further preferably 90% by mass or more, even more preferably 95% by mass or more, and 100% by mass or less.

[0120] <Ingredient (C): A compound having (meth)acryloyloxy and glycidyl groups>

[0121] The component (C) used in this invention is a compound having (meth)acryloyloxy and glycidyl groups.

[0122] There are no particular limitations on component (C) as long as it is a compound having at least one (meth)acryloyloxy group and at least one glycidyl group. From the viewpoint of improving the Tg, elongation, tensile stress and tensile modulus of the cured product, it is preferred to be a compound having 1 to 3 (meth)acryloyloxy groups and 1 to 3 glycidyl groups, more preferably a compound having 1 to 2 (meth)acryloyloxy groups and 1 to 2 glycidyl groups, and even more preferably a compound having 1 (meth)acryloyloxy group and 1 glycidyl group.

[0123] From the viewpoint of improving the Tg, tensile stress, and tensile modulus of the cured product by acting as a crosslinking agent, component (C) is preferably a low molecular weight compound, specifically, a compound with a molecular weight of 1,000 or less, preferably 800 or less, and more preferably 600 or less. Furthermore, from the viewpoint of having (meth)acryloyloxy and glycidyl groups, this molecular weight is preferably 140 or more.

[0124] Component (C) is further preferably a compound represented by the following general formula (1).

[0125]

[0126] In equation (1), R 11 Represents a hydrogen atom or a methyl group. Z represents a single bond, -(CH2). m -O- (m is a number from 2 to 8) or a divalent group as shown in the following general formula (2).

[0127]

[0128] In equation (2), R 12 and R 13 Each atom can be represented independently as a hydrogen atom or a methyl group. n is a number from 1 to 5. * indicates a connecting bond.

[0129] In equation (1), R 11 Preferably, it is a methyl group. Z is preferably a single bond or a divalent group as shown in the aforementioned general formula (2).

[0130] In equation (2), R 12 and R 13 The preferred form is methyl, and n is preferably 1 to 3, more preferably 1 to 2, and even more preferably 1.

[0131] As a specific example of the compound represented by the aforementioned general formula (1), at least one can be selected from the group consisting of glycidyl methacrylate, the compound represented by the following general formula (C-1), and the compound represented by the following general formula (C-2). Among these, from the viewpoint of improving the Tg, elongation, tensile stress, and tensile modulus of the cured product, component (C) preferably contains at least one selected from the group consisting of glycidyl methacrylate and the compound represented by the following general formula (C-2), and more preferably contains at least one selected from the group consisting of glycidyl methacrylate and the compound represented by the following general formula (C-2).

[0132]

[0133] In the formula, R 11 It represents a hydrogen atom or a methyl group.

[0134] The compound represented by the aforementioned general formula (C-2) is also known as a bisphenol A type semi-epoxy (meth)acrylate compound. Commercially available examples include "BAEM-50" (active ingredient content: 50% by mass) manufactured by KSM Corporation.

[0135] <Component (D): Epoxy resin curing agent containing boronamine complex>

[0136] From the viewpoint of improving the pot life of the composition, the component (D) used in this invention comprises a boronamine complex.

[0137] From the viewpoint of improving the pot life of the composition, the content of the boronamine complex in component (D) is preferably 30% by mass or more, more preferably 50% by mass or more, even more preferably 70% by mass or more, even more preferably 80% by mass or more, even more preferably 90% by mass or more, and 100% by mass or less.

[0138] Examples of boronamine complexes include boronamine halide complexes. Examples of boronamine halide complexes include boronamine trifluoride complexes and boronamine trichloride complexes. From the viewpoint of improving the pot life of the composition, it is preferable to include a boronamine trichloride complex.

[0139] Examples of amine components in boronamine complexes include alkylamines, alkanolamines, and cyclic aliphatic amines.

[0140] Examples of alkylamines include monoalkylamines such as monoethylamine, monopropylamine, monobutylamine, monohexylamine, monooctylamine, and monolauramine; dialkylamines such as dimethylamine, diethylamine, dipropylamine, dibutylamine, dihexylamine, dioctylamine, and dilauramine; and trialkylamines such as triethylamine, tripropylamine, tributylamine, trihexylamine, trioctylamine, trilauramine, N,N-dimethylethylamine, N,N-dimethylpropylamine, N,N-dimethylbutylamine, N,N-dimethylhexylamine, N,N-dimethyloctylamine, and N,N-dimethyllauramine.

[0141] Examples of alkanolamines include monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine, N-methylethanolamine, N-methylisopropanolamine, N-butylethanolamine, N-methyldiethanolamine, N-butyldiethanolamine, and N-methyldiisopropanolamine.

[0142] Examples of cyclic aliphatic amines include piperidine and N,N-dicyclohexylmethylamine.

[0143] From the viewpoint of improving the pot life of the composition, the amine component in the boroamine complex is preferably a trialkylamine, more preferably at least one selected from the group consisting of N,N-dimethylethylamine, N,N-dimethylpropylamine, N,N-dimethylbutylamine, N,N-dimethylhexylamine, N,N-dimethyloctylamine and N,N-dimethyllauroamine, and even more preferably N,N-dimethyloctylamine.

[0144] Commercially available products that use boronamine complexes as component (D) include HUNTSMAN's "Accelerator DY9577" (boronamine trichloride complex, amine component: N,N-dimethyl-n-octylamine), etc.

[0145] Component (D) may also contain epoxy resin curing agents other than boron-amine complexes. Examples of epoxy resin curing agents other than boron-amine complexes include amine curing agents, phenol curing agents, acid anhydride curing agents, and acyl hydrazine curing agents, and one or more of them may be used.

[0146] From the viewpoint of improving the pot life of the composition, the content of epoxy resin curing agent other than boronamine complex in component (D) is preferably 70% by mass or less, more preferably 50% by mass or less, further preferably 30% by mass or less, even more preferably 20% by mass or less, even more preferably 10% by mass or less, even more preferably 5% by mass or less, and the lower limit is 0% by mass.

[0147] <Component (E): Thermal free radical polymerization initiator>

[0148] The component (E) used in this invention can be any compound that generates free radicals by heating and can polymerize the (meth)acryloyloxy group in components (B) and (C), for example, azo compounds and organic peroxides.

[0149] Examples of azo compounds include azobisisobutyronitrile (AIBN), 2,2'-azobis(2,4-dimethylvaleronitrile) (ABVN), 4,4'-azobis(4-cyanopentanoic acid) (ABCVA), 2,2'-azobis(2-methylbutyronitrile) (AMBN), 2,2'-azobis(2-methylpropanediamine) dihydrochloride (AAPH), 2,2'-azobis(2-methylpropionic acid) dimethyl ester, and 2,2'-azobis[2-(2-imidazolin-2-yl)propane] dihydrochloride, and one or more of them may be used.

[0150] Examples of organic peroxides include 2,2-bis(4,4-di-tert-butylperoxycyclohexyl)propane, 1,1-di(tert-hexylperoxycyclohexane), 1,1-di(tert-butylperoxycyclohexane), n-butyl-4,4-di(tert-butylperoxy)valerate, and 2,2-di(tert-butylperoxy)butane peroxide ketals; tert-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, p-menthane hydroperoxide, and 1,1,3,3-tetramethylbutyl hydroperoxide; tert-butyl cumyl peroxide, di... Dialkyl peroxides including tert-butyl peroxide, di-tert-hexyl peroxide, dicumyl peroxide, α,α'-di(tert-butylperoxide)diisopropylbenzene, tert-butylcumyl peroxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, 2,5-dimethyl-2,5-bis(tert-butylperoxide)hexyn-3, etc.; diisobutyl peroxide, di(3,5,5-trimethylhexanol) peroxide, dilauroyl peroxide, disuccinic acid peroxide, benzoyl peroxide, etc.; diisopropyl peroxide dicarbonate, peroxide... Dicarbonates such as di-n-propyl dicarbonate, bis(4-tert-butylcyclohexyl) dicarbonate peroxide, di-2-ethylhexyl dicarbonate peroxide, and di-sec-butyl dicarbonate peroxide; cumyl peroxide neodecanoate, 1,1,3,3-tetramethylbutyl peroxide neodecanoate, tert-hexyl peroxide neodecanoate, tert-butyl peroxide neodecanoate, tert-hexyl pervalerate, tert-butyl pervalerate, 2,5-dimethyl-2,5-di(2-ethylhexanoylperoxide)hexane, and 1,1,3,3-tetramethylbutyl peroxide-2-ethylhexanoate. Tert-hexyl peroxide-2-ethylhexanoate, tert-butyl peroxide-2-ethylhexanoate, tert-butyl peroxide lauryl ester, tert-butyl peroxide-3,5,5-trimethylhexanoate, tert-hexyl peroxide isopropyl monocarbonate, tert-butyl peroxide isopropyl monocarbonate, tert-butyl peroxide-2-ethylhexyl monocarbonate, 2,5-dimethyl-2,5-di(benzoyl peroxide)hexane, tert-butyl peroxide acetate, tert-hexyl peroxide benzoate, tert-butyl peroxide benzoate, etc., may use one or more of these peroxide esters.

[0151] From the viewpoint of improving the pot life of the composition, component (E) is preferably a thermal free radical polymerization initiator with a 10-hour half-life temperature of 100°C or more, and more preferably an organic peroxide with a 10-hour half-life temperature of 100°C or more.

[0152] Examples of organic peroxides with a 10-hour half-life temperature of 100°C or higher include at least one selected from the group consisting of peroxy ketals, hydroperoxides, dialkyl peroxides, and peroxide esters.

[0153] From the viewpoint of curability of components (B) and (C) and from the viewpoint of improving the pot life of the composition, component (E) preferably contains a dialkyl peroxide, more preferably contains 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane.

[0154] <Content>

[0155] From the viewpoint of improving the pot life of the composition, improving the Tg, elongation, tensile stress and tensile modulus of the cured product, the content of component (A) in the thermosetting resin composition is preferably 30 to 85% by mass, more preferably 40 to 85% by mass, even more preferably 50 to 80% by mass, and even more preferably 60 to 80% by mass.

[0156] From the viewpoint of improving the pot life of the composition, improving the Tg, elongation, tensile stress and tensile modulus of the cured product, the content of component (B) in the thermosetting resin composition is preferably 5 to 60% by mass, more preferably 10 to 50% by mass, even more preferably 15 to 40% by mass, and even more preferably 15 to 30% by mass.

[0157] Furthermore, relative to 100 parts by weight of component (A), the content of component (B) in the thermosetting resin composition is preferably 5 to 70 parts by weight, more preferably 10 to 60 parts by weight, even more preferably 10 to 50 parts by weight, even more preferably 15 to 50 parts by weight, even more preferably 20 to 50 parts by weight, and even more preferably 30 to 50 parts by weight. If the content of component (B) in the thermosetting resin composition is 5 parts by weight or more relative to 100 parts by weight of component (A), a long pot life can be easily achieved. Furthermore, if it is 70 parts by weight or less, it is easier to maintain the Tg, tensile stress, and tensile modulus of the cured product.

[0158] From the viewpoint of improving the pot life of the composition, improving the Tg, elongation, tensile stress and tensile modulus of the cured product, the content of component (C) in the thermosetting resin composition is preferably 0.1 to 20% by mass, more preferably 0.3 to 10% by mass, even more preferably 0.5 to 7.0% by mass, and even more preferably 0.8 to 5.0% by mass.

[0159] The content of component (C) in the thermosetting resin composition is preferably 0.1 to 30 parts by mass relative to the total amount of components (A) and (B) 100 parts by mass, more preferably 0.5 to 20 parts by mass, further preferably 0.5 to 10 parts by mass, and even more preferably 0.8 to 6.0 parts by mass. If the content of component (C) in the thermosetting resin composition is 0.1 parts by mass or more relative to the total amount of components (A) and (B) 100 parts by mass, it is likely to help improve the Tg, tensile stress, and tensile modulus of the cured product; if it is 30 parts by mass or less, the elongation of the cured product can be maintained.

[0160] The content of component (D) in the thermosetting resin composition is preferably 0.1 to 40 parts by weight relative to 100 parts by weight of component (A), more preferably 0.5 to 20 parts by weight, further preferably 1 to 10 parts by weight, even more preferably 2 to 10 parts by weight, and even more preferably 3 to 8 parts by weight. If the content of component (D) in the thermosetting resin composition is 0.1 parts by weight or more relative to 100 parts by weight of component (A), curability is easily ensured; if it is 40 parts by weight or less, a long pot life is easily achieved.

[0161] The content of component (E) in the thermosetting resin composition is preferably 0.01 to 5 parts by weight relative to 100 parts by weight of component (B), more preferably 0.05 to 4 parts by weight, further preferably 0.1 to 3 parts by weight, and even more preferably 0.5 to 2 parts by weight. If the content of component (E) in the thermosetting resin composition is 0.01 parts by weight or more relative to 100 parts by weight of component (B), curability is easily ensured; if it is 5 parts by weight or less, a long pot life is easily achieved.

[0162] From the viewpoint of effectively demonstrating the effects of the present invention, the total content of components (A) to (E) in the thermosetting resin composition is preferably 70% by mass or more, more preferably 80% by mass or more, further preferably 90% by mass or more, and even more preferably 95% by mass or more, and is 100% by mass or less in the solid components of the thermosetting resin composition. It should be noted that "solid components of the thermosetting resin composition" refers to the amount after removing water and organic solvents from the total amount of the thermosetting resin composition.

[0163] <Other Ingredients>

[0164] Thermosetting resin compositions may further contain, depending on the application, other components such as fillers, plasticizers and other modifying agents, thixotropic agents and other flow modifiers, reactive or non-reactive diluents, pigments, leveling agents, tackifiers, stress relaxation agents and other components.

[0165] Examples of stress relaxation components include silicone-based elastomer particles, butyl acrylate-based elastomer particles, polyetheramine-based elastomer particles, and other rubber particles. Liquid rubber components such as epoxidized polybutadiene can also be used. Commercially available stress relaxation components include KANEKA Co., Ltd.'s "KANE ACE" B series, FM series, M series, and MX series, and Daicel Co., Ltd.'s liquid epoxidized polybutadiene, namely "EPOLEADPB3600" and "EPOLEAD PB4700".

[0166] When the thermosetting resin composition contains a stress relaxation component, its content in the solid component of the thermosetting resin composition is preferably 0.1 to 15% by mass, more preferably 0.5 to 10% by mass.

[0167] Solvent

[0168] From the viewpoint of improving the permeability to reinforcing fibers, the thermosetting resin composition of the present invention may further contain a solvent.

[0169] Examples of solvents include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methoxyethanol, 2-ethoxyethanol, 2-propoxyethanol, 2-butoxyethanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1-propoxy-2-propanol, etc.; ester solvents such as ethyl acetate and butyl acetate; ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; ether solvents such as diethyl ether and diisopropyl ether; and hydrocarbon solvents such as toluene. One or more of these solvents may be used.

[0170] From the viewpoint of the solubility of the mixed components and the ease of solvent removal, the solvent is preferably selected from at least one of the group consisting of alcohol solvents, ester solvents, ketone solvents and hydrocarbon solvents having 8 or fewer carbon atoms, and more preferably from at least one of the group consisting of methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, ethyl acetate, methyl ethyl ketone, methyl isobutyl ketone and toluene.

[0171] When the thermosetting resin composition contains a solvent, its content is not particularly limited. From the viewpoint of improving the permeability to the reinforcing fibers, it is preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 15% by mass or more in the thermosetting resin composition. From the viewpoint of ease of solvent removal, it is preferably 80% by mass or less, and more preferably 70% by mass or less.

[0172] The thermosetting resin composition can be a solvent-free composition that is substantially free of solvent. A solvent-free thermosetting resin composition refers to a thermosetting resin composition in which the solvent content is preferably less than 5% by mass, more preferably less than 2% by mass, further preferably less than 1% by mass, even more preferably less than 0.5% by mass, and even more preferably 0% by mass.

[0173] Furthermore, the thermosetting resin composition of the present invention is preferably a non-aqueous thermosetting resin composition, and preferably has a low water content. The water content in the thermosetting resin composition is preferably less than 10% by mass, more preferably less than 5% by mass, further preferably less than 2% by mass, even more preferably less than 1% by mass, even more preferably less than 0.1% by mass, and even more preferably 0% by mass. The water content mentioned here refers to the amount of water intentionally added to the thermosetting resin composition, and does not exclude the presence of small amounts of water as impurities.

[0174] <Applicable Period>

[0175] The thermosetting resin composition of the present invention has a long pot life, for example, it can reach a pot life of more than 180 days when stored at room temperature (23°C).

[0176] There are no particular limitations on the preparation method of the thermosetting resin composition. Known methods and apparatus can be used to mix components (A) to (E) with other components as needed. There are also no particular limitations on the mixing order of the components in the thermosetting resin composition. However, if any of components (A) to (C) as resin components has a high viscosity, it is preferable to preheat components (A) to (C) to 80-120°C and mix them, then cool them to below 80°C, and then mix components (D) and (E). This is to avoid heat curing during the preparation of the thermosetting resin composition.

[0177] [cured material]

[0178] The cured product of the thermosetting resin composition of the present invention (hereinafter also referred to as "the cured product of the present invention") is obtained by heat curing the above-described thermosetting resin composition of the present invention using a known method. The curing conditions of the thermosetting resin composition are appropriately selected according to the application and form, and the curing temperature is preferably 80~180°C, more preferably 100~160°C, and the curing time is preferably 1 minute to 12 hours, more preferably 5 minutes to 6 hours.

[0179] The morphology of the cured product of the present invention is not particularly limited and can be selected according to the application. For example, when the thermosetting resin composition is used as a coating, the cured product of the composition is usually in the form of a film. It should be noted that, from the viewpoint of effectively exerting the effects of the present invention, the cured product of the present invention is preferably the matrix resin of the fiber-reinforced composite material described later.

[0180] From the viewpoint of the matrix resin, etc., used in the fiber-reinforced composite materials described later, the glass transition temperature (Tg) of the cured product of the present invention is preferably 100°C or higher, more preferably 110°C or higher, even more preferably 115°C or higher, and even more preferably 120°C or higher, and is generally 200°C or lower. Specifically, the Tg of the cured product can be measured by the method described in the examples.

[0181] From the viewpoint of improving the impact resistance of the matrix resin used in the fiber-reinforced composite material described later, the tensile elongation of the cured product of the present invention is preferably 4.0% or more, more preferably 4.5% or more, and even more preferably 5.0% or more. From the viewpoint of obtaining high hardness, it is preferably 20% or less, and more preferably 10% or less.

[0182] From the viewpoint of improving the hardness of the matrix resin used in the fiber-reinforced composite material described later, the tensile stress of the cured product of the present invention is preferably 40 MPa or more, more preferably 43 MPa or more, and even more preferably 45 MPa or more.

[0183] From the viewpoint of improving the hardness of the matrix resin used in the fiber-reinforced composite material described later, the tensile modulus of the cured product of the present invention is preferably 1.2 GPa or more, more preferably 1.3 GPa or more, and even more preferably 1.5 GPa or more.

[0184] The tensile elongation, tensile stress, and tensile modulus of the cured product can be measured according to JIS K7161-1:2014 and JIS K7161-2:2014, specifically by the methods described in the examples.

[0185] [Prepreg]

[0186] The prepreg of the present invention comprises the aforementioned thermosetting resin composition and reinforcing fibers.

[0187] Examples of reinforcing fibers used in prepregs include short fibers, long fibers, and continuous fibers. Among these, from the viewpoint of manufacturing large structures using the resulting prepreg, long fibers or continuous fibers are preferred, and continuous fibers are more preferred.

[0188] It should be noted that, in this specification, short fibers refer to fibers with a length of 0.1 mm or more but less than 10 mm, and long fibers refer to fibers with a length of 10 mm or more but less than 100 mm. Furthermore, continuous fibers refer to fiber bundles with a fiber length exceeding 100 mm.

[0189] Examples of continuous fiber shapes include tows, sheets, and tapes. Examples of continuous fibers that make up sheets or tapes include unidirectional (UD) materials, fabrics, and nonwovens.

[0190] From the viewpoint of manufacturing fiber-reinforced composite materials using prepregs and through fiber winding or tape winding, the shape of the continuous fibers is preferably a bundle or tape, and more preferably a bundle. From the viewpoint of easily obtaining high strength and high elastic modulus, the number of continuous fiber bundles (number of filaments) constituting the bundle is preferably 3K to 50K, and more preferably 6K to 40K.

[0191] In continuous fibers, the average fiber length of the continuous fiber bundle is not particularly limited, but from the viewpoint of forming processability, it is preferably 1 to 10,000 m, and more preferably 100 to 10,000 m.

[0192] From the viewpoint of formability and ease of obtaining high strength and high elastic modulus, the average fineness of the continuous fiber bundle is preferably 50 to 2000 tex (g / 1000m), more preferably 200 to 1500 tex, and even more preferably 500 to 1500 tex.

[0193] In addition, the average tensile modulus of the continuous fiber bundle is preferably 50~1000 GPa.

[0194] Examples of materials that can be used as reinforcing fibers include inorganic fibers such as carbon fiber, glass fiber, basalt fiber, metal fiber, boron fiber, and ceramic fiber; and organic fibers such as aramid fiber, polyoxymethylene fiber, aromatic polyamide fiber, poly(p-phenylenebenzobisoxazole) fiber, and ultra-high molecular weight polyethylene fiber. Among these, inorganic fibers are preferred from the viewpoint of achieving high strength; from the viewpoint of lightweight yet high strength and high modulus of elasticity, at least one fiber selected from the group consisting of carbon fiber, glass fiber, and basalt fiber is preferred; and from the viewpoint of strength and lightweight, carbon fiber is more preferred.

[0195] Examples of carbon fibers include polyacrylonitrile-based carbon fibers and pitch-based carbon fibers. Additionally, carbon fibers derived from plant-based raw materials such as lignin and cellulose can also be used.

[0196] The reinforcing fibers can be treated with a treatment agent. Examples of treatment agents include surface treatment agents or bundling agents.

[0197] As the surface treatment agent described above, a silane coupling agent is preferred. Examples include silane coupling agents having vinyl groups, silane coupling agents having amino groups, silane coupling agents having epoxy groups, silane coupling agents having (meth)acryloyl groups, and silane coupling agents having mercapto groups.

[0198] Examples of such bundlers include urethane-based bundlers, epoxy-based bundlers, acrylic-based bundlers, polyester-based bundlers, vinyl ester-based bundlers, polyolefin-based bundlers, polyether-based bundlers, and carboxylic acid-based bundlers. One or more of these can be used. Examples of bundlers combining two or more of these compounds include urethane / epoxy bundlers, urethane / acrylic bundlers, and urethane / carboxylic acid bundlers.

[0199] From the viewpoint of improving the interfacial adhesion of the cured product with the thermosetting resin composition and further improving the strength and impact resistance of the obtained prepreg and fiber-reinforced composite material, the amount of the aforementioned treatment agent relative to the reinforcing fiber is preferably 0.001 to 5% by mass, more preferably 0.1 to 3% by mass, and even more preferably 0.5 to 2% by mass.

[0200] Commercially available products can also be used as reinforcing fibers. Examples of commercially available continuous carbon fiber (tow) products include Toray Industries, Inc.'s Torayca yarn series "T300", "T300B", "T400HB", "T700SC", "T800SC", "T800HB", "T830HB", "T1000GB", "T100GC", "M35JB", "M40JB", "M46JB", "M50JB", "M55J", "M55JB", "M60JB", "M30SC", and "Z600", etc.; and Teijin Corporation's Tenax "HTA40" series and "HTS40" series. The product lines include: “HTS45” series, “HTS45P12” series, “STS40” series, “UTS50” series, “ITS50” series, “ITS55” series, “IMS40” series, “IMS60” series, “IMS65” series, “IMS65P12” series, “HMA35” series, “UMS40” series, “UMS45” series, “UMS55” series, “HTS40MC” series, etc.; and carbon fiber tows from Mitsubishi Chemical Corporation, including PYROFIL “HT”, “IM”, “HM” series, GRAFIL “HT” series, and “DIALEAD” series.

[0201] In addition, commercially available continuous carbon fiber products other than towed fibers include Torayca fabrics manufactured by Toray Industries, Ltd., such as "CO6142", "CO6151B", "CO6343", "CO6343B", "CO6347B", "CO6644B", "CK6244C", "CK6273C", "CK6261C", "UT70" series, "UM46" series, "BT70" series, "T300" series, "T300B" series, "T400HB" series, "T700SC" series, "T800SC" series, "T800HB" series, "T1000GB" series, and "M35JB" series. Series including “M40JB”, “M46JB”, “M50JB”, “M55J”, “M55JB”, “M60JB”, “M30SC”, and “Z600GT”; and PYROFIL carbon fiber fabrics manufactured by Mitsubishi Chemical Corporation, including “TR3110M”, “TR3523M”, “TR3524M”, “TR6110HM”, “TR6120HM”, “TRK101M”, “TRK510M”, “TR3160TMS”, “TRK979PQRW”, “TRK976PQRW”, “TR6185HM”, and “TRK180M”.

[0202] Regarding the content of reinforcing fibers in the prepreg, from the viewpoint of obtaining high strength and high elastic modulus, the volume fraction of reinforcing fibers in the prepreg is preferably 0.10 or more, more preferably 0.20 or more, further preferably 0.30 or more, and even more preferably 0.40 or more. Furthermore, from the viewpoint of improving impact resistance and processability, the volume fraction of reinforcing fibers in the prepreg is preferably 0.85 or less, more preferably 0.80 or less, and even more preferably 0.70 or less.

[0203] The volume fraction Vf1 of reinforcing fibers in the prepreg can be calculated using the following formula.

[0204] Vf1 = {Mass of reinforcing fiber (g) / Specific gravity of reinforcing fiber} ÷ [{Mass of reinforcing fiber (g) / Specific gravity of reinforcing fiber} + {Mass of solid component of the impregnated thermosetting resin composition (g) / Specific gravity of solid component of the thermosetting resin composition}]

[0205] Furthermore, from the viewpoint of obtaining the effects of the present invention, the total content of solid components and reinforcing fibers in the thermosetting resin composition constituting the prepreg is preferably 70% by mass or more, more preferably 80% by mass or more, even more preferably 90% by mass or more, and 100% by mass or less.

[0206] <Prepreg Shape and Manufacturing Method>

[0207] The shape of the prepreg varies depending on the morphology of the reinforcing fibers used, but from the viewpoint of manufacturing fiber-reinforced composite materials by fiber winding or tape winding, the prepreg of the present invention is preferably a tow prepreg or a tape prepreg. Examples of tape prepregs include UD tape prepregs using unidirectional (UD) materials.

[0208] Alternatively, the prepreg of the present invention can also be a sheet-shaped prepreg made of continuous fibers in the form of UD material, fabric, non-woven fabric, etc.

[0209] There are no particular limitations on the manufacturing method of the prepreg; it can be manufactured using conventional methods. For example, by impregnating the aforementioned thermosetting resin composition into reinforcing fibers and then removing the solvent in a drying process as needed, a prepreg can be obtained.

[0210] There are no particular limitations on the method for impregnating the thermosetting resin composition into the reinforcing fibers, and known methods can be appropriately used depending on the morphology of the reinforcing fibers. For example, in the case of manufacturing tow prepreg, a method can be described as follows: a continuous fiber bundle wound from a roller is impregnated in a resin bath filled with the aforementioned thermosetting resin composition, and after the composition has impregnated, it is lifted out of the resin bath. Then, a step can be performed to remove the remaining thermosetting resin composition using a squeeze roller or the like.

[0211] Impregnation of thermosetting resin compositions can be carried out under pressure or depressurization conditions as needed.

[0212] Next, as needed, the reinforcing fibers impregnated with the thermosetting resin composition are subjected to a drying process to remove the solvent. There are no particular limitations on the drying conditions in the drying process, but conditions that remove the solvent and prevent excessive curing of the thermosetting resin composition are preferred. From this perspective, for example, the drying temperature can be selected in the range of 30 to 120°C, and the drying time can be selected in the range of 10 seconds to 5 minutes.

[0213] The prepreg obtained after the above drying process can be temporarily wound up to make prepreg products, or it can be continuously supplied to the manufacture of fiber-reinforced composite materials after the drying process without being wound up.

[0214] The prepreg of the present invention has a long service life, for example, it can be stored at room temperature (23°C) for more than 180 days.

[0215] [Fiber-reinforced composite materials]

[0216] The fiber-reinforced composite material (hereinafter also simply referred to as "composite material") of the present invention is a cured product of the above-mentioned prepreg, comprising a cured product of the above-mentioned thermosetting resin composition and reinforcing fibers. The fiber-reinforced composite material of the present invention, through the cured product comprising the above-mentioned thermosetting resin composition, exhibits high heat resistance and impact resistance due to the high glass transition temperature and elongation of the cured product.

[0217] The prepregs, thermosetting resin compositions, reinforcing fibers, and their preferred methods for the manufacture of composite materials are the same as described above.

[0218] <Content>

[0219] Regarding the content of reinforcing fibers in fiber-reinforced composite materials, from the viewpoint of obtaining high strength and high elastic modulus, the volume fraction of reinforcing fibers in the fiber-reinforced composite material is preferably 0.10 or more, more preferably 0.20 or more, further preferably 0.30 or more, and even more preferably 0.40 or more. Furthermore, from the viewpoint of improving impact resistance and processability, the volume fraction of reinforcing fibers in the fiber-reinforced composite material is preferably 0.85 or less, more preferably 0.80 or less, and even more preferably 0.70 or less.

[0220] The volume fraction Vf of reinforcing fibers in fiber-reinforced composites can be calculated using the following formula.

[0221] Vf = {Mass of reinforcing fiber (g) / Specific gravity of reinforcing fiber} ÷ [{Mass of reinforcing fiber (g) / Specific gravity of reinforcing fiber} + {Mass of cured thermosetting resin composition (g) / Specific gravity of cured thermosetting resin composition}]

[0222] <Manufacturing Methods of Fiber Reinforced Composite Materials>

[0223] The composite material can be manufactured by preforming it into the desired shape using the aforementioned prepreg and then curing the prepreg. For example, when applying the composite material of the present invention to hollow shaped bodies such as pipes, shafts, gas cylinders, and tanks, the composite material can be manufactured using filament or strip-shaped prepregs through fiber winding, strip winding, weaving, 3D printing, or other methods.

[0224] In fiber winding or tape winding, specifically, a prepreg in the shape of a filament or tape is wound around the outer surface of a bulb, mandrel, or liner and then heated and cured, thereby enabling the manufacture of a composite material of the desired shape.

[0225] In the weaving method, for example, the following steps are performed: using a ball or mandrel, the prepreg in the shape of a filament bundle or tape is woven into a prepreg using a tape weaving machine in one direction or in a tape structure to form the prepreg; then, the prepreg is heated and cured. It should be noted that in the weaving method, the prepreg in the shape of a filament bundle or tape can also be roped and shaped without using a ball or mandrel.

[0226] When using sheet-like prepregs with unidirectional (UD) materials, fabrics, nonwovens, etc. as continuous fibers, one or more sheets of prepregs can be stacked in a mold and heated and cured under vacuum or pressure conditions to manufacture composite materials.

[0227] There are no particular restrictions on the curing method of the prepreg in the manufacture of the composite material. It can be carried out by known methods at a temperature and time sufficient to cure the thermosetting resin composition contained in the prepreg. The curing conditions of the prepreg also depend on the thickness of the prepreg and the resulting composite material. For example, the curing temperature is preferably selected in the range of 80 to 180°C, more preferably in the range of 100 to 160°C, and the curing time is preferably selected in the range of 1 minute to 12 hours, more preferably in the range of 5 minutes to 6 hours.

[0228] From the viewpoint of manufacturing using prepregs in the form of filaments or strips, the composite material of the present invention is suitable for use in shaped bodies with hollow forms, such as tubes, shafts, gas cylinders, and tanks. This composite material is, for example, suitable as a material for forming high-pressure gas containers.

[0229] [High-pressure gas container]

[0230] The high-pressure gas container of the present invention comprises the aforementioned fiber-reinforced composite material. At least a portion of the high-pressure gas container of the present invention may be constituted by the aforementioned fiber-reinforced composite material. For example, if it is a high-pressure gas container having an inner liner and an outer layer disposed such that it covers the outer surface of the inner liner, examples can be given of high-pressure gas containers in which at least one of the inner liner and the outer layer is constituted by the aforementioned fiber-reinforced composite material. Furthermore, if it is a high-pressure gas container without an inner liner, examples can be given of containers whose entire contents are constituted by the aforementioned fiber-reinforced composite material.

[0231] Specific examples of high-pressure gas containers comprising fiber-reinforced composite materials include: (1) a configuration having a metal liner and an outer layer formed of the fiber-reinforced composite material of the present invention; (2) a configuration having a resin liner and an outer layer formed of the fiber-reinforced composite material of the present invention; (3) a configuration having a liner formed of the fiber-reinforced composite material of the present invention and an outer layer formed of a material other than the fiber-reinforced composite material; and (4) a configuration consisting only of a container formed of the fiber-reinforced composite material of the present invention (without a liner).

[0232] The metal used in the “metal lining” mentioned in (1) above can be exemplified by light alloys such as aluminum alloys and magnesium alloys.

[0233] As for the resin used in the "resin liner" mentioned in (2) above, there are no particular restrictions as long as it is a resin with excellent gas barrier properties and pressure resistance. Examples include thermoplastic resins, cured thermosetting resins, and cured light-curing resins. Among these, thermoplastic resins are preferred from the viewpoint that the liner can be easily formed.

[0234] Examples of thermoplastic resins 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, polyarylate resins, liquid crystal polymers, polyetheretherketone resins, polyetherketone resins, polyetherketoneketone resins, polyetheretherketoneketone resins, polybenzimidazole resins, etc., and one or more of them may be used.

[0235] From the viewpoint of gas barrier properties and pressure resistance, the thermoplastic resin is preferably at least one selected from the group consisting of polyamide resin and polyolefin resin, and more preferably polyamide resin.

[0236] In addition, from the viewpoint of improving impact resistance, the resin liner may also contain the aforementioned stress relaxation components.

[0237] Regarding the “outer layer formed of a material other than the fiber-reinforced composite material” in (3) above, from the viewpoint of improving reinforcement, it is preferable to cite an outer layer formed of a fiber-reinforced composite material other than the fiber-reinforced composite material of the present invention.

[0238] In the aforementioned (1) to (3) methods, the outer layer can be formed in such a way that it covers the outer surface of the main body of the inner lining without gaps.

[0239] The outer layer can also be directly applied to the outer surface of the inner lining. Alternatively, one or more other layers can be applied to the outer surface of the inner lining, on the surface of these other layers. For example, to improve the adhesion between the inner lining and the outer layer, an adhesive layer can be applied between them.

[0240] When the high-pressure gas container is in the manner described in (1) or (2) above, the thickness of the outer layer formed by the fiber-reinforced composite material of the present invention can be appropriately selected according to the capacity, shape, etc. of the high-pressure gas container. From the viewpoint of imparting high gas barrier properties and impact resistance, it is preferably 100 μm or more, more preferably 200 μm or more, and even more preferably 400 μm or more. From the viewpoint of miniaturization and lightweighting of the high-pressure gas container, it is preferably 80 mm or less, more preferably 60 mm or less.

[0241] When the high-pressure gas container is in the manner described in (3) above, the thickness of the liner formed by the fiber-reinforced composite material of the present invention can be appropriately selected according to the capacity, shape and other properties of the high-pressure gas container. From the viewpoint of gas barrier and pressure resistance, it is preferably 100 μm or more, more preferably 200 μm or more, and even more preferably 400 μm or more. From the viewpoint of miniaturization and lightweighting of the high-pressure gas container, it is preferably 60 mm or less, and more preferably 40 mm or less.

[0242] When the high-pressure gas container is in the manner described in (4) above, the thickness of the container formed by the fiber-reinforced composite material of the present invention can be appropriately selected according to the capacity, shape and other properties of the high-pressure gas container. From the viewpoint of gas barrier and pressure resistance, it is preferably 1 mm or more, more preferably 2 mm or more, and even more preferably 5 mm or more. From the viewpoint of miniaturization and lightweighting of the high-pressure gas container, it is preferably 80 mm or less, and more preferably 60 mm or less.

[0243] Regarding the content of reinforcing fibers in the liner, outer layer, or high-pressure gas container formed from the fiber-reinforced composite material of the present invention, from the viewpoint of obtaining high strength and high elastic modulus, the volume fraction of the reinforcing fibers is preferably 0.10 or more, more preferably 0.20 or more, further preferably 0.30 or more, and even more preferably 0.40 or more. Furthermore, from the viewpoint of gas barrier properties, impact resistance, and processability, the volume fraction of the reinforcing fibers is preferably 0.85 or less, more preferably 0.80 or less, further preferably 0.75 or less, and even more preferably 0.70 or less.

[0244] The volume fraction of the aforementioned reinforcing fibers can be calculated using the same method as described above.

[0245] From the perspective of lightweight and the requirement for high gas barrier properties of fiber-reinforced composite materials, the high-pressure gas container is preferably any of the above-mentioned (2), (3) or (4), and more preferably (3) or (4).

[0246] It should be noted that high-pressure gas containers may also have components such as pipe heads and valves made of materials other than fiber-reinforced composite materials. Additionally, any layer, such as a protective layer, coating layer, or rust-preventive layer, can be formed on the surface of the high-pressure gas container.

[0247] The gas to be stored in the high-pressure gas container can be any gas that is gaseous at 25°C and 1 atm. In addition to hydrogen, other examples include oxygen, carbon dioxide, nitrogen, argon, LPG, alternative Freon, and methane. From the viewpoint of the effectiveness of this invention, hydrogen is preferred.

[0248] <Manufacturing Method of High-Pressure Gas Containers>

[0249] As a method for manufacturing the high-pressure gas container of the present invention, the manufacturing method described in the aforementioned method for manufacturing fiber-reinforced composite materials can be appropriately used depending on the form of the reinforcing fiber or prepreg used. When manufacturing a high-pressure gas container using a tow or strip-shaped prepreg, the tow or strip-shaped prepreg can be shaped by fiber winding, strip winding, weaving, 3D printing, etc., to manufacture the high-pressure gas container.

[0250] In the case of a high-pressure gas container in the manner described in (1) or (2) above, a fiber winding or tape winding method is used to wind a prepreg in the shape of a filament or tape to cover the outer surface of a metal or resin liner, and then heat-curing is performed to form an outer layer made of fiber-reinforced composite material, thereby enabling the manufacture of a high-pressure gas container.

[0251] In the case of a high-pressure gas container in the manner described in (3) or (4) above, a prepreg in the shape of a filament or strip is formed into a container shape by means of fiber winding, tape winding, weaving, 3D printing, etc., and then heated and cured, thereby manufacturing a high-pressure gas container.

[0252] Example

[0253] The present invention will be described in detail below with examples and comparative examples, but the present invention is not limited to the following examples. It should be noted that the measurement and evaluation in this embodiment were performed by the following methods.

[0254] Glass transition temperature (Tg)

[0255] The thermosetting resin compositions prepared in each example were shaped into flat plates with a thickness of 200 mm × 200 mm × 2 mm and thermo-cured in a hot air oven at 130 °C for 180 minutes to produce cured products. Strips with a thickness of 50 mm × 10 mm × 2 mm were cut from the cured products as samples for dynamic viscoelasticity (DMA) testing.

[0256] Using the aforementioned samples, DMA bending measurements were performed using a rotational rheometer "ARES G2" (manufactured by TA Instruments) under the following conditions. The vertical axis represents tanδ, and the horizontal axis represents the peak value of tanδ at the measurement temperature, which is taken as the Tg of the cured product.

[0257] (Measurement conditions)

[0258] Measurement mode: Bending DMA measurement

[0259] Measurement temperature: 30~180℃

[0260] Heating rate: 5℃ / minute

[0261] <Tension elongation, tensile stress, tensile modulus>

[0262] The thermosetting resin compositions prepared in each example were formed into flat plates with a thickness of 200 mm × 200 mm × 2 mm and thermo-cured in a hot air oven at 130°C for 180 minutes to produce cured products. Strips with a thickness of 180 mm × 15 mm × 2 mm were cut from the cured products to serve as tensile test pieces.

[0263] Using the above-mentioned test specimens, tensile tests (N=3) were conducted under the following conditions using a precision universal testing machine (Autograph AGX-plus, manufactured by Shimadzu Corporation) according to JIS K7161-1:2014 and JIS K7161-2:2014. The tensile elongation, tensile stress, and tensile modulus were calculated using the following formulas. The length of the test specimen at fracture was calculated from the displacement of the force sensor at fracture.

[0264] (Measurement conditions)

[0265] Spacing between fixtures: 115mm

[0266] Distance between markings: 75mm

[0267] Force sensor (tensile force): 1kN

[0268] Tensile speed: 1 mm / min (Tension direction: along the length of the test piece)

[0269] (Calculation formula)

[0270] Tensile elongation (%) = (Length of the test piece at fracture - Initial length of the test piece) / (Initial length of the test piece) × 100

[0271] Tensile stress (MPa) = Load at fracture of the specimen (N) / Initial cross-sectional area of ​​the specimen (mm²) 2 )

[0272] Tensile modulus (GPa) = Elastic modulus gradient (N / mm) × Initial specimen length (mm) / Initial specimen cross-sectional area (mm²) 2 )×10 -3

[0273] The elastic modulus gradient mentioned here refers to the slope of the stress-strain curve between two points corresponding to tensile strain (the increase in the distance between the gauges divided by the distance between the gauges) of 0.05% and 0.25%.

[0274] <Applicable Period>

[0275] After determining the initial viscosity of the thermosetting resin compositions prepared in each example at 23°C, 10g of the thermosetting resin composition was placed in a plastic cup (46mm in diameter) and stored at 23°C. The time it took for the viscosity of the thermosetting resin composition to reach more than twice the initial viscosity is shown in the table.

[0276] The viscosity of the thermosetting resin composition was measured using a Type E viscometer, “TVE-22H type cone-plate viscometer” (manufactured by Toki Sangyo Co., Ltd.).

[0277] Examples 1-14 and Comparative Examples 1-5 (Preparation and Evaluation of Thermosetting Resin Compositions)

[0278] The components shown in Table 1 were mixed and blended in the parts by mass shown in Table 1 to obtain a thermosetting resin composition. The obtained thermosetting resin composition was evaluated by the methods described above. The results are shown in Table 1.

[0279] It should be noted that the mixing amounts (parts by mass) in Table 1 are all amounts of active ingredients.

[0280] [Table 1]

[0281]

[0282] The components listed in Table 1 are as follows.

[0283] <Multifunctional Epoxy Resin (A)>

[0284] • A bisphenol A-derived polyfunctional epoxy resin with glycidyl groups (liquid): Mitsubishi Chemical Corporation "jER828", liquid epoxy resin, epoxy equivalent: 186 g / equivalent, s=0.11 in the following structural formula.

[0285] It should be noted that for compositions using bisphenol A type semi-epoxy methacrylate (manufactured by KSM Corporation, "BAEM-50") as component (C), "the multifunctional epoxy resin (liquid) derived from bisphenol A with glycidyl group" contains, in addition to "jER828", bisphenol A diglycidyl ether in a "BAEM-50" content (25% by mass).

[0286] • A polyfunctional epoxy resin (solid) derived from bisphenol A with glycidyl groups: "jER1004" manufactured by Mitsubishi Chemical Corporation, a polymeric / solid epoxy resin, with an epoxy equivalent of 1026 g / equivalent, and s=6.0 in the following structural formula.

[0287]

[0288] <Compounds (B) without glycidyl groups>

[0289] • (B1) Poly(butadiene-CO-acrylonitrile) with methacryloyloxy groups at both ends, GLEX "Hypro1300X33LC"

[0290] • (B2-1) Ethoxylated bisphenol A dimethacrylate, where k+l in the following structural formula is approximately 10, manufactured by Shin-Nakamura Chemical Industry Co., Ltd. as "BPE-500"

[0291] • (B2-1) Ethoxylated bisphenol A dimethacrylate, where k+l in the following structural formula is approximately 17, manufactured by Shin-Nakamura Chemical Industry Co., Ltd. as "BPE-900"

[0292]

[0293] • (B2-2) Bisphenol A type epoxy dimethacrylate, the compound shown in the following structural formula, KES Corporation "BAEM-50" content (25% by mass)

[0294]

[0295] <Compounds containing (meth)acryloyloxy and glycidyl groups (C)>

[0296] • Glycidyl methacrylate, manufactured by Mitsubishi Gas Chemical Co., Ltd.

[0297] • Bisphenol A type semi-epoxy methacrylate, the compound shown in the following structural formula, "BAEM-50" manufactured by KES Co., Ltd. (content of bisphenol A type semi-epoxy methacrylate: 50% by mass)

[0298]

[0299] <Epoxy Resin Curing Agent (D)>

[0300] • Boron trichloride ammonium complex (amine component: N,N-dimethyl-n-octylamine), HUNTSMAN's "AcceleratorDY 9577"

[0301] <Thermal free radical polymerization initiator (E)>

[0302] • 2,5-Dimethyl-2,5-di(tert-butylperoxy)hexane, manufactured by Nippon Oil Co., Ltd., "PERHEXA 25B", 10-hour half-life temperature: 117.9℃

[0303] As shown in Table 1, the cured thermosetting resin composition of the present invention can achieve a glass transition temperature of 100°C or higher, an elongation at break of 4% or higher, a tensile modulus of 1.2 GPa or higher, and a tensile stress of 40 MPa or higher. Furthermore, the thermosetting resin composition also has a long pot life.

[0304] In contrast, the cured thermosetting resin compositions of Comparative Examples 1-5, which do not contain component (C), all have a tensile stress of less than 40 MPa. Furthermore, for Comparative Examples 4 and 5, the tensile modulus is also less than 1.2 GPa, and excellent mechanical properties cannot be obtained.

[0305] Industrial availability

[0306] According to the present invention, it is possible to provide a thermosetting resin composition having a long pot life, which yields a cured product with high glass transition temperature, elongation, tensile stress, and tensile modulus, and the cured product thereof, comprising...

[0307] The thermosetting resin composition is used in prepregs, fiber-reinforced composites, and high-pressure gas containers.

Claims

1. A thermosetting resin composition comprising: Component A: Multifunctional epoxy resin, Ingredient B: (meth)acrylate compounds without glycidyl groups. Ingredient C: A compound containing (meth)acryloyloxy and glycidyl groups. Component D: Epoxy resin curing agent containing boronamine complex, and Component E: Thermal free radical polymerization initiator.

2. The thermosetting resin composition according to claim 1, wherein, The component B includes component B1: poly(butadiene-CO-acrylonitrile) with (meth)acryloyloxy groups at both ends.

3. The thermosetting resin composition according to claim 1 or 2, wherein, Component B includes component B2: a polyfunctional (meth)acrylate having an aromatic ring.

4. The thermosetting resin composition according to any one of claims 1 to 3, wherein, The component C comprises a compound represented by the following general formula (1). In equation (1), R 11 Represents a hydrogen atom or a methyl group; Z represents a single bond or -(CH2). m -O-, or a divalent group represented by the following general formula (2), -(CH2) m In -O-, m is a number from 2 to 8. In equation (2), R 12 and R 13 Each atom can be independently represented by a hydrogen atom or a methyl group, n is a number from 1 to 5, and * indicates a connecting bond.

5. The thermosetting resin composition according to any one of claims 1 to 4, wherein, The amine component in the boronamine complex is a trialkylamine.

6. A cured product, which is a cured product of the thermosetting resin composition according to any one of claims 1 to 5.

7. A prepreg comprising the thermosetting resin composition according to any one of claims 1 to 5 and reinforcing fibers.

8. The prepreg according to claim 7, wherein, The reinforcing fiber is selected from at least one of the group consisting of carbon fiber, glass fiber and basalt fiber.

9. The prepreg according to claim 7 or 8, wherein, The prepreg is either a tow prepreg or a strip prepreg.

10. A fiber-reinforced composite material, which is a cured product of the prepreg according to any one of claims 7 to 9.

11. A high-pressure gas container comprising the fiber-reinforced composite material of claim 10.

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