Fiber-reinforced composite material intermediate, and method for producing fiber-reinforced composite material

Abstract

To provide a method for producing a fiber-reinforced composite material intermediate which protects a surface of a base material such as a prepreg with a material having rich UV resistance and can prevent degradation by UV, and prevents mixing a resin of a base material inferior in UV resistance and an epoxy resin composition having UV resistance in thermosetting.SOLUTION: A method for producing a fiber-reinforced composite material intermediate includes sticking a resin film containing an epoxy resin composition containing the following components [A] to [D] to a mold, then photocuring the epoxy resin composition, and laminating a preliminary body of a fiber-reinforced composite material onto the resin film. [A] non-aromatic epoxy resin. [B] pigment having a volume average particle diameter of 0.1-10 μm. [C] non-aromatic thermoplastic resin. [D] cation curing agent or anion curing agent.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a method for producing a fiber-reinforced composite material, which comprises photocuring a sheet-shaped film of an epoxy resin composition having excellent UV resistance and UV shielding properties that is attached to a molding die, and then laminating a fiber-reinforced composite material intermediate, which is obtained by laminating a fiber-reinforced composite material preliminary body, onto the photocured film to form a fiber-reinforced composite material intermediate. [Background technology]

[0002] Products requiring high structural performance, such as aircraft structural components, wind turbine blades, automobile exterior panels, and computer applications such as IC trays and laptop computer cases, often use prepregs, which are made by impregnating fibers with thermosetting resins such as epoxy resin, or resin transfer molding (RTM) materials, in which preformed fibers are injected with thermosetting resin and then heated to harden. However, fiber-reinforced composite materials obtained by curing typical prepregs or RTM materials have poor UV resistance (the ability of the material's chemical structure to remain unchanged after UV exposure), and their surfaces deteriorate and degrade when exposed to light. Therefore, in recent years, there has been an increasing demand for adding UV resistance to the surface of carbon fiber-reinforced composite materials.

[0003] Patent Document 1 discloses a sheet material having UV blocking properties (the effect of the material absorbing or reflecting UV) as a surface protection film for carbon fiber reinforced composite materials. Patent Document 2 also discloses a resin composition having UV resistance, which is a combination of an epoxy resin containing no aromatic ring, a carboxylic acid anhydride containing no aromatic ring, and an ultraviolet absorber, and can be used as a coating agent for carbon fiber reinforced composite materials. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Special Publication No. 2015-507648 [Patent Document 2] International Publication No. 2003 / 002661 Summary of the Invention [Problem to be solved by the invention]

[0005] However, the technology disclosed in Patent Document 1 has a problem in that the epoxy resin composition used in the film material contains an aromatic ring, and the film material itself has poor UV resistance. Also, in the technology disclosed in Patent Document 2, although the coating agent itself has UV resistance, when the coating agent is applied to the surface of the prepreg used in the fiber-reinforced composite material and then thermally cured, the coating agent and the prepreg resin, which does not have UV resistance, may mix, resulting in a loss of UV resistance or a deterioration in the mechanical properties of the fiber-reinforced composite material.

[0006] Therefore, the challenge is to realize a method for producing a fiber-reinforced composite material intermediate that can protect the surface of a base material such as a prepreg with a material that is highly UV-resistant and UV-blocking, thereby preventing deterioration due to UV, and that prevents the base material resin, which has poor UV resistance, from mixing with a UV-resistant resin composition during thermal curing. [Means for solving the problem]

[0007] In order to solve the above problems, the present invention has the following configuration: Namely, the method for producing a fiber-reinforced composite material of the present invention is a method for producing a fiber-reinforced composite material intermediate by attaching a resin film containing an epoxy resin composition containing the following components [A] to [D] to a molding die, photocuring the epoxy resin composition, and laminating a fiber-reinforced composite material preform on the resin film. [A] Non-aromatic epoxy resin [B] Pigment with a volume average particle size of 0.1 to 10 μm [C] Non-aromatic thermoplastic resin [D] Cationic or anionic curing agent.

[0008] The method for producing a fiber-reinforced composite material of the present invention is characterized in that the fiber-reinforced composite material intermediate produced by the method for producing a fiber-reinforced composite material intermediate described above is further post-cured by heating and / or pressing.

[0009] In order to solve the above problems, the present invention also provides a resin film having the following configuration: a photocurable resin film comprising an epoxy resin composition containing the following components [A] to [D]: [A] Non-aromatic epoxy resin [B] Pigment with a volume average particle size of 0.1 to 10 μm [C] Non-aromatic thermoplastic resin [D] Cationic or anionic curing agent.

[0010] In the present invention, photocurability refers to a property in which a curing reaction proceeds when irradiated with a light source such as visible light, ultraviolet light, or infrared light. [Effects of the Invention]

[0011] The present invention can provide a fiber-reinforced composite material intermediate and a fiber-reinforced composite material that can protect the surface of a base material such as a prepreg with a resin film containing an epoxy resin composition that has excellent UV resistance and UV shielding properties, thereby preventing deterioration due to UV, and that inhibits mixing of the resin film with the base material resin that has poor UV resistance during heat and / or pressure curing. DETAILED DESCRIPTION OF THE INVENTION

[0012] The method for producing a fiber-reinforced composite material intermediate of the present invention is characterized by attaching a resin film containing an epoxy resin composition containing the following components [A] to [D] to a molding die, photocuring the epoxy resin composition, and laminating a fiber-reinforced composite material preform on the resin film. [A] Non-aromatic epoxy resin [B] Pigment with a volume average particle size of 0.1 to 10 μm [C] Non-aromatic thermoplastic resin [D] Cationic or anionic curing agent.

[0013] The component [A] of the present invention is a non-aromatic epoxy resin. Here, "aromatic" refers to a resin that contains aromatic hydrocarbons, compounds with resonance structures, or conjugated unsaturated heterocyclic compounds in its chemical structure, while anything other than that is "non-aromatic." In other words, a non-aromatic epoxy resin refers to an epoxy resin that does not contain aromatic hydrocarbon groups or unsaturated heterocyclic rings in its chemical structure.Examples of non-aromatic epoxy resins include alicyclic epoxy resins (epoxy resins containing a cycloalkane ring), such as tetrahydroindene diepoxide, vinylcyclohexene oxide, (3',4'-epoxycyclohexane)methyl 3,4-epoxycyclohexanecarboxylate, dipentene dioxide, bis(3,4-epoxycyclohexylmethyl) adipate, dicyclopentadiene dioxide, bis(2,3-epoxycyclopentyl)ether, and 1,2-epoxy-2,2-bis(hydroxymethyl)-1-butanol. 4-(2-oxiranyl)cyclohexane adduct, epoxidized butanetetracarboxylic acid tetrakis-(3-cyclohexenylmethyl) modified epsilon-caprolactone, bi-7-oxabicyclo[4.1.0]heptane, dodecahydrobisphenol A diglycidyl ether, dodecahydrobisphenol F diglycidyl ether, 1,4-cyclohexanedimethanol diglycidyl ether, hexahydrophthalic acid diglycidyl ester, hexahydroterephthalic acid diglycidyl ester, 2,2-bis(4-hydroxycyclohexyl) Specific examples of epoxy resins that do not contain any of an aromatic ring, an amine nitrogen atom, a cycloalkane ring, or a cycloalkene ring include ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1,4-butanediol glycidyl ether, 1,6-hexanediol diglycidyl ether, neopentylene glycol diglycidyl ether, glycerol polyglycidyl ether, and diglycerol polyglycidyl ether. Specific examples of trimethylolpropane polyglycidyl ether, sorbitol polyglycidyl ether, 1,4-bis(2-oxiranyl)butane, pentaerythritol polyglycidyl ether, and monofunctional epoxy compounds (epoxy compounds containing only one oxirane ring) that do not contain any aromatic ring or amine nitrogen atom include 4-tert-butyl glycidyl ether, butyl glycidyl ether, 1-butene oxide, 1,2-epoxy-4-vinylcyclohexane, and 2-ethylhexyl glycidyl ether.

[0014] From the viewpoint of heat resistance, the non-aromatic epoxy resin is preferably an alicyclic epoxy or one having a cycloalkane structure such as a cyclohexane ring in the molecule.

[0015] The non-aromatic epoxy resin may be a commercially available product. For example, "Celloxide" (registered trademark) 2021P, "Celloxide" (registered trademark) 8010, "Celloxide" (registered trademark) 2000, "Epolead" (registered trademark) GT401, "Celloxide" (registered trademark) 2081, EHPE3150 (manufactured by Daicel Corporation), THI-DE (manufactured by JXTG Nippon Oil & Energy Corporation), TTA21, AAT15, TTA22 (manufactured by Sun Chemical Co., Ltd.), etc. ), Ex-121, Ex-211, Ex-212, Ex-313, Ex-321, Ex-411 (manufactured by Nagase Chemtec), "Epolite" (registered trademark) 4000 (manufactured by Kyoeisha Chemical Co., Ltd.), ST-3000, ST-4000 (manufactured by Nippon Steel Chemical & Material Co., Ltd.), YX8000 (manufactured by Mitsubishi Chemical Corporation), EPALOY5000 (manufactured by HUNTSMAN), and the like.

[0016] By using at least two types of the non-aromatic epoxy resins, the reactivity of the epoxy resin composition can be controlled, and a good balance between the rapid curing property and the pot life of the epoxy resin composition can be obtained.

[0017] By including the non-aromatic epoxy resin in an amount of 90 mass % or more based on the entire epoxy resin composition, high light resistance (UV resistance) can be obtained.

[0018] Component [B] is a pigment (volume average particle size: 0.1 to 10 μm). Examples of pigments include barium sulfate, zinc sulfide, titanium oxide, molybdenum red, cadmium red, chromium oxide, titanium yellow, cobalt green, cobalt blue, ultramarine, barium titanate, carbon black, iron oxide, red phosphorus, and copper chromate. The volume average particle size of the pigment is 0.1 to 10 μm, preferably 0.1 to 5 μm, and more preferably 0.3 to 5 μm, to obtain an epoxy resin composition with high UV-shielding properties. Furthermore, the pigment is preferred in that it forms aggregates with a volume average particle size of 0.3 μm or more in the epoxy resin composition, thereby exhibiting high UV-shielding properties. The volume average particle size here is measured using a laser diffraction scattering method with an LA-950 (manufactured by Horiba, Ltd.). The volume-converted results measured using "Araldite" (registered trademark) GY282 (component: bisphenol F type epoxy resin, manufactured by Huntsman Japan Co., Ltd.) as the dispersion medium were adopted as the particle size distribution measurement results, and the particle size (median diameter) at 50% of the cumulative curve of the obtained particle size distribution was taken as the volume-average particle size.

[0019] By including the pigment in an amount of preferably 15 to 75 parts by mass, more preferably 25 to 55 parts by mass, and even more preferably 30 to 50 parts by mass relative to 100 parts by mass of the total epoxy resin contained in the epoxy resin composition, it is possible to obtain a good balance between the UV screening properties of the cured resin product and the tackiness of a resin film containing the epoxy resin composition according to the present invention and the UV screening properties of the cured product.

[0020] Component [C] is a non-aromatic thermoplastic resin. Here, "aromatic" refers to a compound containing aromatic hydrocarbons, compounds with resonance structures, or conjugated unsaturated heterocyclic compounds in its chemical structure; all other compounds are "non-aromatic." In other words, a non-aromatic thermoplastic resin is a thermoplastic resin that does not contain aromatic hydrocarbon groups or unsaturated heterocyclic rings in its chemical structure. Examples of non-aromatic thermoplastic resins include polyvinyl alcohol, polyvinyl acetal, polyvinyl formal, polyvinyl acetoacetal, polyvinyl butyral, polyvinyl acetate, hydrogenated bisphenol A-pentaerythritol phosphite polymer, hydrogenated terpene, and hydrogenated terpene phenol.

[0021] In particular, polyvinyl alcohol, polyvinyl formal, polyvinyl butyral, polyvinyl acetoacetal, and polyvinyl vinyl acetate, which have high solubility in non-aromatic epoxy resins, are preferred because they allow for easy viscosity adjustment of the epoxy resin composition, and polyvinyl acetoacetal and polyvinyl butyral are even more preferred because they can improve the elongation of the cured epoxy resin composition.

[0022] These non-aromatic thermoplastic resins are preferably soluble in the non-aromatic epoxy resin of component [A]. For example, if at least 10 parts by mass of thermoplastic resin powder is added to 100 parts by mass of the non-aromatic epoxy resin of component [A] and kneaded at 100 to 120°C for 1 hour, the thermoplastic resin powder is said to be soluble if it shows a weight loss from the initial weight. Weight loss refers to a decrease in the powder mass that is optically undetectable, or a decrease of 10% or more in mass from the initial weight when the remaining powder is recovered. From the perspective of dissolving in the epoxy resin, it is preferable that the thermoplastic resin powder has a volume average particle size of at least 100 μm as determined by laser diffraction. Furthermore, a volume average particle size of more than 100 nm is preferable because it prevents aggregation during storage and facilitates mixing with the epoxy resin.

[0023] Furthermore, the molecular weight of these non-aromatic thermoplastic resins is preferably 5,000 to 70,000 g / mol, more preferably 7,000 to 65,000 g / mol, and even more preferably 10,000 to 60,000 g / mol, to achieve a good balance between uniform dissolution in the epoxy resin composition and the resin flow suppression effect. Here, the molecular weight refers to the weight average molecular weight in terms of polystyrene measured by gel permeation chromatography using HLC-8420GPC (manufactured by Tosoh Corporation).

[0024] The non-aromatic thermoplastic resin may be a commercially available product, such as "J-POVAL" (registered trademark) (manufactured by Nippon Vinyl Acetate Poval Co., Ltd.), "VINYLEC" (registered trademark) (manufactured by JNC Corporation), "S-LEC" (registered trademark) (manufactured by Sekisui Chemical Co., Ltd.), "Ultrasene" (registered trademark) (manufactured by Tosoh Corporation), JPH-3800 (manufactured by Johoku Chemical Industry Co., Ltd.), or YS Polystar UH130 (manufactured by Yasuhara Chemical Co., Ltd.).

[0025] By including the non-aromatic thermoplastic resin in an amount of 20 to 75 parts by mass, preferably 30 to 65 parts by mass, and more preferably 30 to 55 parts by mass, relative to 100 parts by mass of the total epoxy resin contained in the epoxy resin composition, a resin film having good tackiness can be obtained.

[0026] Furthermore, the molecular weight of these non-aromatic thermoplastic resins is preferably 5,000 to 70,000 g / mol, more preferably 7,000 to 65,000 g / mol, and even more preferably 10,000 to 60,000 g / mol, in order to obtain a good balance between uniform dissolution in the epoxy resin composition and the resin flow suppression effect. Here, the molecular weight refers to the weight average molecular weight in terms of polystyrene measured by gel permeation chromatography using an HLC-8420GPC (manufactured by Tosoh Corporation) (the same applies hereinafter).

[0027] Examples of commercially available products with different molecular weights include polyvinyl formal ("Vinylec" (registered trademark) K, manufactured by JNC Corporation, molecular weight 40,000 to 54,000 g / mol), polyvinyl formal ("Vinylec" (registered trademark) E, manufactured by JNC Corporation, molecular weight 95,000 to 134,000 g / mol), and polyvinyl acetoacetal ("S-LEC" (registered trademark) KS-10, manufactured by Sekisui Chemical Co., Ltd., molecular weight 17,000 g / mol).

[0028] Component [D] is a cationic or anionic curing agent. Examples of cationic curing agents include 1-naphthylmethylmethyl p-hydroxyphenylsulfonium hexafluoroantimonate, 2-methylbenzylmethyl p-hydroxyphenylsulfonium hexafluoroantimonate, benzylmethyl p-hydroxyphenylsulfonium hexafluoroantimonate, dimethyl-p-acetoxyphenylsulfonium hexafluoroantimonate, diaryliodonium salts, boron trifluoride piperidine, boron trifluoride monoethylamine, diaryliodonium salts, and sulfonium salts.

[0029] The cationic curing agent may be a commercially available product. Examples include "ADEKAOPTON" (registered trademark) CP-77, "ADEKAOPTON" (registered trademark) CP-66 (manufactured by ADEKA Corporation), CI-2639, CI-2624 (manufactured by Nippon Soda Co., Ltd.), "SAN-AID" (registered trademark) SI-60, "SAN-AID" (registered trademark) SI-80, "SAN-AID" (registered trademark) SI-100, "SAN-AID" (registered trademark) SI-150, "SAN-AID" (registered trademark) SI-B4, "SAN-AID" (registered trademark) SI-B5 (manufactured by Sanshin Chemical Industry Co., Ltd.), TA-100, IK-1PC(80) (manufactured by San-Apro Co., Ltd.), boron trifluoride piperidine, and boron trifluoride monoethylamine (manufactured by Stella Chemifa Co., Ltd.). The cationic curing agent is preferably a photothermal cationic curing agent or a thermal cationic curing agent. Photothermal cationic curing agents are those that become reactive when exposed to light below a certain wavelength, such as ultraviolet or visible light, or heat above a certain temperature, while thermal cationic curing agents are those that become reactive when exposed to heat. Photothermal cationic curing agents are preferred because they can be cured in a wide variety of environments, while thermal cationic curing agents are preferred because they can achieve high storage stability through temperature control.

[0030] Examples of anionic curing agents include phosphorus hexafluoride, antimony hexafluoride, arsenic hexafluoride, tin hexachloride, iron tetrachloride, bismuth pentachloride, and niobium hexachloride.

[0031] By using two types of the above curing agents, the reactivity of the epoxy resin composition can be controlled, and a good balance between the rapid curing property and the pot life of the epoxy resin composition can be obtained.

[0032] The curing agent is preferably contained in an amount of 0.5 to 10 parts by mass, more preferably 1 to 5 parts by mass, and even more preferably 1 to 3 parts by mass, relative to 100 parts by mass of the total epoxy resin contained in the epoxy resin composition, thereby achieving fast curing properties, an effect of suppressing resin flow and volatilization during molding, and a good balance of fast curing properties, pot life, and UV resistance.

[0033] The epoxy resin composition of the present invention may also contain a thixotropy-imparting agent as the component [E]. Examples of the thixotropy-imparting agent include silicon dioxide, magnesium silicon sodium fluoride hydroxide oxide, alkyl quaternary ammonium salts, synthetic hectorite, clay minerals, modified bentonite, and mixtures of minerals and organically modified bentonite.

[0034] The thixotropy-imparting agent may be a commercially available product, and examples thereof include fumed silica ("Aerosil" (registered trademark) (manufactured by Nippon Aerosil Co., Ltd.)), "OPTIGEL" (registered trademark), "OPTIBENT" (registered trademark), "GARAMITE" (registered trademark), "LAPONITE" (registered trademark), "TIXOGEL" (registered trademark), "CRAYTONE" (registered trademark), "CLOISITE" (registered trademark) (manufactured by BYK), "Somasif" (registered trademark) ME-100, and Micromica MK (manufactured by Katakura Co-op Agri Co., Ltd.).

[0035] By including the thixotropy-imparting agent in an amount of preferably 0.1 to 20 parts by mass, more preferably 0.5 to 10 parts by mass, and even more preferably 0.5 to 5 parts by mass relative to 100 parts by mass of the total epoxy resin contained in the epoxy resin composition, a good balance can be obtained between the effect of suppressing resin flow during molding and the tackiness of the resin film.

[0036] Furthermore, the epoxy resin composition of the present invention may contain a curing aid as component [F]. Examples of the curing aid include 4-hydroxyphenyldimethylsulfonium methylsulfate and 4-(methylthio)phenol.

[0037] The curing aid may be a commercially available product, and examples thereof include "Saneido" (registered trademark) SI-S and "Saneido" (registered trademark) S-ME (manufactured by Sanshin Chemical Industry Co., Ltd.).

[0038] By including the curing aid in an amount of preferably 0.1 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, and even more preferably 0.1 to 2.5 parts by mass relative to 100 parts by mass of the total epoxy resin contained in the epoxy resin composition, it is possible to obtain a good balance between the rapid curing property and the pot life of the epoxy resin composition.

[0039] Furthermore, the epoxy resin composition of the present invention can contain rubber as component [G]. Examples of rubber include natural rubber, diene rubber, and non-diene rubber. Examples of diene rubber include styrene-butadiene rubber, isoprene rubber, butadiene rubber, chloroprene rubber, and acrylonitrile-butadiene rubber. Examples of non-diene rubber include butyl rubber, ethylene-propylene rubber, ethylene-propylene-diene rubber, urethane rubber, silicone rubber, and fluororubber. Non-diene rubber is preferred as a component contained in the epoxy resin composition of the present invention. Among these, ethylene-propylene rubber, ethylene-propylene-diene rubber, silicone rubber, and fluororubber, which do not have double bonds in the polymer backbone, are particularly preferred because they have high light resistance and little effect on the light resistance of the epoxy resin composition of the present invention. Furthermore, powder-like rubber is particularly preferred because it has excellent dispersibility in the epoxy resin composition.

[0040] The content of the rubber is preferably 5 to 50 parts by mass relative to 100 parts by mass of the total epoxy resin. When the rubber is contained in an amount of 5 parts by mass or more relative to 100 parts by mass of the total epoxy resin, the resin flow suppression effect and the elongation of the epoxy resin composition after curing are excellent, thereby preventing cracking after painting, and when the rubber is contained in an amount of 50 parts by mass or less, excellent adhesion is obtained between the resin film and the fiber-reinforced composite material preform in the present invention and the target.

[0041] The rubber may be a commercially available product, and examples thereof include KMP-598, KMP-600, KMP-601, KMP-602, and KMP-605 (manufactured by Shin-Etsu Chemical Co., Ltd.), Cevian (registered trademark) (manufactured by Daicel Miraize Co., Ltd.), JSR N215SL, JSR N222SH, JSR N238H, JSR N241H, JSR N250S, PN30A, PN20HA, and N280 (manufactured by JSR Corporation).

[0042] The epoxy resin composition according to the present invention can be formed into a resin film, for example, by coating it on release paper and forming it into a sheet. This resin film with release paper attached to a molding die is then peeled off, and the surface resin film is photocured using a light source. (In the present invention, a material in which the epoxy resin composition is coated on release paper is referred to as a "resin film with release paper," and the sheet-like epoxy resin composition alone is referred to as a "resin film." Hereinafter, photocuring may also be referred to as UV curing or UV curing.) Photocuring may be performed to the point where the resin film surface loses its fluidity, or the degree of cure may be adjusted as needed to retain a certain degree of fluidity. Photocuring to the point where the resin film surface loses its fluidity is preferred because it allows for the reduction of the amount of resin contained in the fiber-reinforced composite material preform to be mixed with the resin film. Adjusting the degree of cure as needed to retain a certain degree of fluidity is preferred because it improves the adhesion between the resin film and the fiber-reinforced composite material preform in the fiber-reinforced composite material intermediate and the adhesion between the resin film and the fiber-reinforced composite material preform in the fiber-reinforced composite material. The degree of curing of the resin film by photocuring can be calculated by measuring the temperature rise of the resin film before and after photocuring with a DSC to determine the ratio of the residual exothermic peak after photocuring to the exothermic peak before photocuring. A sheet-like support can be used to improve the handleability of the resin film. There are no particular limitations on the support, and it is sufficient if it can hold the resin film, and for example, the release paper mentioned above can be used. The basis weight of the support is 5 to 50 g / m 2 When the weight of the support is 5 g / m, the resin film becomes easy to handle. 2 If the thickness is more than 50g / m, the support will not tear easily when handled. 2A temperature below this range is preferable because it improves the shapability of the resin film. The mold can have any shape, and can be made of metal, FRP, plaster, wood, or other materials. A prepreg, RTM material, or resin film infusion (RFI) material (also referred to as a "fiber-reinforced composite precursor" in the present invention) used in a fiber-reinforced composite material, as well as a semi-cured or fully cured composite material (referred to as a "fiber-reinforced composite preliminary body" in the present invention) can be laminated on top of the photocured resin film in the mold, and then the laminate can be post-cured by heating and / or pressing as necessary to obtain a fiber-reinforced composite material having UV resistance and UV-shielding properties on its surface (in the present invention, the material obtained by laminating the fiber-reinforced composite preliminary body on a photocured resin film is referred to as a "fiber-reinforced composite intermediate," and the fiber-reinforced composite material intermediate that has been further cured is referred to as a "fiber-reinforced composite material"). Here, among the fiber-reinforced composite material preforms, a prepreg is a sheet-like fiber-reinforced composite material precursor obtained by impregnating fibers (in the present invention, the fibers used in the fiber-reinforced composite material precursor or the fiber-reinforced composite material preform are referred to as "reinforced fibers") with a thermosetting resin such as an epoxy resin; an RTM material is a fiber-reinforced composite material precursor obtained by stacking reinforcing fiber substrates in a mold and injecting a liquid thermosetting resin into the reinforcing fiber substrate; and an RFI material refers to a fiber-reinforced composite material precursor obtained by overlaying a thermosetting resin film on a reinforcing fiber substrate and then heating and / or pressurizing the stack to impregnate the reinforcing fiber substrate with the thermosetting resin.

[0043] The resin film may be pre-cured by heating. Heating may be performed using an oven, an IR heater, or by contacting the release paper surface of a resin film with release paper with a hot plate. The temperature of the oven, furnace, IR heater, or hot plate during pre-curing is preferably 40 to 200°C. A temperature of 40°C or higher can shorten the pre-curing time, and a temperature of 200°C or lower can pre-cure the resin film uniformly.

[0044] A degree of cure of 0 to 60% for the fiber-reinforced composite preform is preferable because the resin contained in the fiber-reinforced composite preform is not yet fully cured, resulting in high formability, and chemical bonding with a resin film containing the epoxy resin composition of the present invention can be expected, improving adhesion between the resin film and the fiber-reinforced composite preform in the fiber-reinforced composite material. For a fiber-reinforced composite preform with a degree of cure exceeding 60%, it is preferable to roughen the surface by polishing and / or plasma treatment to physically improve adhesion between the resin film and the fiber-reinforced composite preform in the fiber-reinforced composite material. A degree of cure of 20 to 100% is preferable because it enables the amount of resin contained in the fiber-reinforced composite preform that is mixed with the resin film containing the epoxy resin composition of the present invention during molding to be reduced. Therefore, a degree of cure of 20 to 60% is even more preferable in order to achieve a good balance between adhesion between the resin film and the fiber-reinforced composite preform in the fiber-reinforced composite material and the effect of reducing the amount of resin contained in the fiber-reinforced composite preform that is mixed with the resin film containing the epoxy resin composition of the present invention during molding.

[0045] The epoxy resin composition of the present invention can be formed into a sheet form to produce a photocurable resin film by various methods, such as the wet method in which the epoxy resin composition is dissolved in an organic solvent selected from acetone, methyl ethyl ketone, methanol, etc. to reduce the viscosity, coated onto release paper, and then the organic solvent is evaporated to obtain a film, or the hot melt method in which the epoxy resin composition is heated to reduce the viscosity without using an organic solvent, and then coated onto release paper to obtain a film.

[0046] The weight of the resin film according to the present invention is 30 to 300 g / m 2 It is preferable that the weight of the resin film is 30 g / m 2 If the thickness is 300 g / m or more, the surface of the fiber-reinforced composite material can be covered without being visible through the film, and sufficient UV resistance can be exhibited. 2 If the amount is less than this, heat generation due to curing of the epoxy resin composition can be suppressed when molding together with the fiber-reinforced composite material preform, which is preferable.

[0047] In the manufacturing method of the present invention, a resin film containing an epoxy resin composition is attached to a molding die, photocured, and then a fiber-reinforced composite material preform such as a prepreg, RTM material, or RFI material is laminated onto the photocured resin film to obtain a fiber-reinforced composite material intermediate. The fiber-reinforced composite material intermediate can be molded by various methods.

[0048] When untreated prepreg or RFI material is used as the fiber-reinforced composite material preform, the fiber-reinforced composite material intermediate is cured by heating and / or pressurizing using methods such as press molding, autoclave molding, bagging, wrapping tape, internal pressure molding, and pultrusion. For RFI material, a thermosetting resin film is laminated on top of a photocured resin film, and then a reinforcing fiber substrate is laminated on top of that to obtain a fiber-reinforced composite material intermediate, which is then molded under heat and pressure to cure. For RTM material, the reinforcing fibers are laminated (preformed) on a photocured resin film, and then the fiber-reinforced composite material intermediate is cured by heating and pressurizing and molding using methods such as VaRTM, which injects resin under vacuum pressure, or HP-RTM, which injects resin under high pressure.

[0049] Roughening the surface of the photocured resin film by polishing and / or plasma treatment is preferable because it makes it possible to improve the adhesion to the fiber-reinforced composite material preform to be laminated later and the adhesion between the molded resin film and the fiber-reinforced composite material preform.

[0050] The degree of cure of a fiber-reinforced composite material preform can be adjusted in advance. Various methods are used to adjust the degree of cure. When using prepregs, for example, they can be molded by heating and / or pressure using methods such as press molding, autoclave molding, bagging, tape wrapping, internal pressure molding, and pultrusion molding. Various known methods are also used to adjust the degree of cure of RTM materials. Methods that are used include VaRTM, which injects resin under vacuum pressure, and HP-RTM, which injects resin under high pressure, depending on the characteristics of the thermosetting resin used in the RTM material. The degree of cure is controlled by the temperature and time of the pretreatment. When controlling the degree of cure, using a multi-stage process in which the curing temperature is changed in stages allows for more stable control of the degree of cure and is preferable from the perspective of reducing voids in the fiber-reinforced composite material. The degree of cure of RTM materials can also be controlled by heating them in an oven after demolding.

[0051] As the reinforcing fibers of the fiber-reinforced composite precursor or the fiber-reinforced composite preform, various carbon fibers, graphite fibers, glass fibers, aramid fibers, etc. are preferably used. When a fiber-reinforced composite material is produced by the method of the present invention, it is advantageous in that the amount of resin contained in the fiber-reinforced composite preform, which is mixed with the resin film containing the epoxy resin composition of the present invention during the molding process, can be reduced. Furthermore, the fiber-reinforced composite preform produced by the method of the present invention can be completely cured by pressurizing and heat molding to obtain a fiber-reinforced composite material having UV resistance and UV shielding properties on the surface.

[0052] Various known methods for post-curing are used, but preferred methods include heating in an autoclave, oven, or press, and applying pressure as needed. Post-curing may be performed in a mold or in a free-standing state without a mold. The curing temperature depends on the curing agent and curing catalyst used in the resin of the fiber-reinforced composite material preform, but is preferably performed at a temperature of 100 to 200°C from the viewpoints of suppressing distortion and wrinkles due to thermal stress and maintaining adhesion between the resin layer applied as the outermost layer and the fiber-reinforced composite material preform.

[0053] By roughening the resin film side surface of the fiber-reinforced composite material obtained by molding a fiber-reinforced composite material intermediate by polishing and / or plasma treatment, it is possible to improve the adhesion between the fiber-reinforced composite material surface and the paint, primer, or the like that covers it. [Example]

[0054] The present invention will be described in more detail below with reference to examples. However, the scope of the present invention is not limited to these examples. Measurements of various properties were carried out in an environment of 23°C and 50% relative humidity unless otherwise noted.

[0055] <Materials used in Examples and Comparative Examples> (1) Component [A] Non-aromatic epoxy resin (3',4'-epoxycyclohexane) methyl 3,4-epoxycyclohexanecarboxylate ("Celloxide" (registered trademark) 2021P, manufactured by Daicel Corporation) Epoxy equivalent: 136 (g / eq.) Diglycidyl ether of 2,2-bis(4-hydroxycyclohexyl)propane (YX8000, manufactured by Mitsubishi Chemical Corporation).

[0056] (2) Component [B] Pigment Titanium oxide (rutile type) (“Ti-Pure” (registered trademark) R-960, manufactured by Chemours, Inc., volume average particle size 0.5 μm).

[0057] (3) Component [C] Non-aromatic thermoplastic resin Polyvinyl formal ("Vinylec" (registered trademark) K, manufactured by JNC Corporation).

[0058] (4) Component [D] Cationic curing agent Dimethyl-p-acetoxyphenylsulfonium hexafluoroantimonate "Sanaid" (registered trademark) SI-150, manufactured by Sanshin Chemical Industry Co., Ltd.

[0059] (5) Fiber-reinforced composite material preform T300 / 3631-2 woven fabric (plain weave) prepreg (manufactured by Toray Industries, Inc.) -T300 fabric (plain weave) (manufactured by Toray Industries, Inc.).

[0060] (6) Component [E] Thixotropic agent Fumed silica ("AEROSIL (registered trademark)" RY200S, manufactured by Nippon Aerosil Co., Ltd.).

[0061] (7) Component [F] Curing aid 4-(Methylthio)phenol ("Sanaide (registered trademark)" S-ME manufactured by Sanshin Chemical Industry Co., Ltd.).

[0062] (8) Component [G] Rubber Silicone rubber powder (KPM-601, manufactured by Shin-Etsu Chemical Co., Ltd.).

[0063] <Methods for producing and evaluating epoxy resin compositions and fiber-reinforced composite materials> Epoxy resin compositions and fiber-reinforced composite materials of the respective Examples and Comparative Examples were prepared by the following methods, and various measurements were carried out.

[0064] (1) Preparation of epoxy resin composition An epoxy resin corresponding to component [A], a pigment corresponding to component [B], and, if necessary, a thixotropy-imparting agent [E], and a rubber corresponding to component [G], listed in Tables 1 to 6, were placed in a three-roll mill and mixed at an arbitrary roll rotation speed to obtain a powder mixture preliminarily. The powder mixture preliminarily and a thermoplastic resin corresponding to component [C] listed in Tables 1 to 6 were placed in a mixer and heated and mixed to dissolve the thermoplastic resin. Next, while continuing to knead, the temperature was lowered to 60°C or below, and a cationic curing agent [D] listed in Tables 1 to 6 was added and stirred to obtain an epoxy resin composition.

[0065] (2) Adjusting the degree of hardening of the fiber-reinforced composite material preform A six-ply laminate of T300 / 3631-2 woven fabric (plain weave) prepreg was prepared as a fiber-reinforced composite material. The degree of prepreg cure was adjusted by placing it in an oven at 180°C for a certain period of time. Additionally, a six-ply laminate (also referred to as "preform" in the present invention) was prepared as an RTM material by preforming T300 woven fabric (plain weave) in a molding die. The preform was molded, and a resin composition (also referred to as "Resin A" in the present invention) containing 100 parts by mass of triglycidyl-m-aminophenol ("Araldite"® MY0600, manufactured by Huntsman Corporation, epoxy equivalent: 118) and diethyltoluenediamine ("jER"® Cure W, manufactured by Mitsubishi Chemical Corporation, amine equivalent: 68) was mixed so that the epoxy equivalent / amine equivalent ratio was 1.0 was poured into the mold. The resin composition was then poured into the preform at 60°C to obtain an RTM material. The degree of hardening of the obtained RTM material was adjusted by placing it in an oven at 180°C for a certain period of time.

[0066] (3) Measurement of the degree of hardening of a fiber-reinforced composite material The degree of cure of the fiber-reinforced composite material prep was calculated from the heat release amount on the exothermic curve obtained using a differential scanning calorimeter (DSC Q2500, manufactured by TA Instruments) in a nitrogen atmosphere at a heating rate of 5°C / min. In (2) above, the heat release amount of the fiber-reinforced composite material prep before being placed in the 180°C oven was defined as W1 (mW / g), and the heat release amount of the fiber-reinforced composite material prep after being placed in the 180°C oven was defined as W2 (mW / g), and the degree of cure was calculated using the following formula: W2 / W1 × 100 [%].

[0067] (4) Surface treatment of fiber-reinforced composite material preforms The surface of the fiber-reinforced composite preform was optionally treated (polished) by manually pressing water-resistant abrasive paper C34P#400 (manufactured by Riken Corundum Co., Ltd.) against the surface of the fiber-reinforced composite preform that was in close contact with the resin film, and then reciprocating five times.

[0068] (5) Preparation of resin film from epoxy resin composition The resin composition prepared in (1) was spread on a 30 cm wide release paper so that the basis weight of the epoxy resin composition was 200 g / m2 The resin film was coated using a reverse roll coater so that the resin film had a release liner attached thereto.

[0069] (6) Preparation of fiber-reinforced composite material intermediate The resin film side of the resin film with release paper was attached to a mold, and only the release paper was peeled off. Here, the mold was an aluminum plate coated with a release agent.

[0070] Toscure 401 (Toshiba Lighting & Technology Corporation) was used to apply 70 mW / cm to the resin film. 2 The laminate was then photocured by irradiating it with UV light at an energy density of 1000 kJ / min for 1 minute, and the fiber reinforced composite material preparatory bodies (2) to (4) were laminated on top of it to obtain a fiber reinforced composite material intermediate.

[0071] (7) Thermal curing of fiber-reinforced composite intermediates The fiber-reinforced composite intermediate obtained in (6) above was heat-cured. Fiber-reinforced composite intermediates in which the fiber-reinforced composite preliminary material was a prepreg laminate were heat-cured in an autoclave at 6 atmospheres and 180°C for 2 hours with a temperature increase of 1.7°C / min. Fiber-reinforced composite intermediates in which the fiber-reinforced composite preliminary material with an adjusted degree of cure was an RTM material were heat-cured in an oven at 180°C for 2 hours with a temperature increase of 1.7°C / min. In cases where the RTM material was not pretreated, a preform was laminated on the photocured resin film, and in this state, resin A was poured into the oven at 60°C. The preform was then heat-cured in the oven at 180°C for 2 hours with a temperature increase of 1.7°C / min.

[0072] (8) Adhesion between the resin film and the fiber-reinforced composite material preform after heat curing Repair tape ("Scotch" (registered trademark) DUCT-TP18, manufactured by 3M Corporation) was applied to an area of ​​48 mm x 80 mm on the surface of the resin film of the fiber-reinforced composite material obtained by heat curing in (7) above, and a 10 cm square aluminum plate was placed on top. After leaving it in this state for 5 minutes, the tape was peeled off. If even a small amount of the resin film adhered to the adhesive surface of the tape, the adhesion between the resin film in the fiber-reinforced composite material and the fiber-reinforced composite material pre-body was judged to be "poor," and if there was no adhesion, it was judged to be "good."

[0073] (9) Amount of resin in the fiber-reinforced composite material preform mixed into the resin film during molding The resin film side of the fiber-reinforced composite material prepared in (7) above was subjected to IR measurement by the ATR method (FT / IR-4000 manufactured by JASCO Corporation, prism: diamond, measurement wavelength: 400 to 4,000 cm -1 , cumulative number: 16 times) and 1,715 cm -1 The peak at 1,592 cm represents the benzene ring derived from the cured resin used in the fiber-reinforced composite material preform. -1 By evaluating the value of this peak, it is possible to evaluate the amount of resin used in the fiber reinforced composite preparatory body that mixes with the resin film during molding and is exposed to the surface of the fiber reinforced composite material. -1 If the peak value of this peak was 0.6 or less, the surface of the fiber-reinforced composite material was judged to have good UV resistance. In addition, in Examples 50 to 53, IR measurement was carried out by the ATR method in the same manner as above, and the peak at 1715 cm -1 Normalization was not performed using the peak at 1592 cm , which indicates the benzene ring originating from the cured resin used in the fiber-reinforced composite material preform. -1 In this case, the peak value of 1592 cm , which indicates the benzene ring originating from the cured resin used in the fiber-reinforced composite material preform, was evaluated. -1 If the peak value was 1.0 or less, the UV resistance of the surface of the fiber reinforced composite material was judged to be good.

[0074] <Examples 1 to 22> In Examples 1 to 22, a resin film containing an epoxy resin composition having UV resistance and UV shielding properties was attached to a molding die, and then the resin film was cured by UV irradiation. An untreated or polished fiber-reinforced composite material preform was then laminated on top of the resin film, and the resulting fiber-reinforced composite material intermediate was molded in an autoclave.

[0075] The amount of resin from the prepreg mixed into the resin film during molding was judged to be good in Examples 1 to 22. Furthermore, the higher the degree of cure of the prepreg, the greater the effect of suppressing the amount of resin from the prepreg mixed into the resin film during thermoforming, and this effect was particularly high in Examples 5 to 22.

[0076] In Examples 1 to 14, the adhesion between the resin film and the fiber-reinforced composite material preliminary product after molding was judged to be good. On the other hand, among Examples 15 to 22, in Examples 15, 17, 19, and 21 in which the surface polishing of the prepreg with adjusted cure degree was not performed, the adhesion between the resin film and the fiber-reinforced composite material preliminary product in the fiber-reinforced composite material was judged to be poor, and in Examples 16, 18, 20, and 22 in which the surface polishing of the fiber-reinforced composite material preliminary product was performed, the adhesion between the resin film and the fiber-reinforced composite material preliminary product in the fiber-reinforced composite material was judged to be good.

[0077] <Examples 23 to 43> In Examples 23 to 43, a resin film containing a UV-resistant and UV-shielding epoxy resin composition was attached to a mold, the resin film was cured by UV irradiation, and a fiber-reinforced composite material intermediate was obtained by laminating a fiber-reinforced composite material preform, the surface of which had been untreated or polished, on the RTM material with the degree of cure adjusted. In cases where pretreatment was not performed, a preform was laminated on the photo-cured resin film, and in this state, Resin A was injected at 60°C and thermally cured in an oven.

[0078] The amount of resin from the RTM material mixed into the resin film during thermosetting was judged to be good in Examples 23 to 43. Furthermore, the higher the degree of curing of the RTM material, the greater the effect of suppressing the amount of resin from the RTM material mixed into the resin film during thermoforming, and this effect was particularly high in Examples 26 to 43.

[0079] The adhesiveness between the resin film and the fiber-reinforced composite material after thermal curing was judged to be good in Examples 23 to 35. On the other hand, among Examples 36 to 43, Examples 36, 38, 40, and 42, in which the surface of the fiber-reinforced composite material preliminary body with an adjusted cure was not polished, were judged to have poor adhesiveness between the resin film and the fiber-reinforced composite material preliminary body, and Examples 37, 39, 41, and 43, in which the fiber-reinforced composite material preliminary body was polished, were judged to have good adhesiveness between the resin film and the fiber-reinforced composite material preliminary body.

[0080] <Comparative Examples 1 and 2> In Comparative Example 1, a resin film containing a UV-resistant and UV-shielding epoxy resin composition was attached to a mold, and then an untreated prepreg was laminated onto the resin film without UV irradiation, followed by thermal curing in an autoclave. In Comparative Example 2, a resin film containing a UV-resistant and UV-shielding epoxy resin composition was attached to a mold, and then a preform was laminated onto the resin film without UV irradiation, and then Resin A was injected into the mold at 60°C and thermally cured in an oven, resulting in a fiber composite material made from an RTM material.

[0081] In Comparative Examples 1 and 2, the adhesion between the resin film and the fiber-reinforced composite material preform in the fiber-reinforced composite material was judged to be good, but the amount of resin from the prepreg or RTM material mixed into the resin film during thermoforming was large, and the adhesion was judged to be poor.

[0082] <Examples 1, 5, 44 to 53> In Examples 44 to 53, a resin film containing an epoxy resin composition having UV resistance and UV shielding properties was attached to a molding die, the resin film was cured by UV irradiation, and then a fiber-reinforced composite preliminary body was laminated on top of the resin film, with the surface of an untreated or polished prepreg or prepreg with an adjusted degree of cure being untreated or polished. The resulting fiber-reinforced composite intermediate was molded in an autoclave. Examples 44 to 53 were evaluated as having a good level of prepreg resin contamination in the coating during thermoforming. It was also shown that the higher the degree of cure of the prepreg before coating, the greater the effect of suppressing the amount of prepreg resin contamination in the coating during thermoforming.

[0083] In Examples 44 to 45, a thixotropy-imparting agent (component [E]) was added to the epoxy resin compositions described in the corresponding Examples 1 and 5. Comparing Examples 44 to 45 with Examples 1 and 5, it was shown that Examples 44 to 45 suppressed the amount of prepreg resin mixed into the coating agent during the thermoforming process.

[0084] In Examples 46 to 47, a curing aid (component [F]) was added to the epoxy resin compositions described in the corresponding Examples 1 and 5. Comparing Examples 46 to 47 with Examples 1 and 5, it was found that the addition of the curing aid increased the amount of resin in the prepreg mixed into the coating during the thermoforming process, but the evaluation was favorable. The curing aid (component [F]) has the effect of suppressing the curing reaction and improving processability when preparing the epoxy resin composition, demonstrating that it is possible to control both the processability and the amount of resin in the prepreg mixed into the coating during the thermoforming process.

[0085] In Examples 48 to 49, rubber as component [G] was added to the epoxy resin compositions described in the corresponding Examples 1 and 5. Comparing Examples 48 to 49 with Examples 1 and 5, it was shown that Examples 48 to 49 suppressed the amount of prepreg resin mixed into the coating agent during the thermoforming process.

[0086] Examples 50 and 51 contained two types of non-aromatic epoxy resin as component [A]. Compared with the corresponding Examples 1 and 5, the inclusion of two types of component [A] resulted in an increase in the amount of resin in the prepreg that was mixed into the coating agent during the thermoforming process, but the evaluation was good.

[0087] Examples 52 and 53 contain two types of component [A], and also contain component [E] a thixotropy-imparting agent, component [F] a curing aid, and [G] rubber. The effect of compounding two types of component [A] and adding component [F] a curing aid, which increased the amount of resin in the prepreg mixed into the coating during the thermoforming process, was observed in Examples 46 to 47 and 50 to 51. However, in Examples 44 to 45 and 48 to 49, the effect of adding component [E] a thixotropy-imparting agent and component [G] rubber, which reduced the amount of resin in the prepreg mixed into the coating during the thermoforming process, was greater, demonstrating that it is possible to suppress the amount of resin in the prepreg mixed into the coating during the thermoforming process.

[0088] [Table 1]

[0089] [Table 2]

[0090] [Table 3]

[0091] [Table 4]

[0092] [Table 5]

[0093] [Table 6]

Claims

1. A method for producing a fiber-reinforced composite material intermediate, which is obtained by attaching to a molding die a resin film containing an epoxy resin composition comprising the following components [A] to [D], wherein the component [B] is contained in an amount of 15 to 75 parts by mass per 100 parts by mass of the total epoxy resins contained in the epoxy resin composition, followed by photocuring the epoxy resin composition and laminating a fiber-reinforced composite material preform on the resin film. [A] Non-aromatic epoxy resin [B] Pigment having a volume average particle size of 0.1 to 10 μm [C] Non-aromatic thermoplastic resin [D] Cationic curing agent or anionic curing agent

2. The method for producing a fiber-reinforced composite material intermediate according to claim 1 , wherein the epoxy resin composition further comprises a component [E]. [E] Thixotropy-imparting agent

3. The method for producing a fiber-reinforced composite material intermediate according to claim 1 or 2, wherein the epoxy resin composition further comprises a component [F]. [F] Curing aid

4. The method for producing a fiber-reinforced composite material intermediate according to any one of claims 1 to 3, wherein the epoxy resin composition contains at least two types of component [A].

5. The method for producing a fiber-reinforced composite material intermediate according to any one of claims 1 to 4, wherein a resin film containing the epoxy resin composition containing the components [A] to [D] is photocured, and then the surface of the resin film is subjected to a polishing treatment and / or a plasma treatment.

6. 6. The method for producing a fiber-reinforced composite material intermediate according to claim 1, wherein after the epoxy resin composition is photocured, the degree of cure of the fiber-reinforced composite material preliminary body is adjusted to 20 to 60% before laminating the fiber-reinforced composite material preliminary body on the resin film.

7. 7. The method for producing a fiber-reinforced composite material intermediate according to claim 1, wherein after photo-curing the epoxy resin composition, the degree of cure of the fiber-reinforced composite material preliminary body is adjusted to 20 to 60% before laminating the fiber-reinforced composite material preliminary body on the resin film, and then the surface of the fiber-reinforced composite material preliminary body is subjected to polishing treatment and / or plasma treatment.

8. The method for producing a fiber-reinforced composite material intermediate according to any one of claims 1 to 7, wherein the fiber-reinforced composite material preliminary body contains carbon fibers.

9. A method for producing a fiber-reinforced composite material, comprising further molding the fiber-reinforced composite material intermediate produced by the method for producing a fiber-reinforced composite material intermediate according to any one of claims 1 to 8 by heating or by heating and pressing.

10. The method for producing a fiber-reinforced composite material according to claim 9, wherein a surface of the fiber-reinforced composite material on the side of a resin film containing an epoxy resin composition containing the components [A] to [D] is subjected to a polishing treatment and / or a plasma treatment.

11. A photocurable resin film comprising an epoxy resin composition containing the following components [A] to [E], wherein the component [B] is contained in an amount of 15 to 75 parts by mass per 100 parts by mass of the total epoxy resin contained in the epoxy resin composition. [A] Non-aromatic epoxy resin [B] Pigment having a volume average particle size of 0.1 to 10 μm [C] Non-aromatic thermoplastic resin [D] Cationic curing agent or anionic curing agent [E] Thixotropy-imparting agent

12. The photocurable resin film according to claim 11, wherein the epoxy resin composition further comprises a component [F]. Component [F] Curing aid

13. The photocurable resin film according to claim 11 or 12, wherein the epoxy resin composition contains at least two types of component [A].

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