JP2020176268A - Resin composition for carbon fiber-reinforced composite material, carbon fiber member and carbon fiber-reinforced composite material - Google Patents

Abstract

To provide a resin composition for carbon fiber-reinforced composite materials that can be prepared with general-purpose materials to satisfy quick curability, high heat resistance, high toughness and low curing shrinkage at the same time, and a carbon fiber-reinforced composite material.SOLUTION: A resin composition for carbon fiber-reinforced composite materials comprises an epoxy compound (A), and a cationic photopolymerization initiator (B), the epoxy compound (A) comprising an aromatic ring-containing epoxy compound (A1).SELECTED DRAWING: None

Description

The present invention relates to a resin composition for a carbon fiber reinforced composite material, a carbon fiber member, and a carbon fiber reinforced composite material.

In recent years, carbon fiber reinforced composite materials composed of carbon fiber and matrix resin have been widely used in the fields of sports, automobiles, aerospace, building materials, etc. because they are lightweight and have excellent mechanical properties.
As the matrix resin (resin composition for carbon fiber reinforced composite material), a thermosetting resin typified by an epoxy resin is mainly used. However, although thermosetting resins have excellent physical properties after curing, they have a problem of low productivity because they take a long time to cure. Further, a thermoplastic resin typified by polypropylene resin is used in order to increase productivity, but its physical properties are inferior to those of a thermosetting resin. At present, there is a demand for a matrix resin that realizes a high-strength carbon fiber reinforced composite material at low cost, which is difficult to realize for both thermosetting resins and thermoplastic resins.

When the carbon fiber bundle is impregnated with the resin composition, the viscosity of the resin is generally required to be 20 Pa · s or less. This is because when the viscosity of the resin composition is high, the reinforcing fiber bundle is not sufficiently impregnated with the resin and the prepreg cannot be cured.
Generally, the carbon fiber bundle is impregnated with a thermosetting resin. Since the thermosetting resin has a relatively low viscosity before heat curing, the carbon fiber bundle is likely to be uniformly impregnated. Since the resin is cured by heating in a state where the carbon fiber bundle is uniformly impregnated, when stress is applied to the carbon fiber reinforced composite material, the stress is totally dispersed and relaxed, so that high strength is exhibited. However, since the curing temperature is about 120 degrees and the total curing time is 24 hours or more, the productivity is extremely low. (Patent Document 1)
When the thermoplastic resin is impregnated, the curing (solidification) rate after impregnation is excellent and the productivity is good. However, the thermoplastic resin melts again by reheating and has low adhesion to carbon fibers, so its strength is low and its use is limited. Therefore, it is particularly suitable for applications requiring reliability such as high-pressure containers. Not suitable. Further, since the impregnation property is low, it is necessary to impregnate by applying pressure, and a pressurizing facility is required separately from the heating furnace, resulting in low productivity. (Patent Document 2)

Radiation-curable resins using ultraviolet rays, electron beams, etc. have been reported in order to achieve both impregnation property and strength after curing. The radiation-curable resin has a low viscosity equal to or less than that of the uncured thermosetting resin in the uncured state before irradiation, and is therefore excellent in impregnation property. Further, after impregnation, the curing is completed by irradiating with radiation for several tens of seconds to several minutes, so that the curing is completed in the same time as the thermoplastic resin. Since the melting temperature after curing is the same as or higher than that of the thermosetting resin, reliability can be ensured, and in general, the curing density is higher than that of the thermosetting resin, so that the durability as a resin is also excellent. (Patent Documents 3, 4, 5)
Patent Document 3 discloses an epoxy resin composition for radiation curing, which comprises a resin component mainly composed of an epoxy resin and a photocation generator ((trilucmil) ionium tetrakis (pentafluorophenyl) boreate). Curability is improved by using (trilucmil) ionium tetrakis (pentafluorophenyl) boletate as the photocation generator, but the degree of curing varies greatly depending on the type of epoxy, and there are few more effective photocation generators. , The resin composition that fully exerts the effects of the reported invention is limited and its use is limited.
Patent Document 4 discloses an initiator composed of a photopolymerization initiator and a photo / thermal polymerization initiator, and reports a resin composition having excellent photocurability in a carbon fiber reinforced composite material. Since the initiator is a binary system, a curing reaction by light and a curing reaction by heat energy at that time occur, and curing proceeds effectively even in the presence of carbon fibers having high shielding properties. Since various epoxy resins and initiators can be used in this system, it seems to be highly versatile at first glance, but the thermal energy generated by the photocuring reaction generated by the first initiator is the initiator and the initiator. There is no guarantee that the amount of energy that will cause the reaction with the second initiator will be obtained. Furthermore, since overall curing reaction control is performed only on the initial light irradiation dose, the environment in which the reaction proceeds (room temperature, humidity, illuminance, etc.) must always be kept strictly constant, and such complex energies are required. It is not practical to try to obtain a reliable carbon fiber reinforced composite material by a chain reaction.
Patent Document 5 discloses a resin composition for a fiber reinforcing material containing a type of curing agent consisting of a photoacid generator, a thermoacid generator, and an epoxy curing agent, and a bridging ring-type alicyclic diepoxy compound. There is. Since the cross-linked alicyclic diepoxy compound has low viscosity and low curing shrinkage, the curing rate and heat resistance are improved. With any of the curing agents, a cured product having excellent heat resistance and toughness, and a fiber-reinforced composite material having excellent tensile strength and heat cycle resistance can be obtained, but in the thermosetting system, the temperature is 100 to 150 ° C. It takes a total of 3 hours of temperature and time, which is inferior in productivity. In addition, both thermosetting and photocuring systems are costly because a bridging cyclic alicyclic diepoxy compound having a special structure with low versatility is indispensable. Furthermore, the bridging cyclic structure has intramolecular strain. Since the stress is very large, the stress is concentrated on the bridging annular portion. Therefore, it is considered that the curing rate is improved by the addition, but the stress relaxation after curing does not occur sufficiently and the strength is inferior. In fact, in the literature, in terms of toughness indicating strength, even a cured product to which a simple general-purpose alicyclic diepoxy compound is added has the same level of toughness as a cured product of a bridged alicyclic diepoxy compound. Also disclosed are examples of fiber-reinforced composite materials in which the tensile strength using a ring-type alicyclic diepoxy compound is lower than the tensile strength using a simple general-purpose alicyclic diepoxy compound.

Japanese Unexamined Patent Publication No. 2001-098175 JP-A-2015-187202 Japanese Unexamined Patent Publication No. 2005-281606 Japanese Unexamined Patent Publication No. 2005-206847 JP 2015-193830

The present invention provides a resin composition for a carbon fiber reinforced composite material and a carbon fiber reinforced composite material that simultaneously satisfy high-speed curing, high heat resistance, high toughness, and low curing shrinkage using a general-purpose material.

As a result of intensive studies to solve the above problems, the present inventors have found a resin composition for a carbon fiber reinforced composite material containing an epoxy compound (A) and a cationic photopolymerization initiator (B). It has been found that the above-mentioned problems can be solved by a resin composition for a carbon fiber reinforced composite material, wherein the epoxy compound (A) contains an aromatic ring-containing epoxy compound (A1).

That is, the present invention is a resin composition for a carbon fiber reinforced composite material containing an epoxy compound (A) and a cationic photopolymerization initiator (B), wherein the epoxy compound (A) is an aromatic ring-containing epoxy compound ( The present invention relates to a resin composition for a carbon fiber reinforced composite material, which comprises A1).

Further, the present invention is characterized in that the epoxy compound (A) further contains at least one selected from a glycidyl ether-based epoxy compound (A2) and an alicyclic epoxy compound (A3). Regarding resin compositions for materials.

Further, the present invention further contains a compound (C) containing at least one hydroxyl group in the molecule (excluding the epoxy compound (A)), and the compound (C) containing at least one hydroxyl group in the molecule. ) Is 0.1 to 30% by weight based on 100% by weight of the resin composition for carbon fiber reinforced composite material, the present invention relates to the resin composition for carbon fiber reinforced composite material.

Further, the present invention is characterized in that the content of the cationic photopolymerization initiator (B) is 0.1 to 20% by weight based on 100% by weight of the resin composition for a carbon fiber reinforced composite material. The present invention relates to a resin composition for a fiber-reinforced composite material.

Further, the present invention further comprises a photosensitizer, and the content of the photosensitizer is 0.1 to 10% by weight based on 100% by weight of the resin composition for a carbon fiber reinforced composite material. The present invention relates to the resin composition for a carbon fiber reinforced composite material.

Further, the present invention further contains an oxetane group-containing compound, and the content of the oxetane group-containing compound is 0.1 to 30% by weight based on 100% by weight of the resin composition for a carbon fiber reinforced composite material. The present invention relates to the resin composition for a carbon fiber reinforced composite material.

Further, the present invention is further characterized in that it contains a vinyl group-containing compound, and the content of the vinyl group-containing compound is 0.1 to 10% by weight based on 100% by weight of the resin composition for a carbon fiber reinforced composite material. The present invention relates to the resin composition for a carbon fiber reinforced composite material.

The present invention also relates to a carbon fiber material containing a photocured product and carbon fibers of the resin composition for a carbon fiber reinforced composite material.

The present invention also relates to a carbon fiber reinforced composite material, which comprises impregnating the carbon fiber material with at least one resin selected from a thermoplastic resin, a thermosetting resin, and a photocurable resin.

Further, the present invention is characterized in that the carbon fiber-reinforced composite material resin composition is impregnated into carbon fibers as a matrix resin, and the carbon fiber-reinforced composite material resin composition is cured by light irradiation. The present invention relates to a method for producing a fiber-reinforced composite material.

The resin composition for a carbon fiber reinforced composite material of the present invention can simultaneously satisfy high-speed curing, high heat resistance, high toughness and low curing shrinkage.

The resin composition for a carbon fiber reinforced composite material of the present invention is a resin composition for a carbon fiber reinforced composite material containing an epoxy compound (A) and a cationic photopolymerization initiator (B), and the epoxy compound (A). Of 100 parts by weight of the epoxy compound constituting the above, 50 to 100 parts by weight of the aromatic ring-containing epoxy compound (A1), at least one of the glycidyl ether-based epoxy compound (A2) and the alicyclic epoxy compound (A3) is selected. Contains 0 to 50 parts by weight of the epoxy compound. Further, the range expressed by XX to Δ△ in the present invention means that it is XX or more and Δ△ or less.

<Resin composition for carbon fiber reinforced composite material>
(Epoxy compound (A))
The "epoxy compound" in the present invention is a compound having a plurality of epoxy groups in the molecule. Of 100 parts by weight of the epoxy compound constituting the epoxy compound (A), 50 to 100 parts by weight of the aromatic ring-containing epoxy compound (A1), at least one of the glycidyl ether-based epoxy compound (A2) or the alicyclic epoxy compound (A3). It is preferable to contain 0 to 50 parts by weight of one or more selected epoxy compounds. Since the surface of the carbon fiber is composed of an aromatic ring plan surface in which the π-electron system is continuously spread, the epoxy compound (A) contains the aromatic ring-containing epoxy compound (A1) to form a resin composition. Π-π interaction works between carbon fiber and carbon fiber to improve adhesion. By improving the adhesion between the resin composition and the carbon fiber, the strength is improved when the carbon fiber reinforced composite material is used. By the same principle, the same effect can be obtained when the sizing treatment site contains a compound having an aromatic ring even for carbon fibers whose surface has been sized, and the sizing treatment site contains ions such as acid or base. The same effect can be obtained by the ion-π interaction when the compound is included. The aromatic ring-containing epoxy compound (A1) is preferably contained in an amount of 50 to 100 parts by weight, more preferably 60 to 100 parts by weight, based on 100 parts by weight of the epoxy compound (A).

The aromatic ring-containing epoxy compound (A1) is not particularly limited as long as it contains an aromatic ring and an epoxy group in the molecule, and known ones can be used. For example, bisphenol A type epoxy compound and bisphenol. AD type epoxy compound, bisphenol F type epoxy compound, phenol novolac type epoxy compound, cresol novolac type epoxy compound, naphthalene type epoxy compound, anthracene type epoxy compound, biphenyl type epoxy compound and the like can be mentioned. Examples of product names include Mitsubishi. Jer152, jer157S70, jer806, jer807, jer827, jer828, jer834, jer1001, jer1256, jer4004P, jer4005P, jer4007P, jer4010P, jer4250, jer4275, YX4000, YL6810, DIC Co., Ltd. EPICLON 153-60T, EPICLON 153-60M, EPICLON 1121N-80M, EPICLON 1123P-73M, EPICLON 830, EPICLON 830-S, EPICLON 830-LVP, EPICLON 835, EPICLON 835-LV, EPICLON
840-S, EPICLON 850, EPICLON 850-S, EPICLON
850-CRP, EPICLON 850-LC, EPICLON 860, EPICLON 860-90X, EPICLON 1050, EPICLON 1050-70X, EPICLON 1050-75X, EPICLON 1055, EPICLON 1055-75X, EPICLON HM-091 EPICLON HM-101, EPICLON N-660, EPICLON
N-665, EPICLON N-670, EPICLON N-673, EPICLON N-680, EPICLON N-695, EPICLON N-740, EPICLON N-770, EPICLON N-775, EPICLON N-740-80M, EPICLON N-7 -70M, EPICLON N-865, EPICLON N-856-80M, Denacol EX-141, Denacol EX-145, Denacol EX-146, Denacol EX-147, Denacol EX-201, Denacol EX-manufactured by Nagase ChemteX Corporation. 203, Denacol EX-711, Denacol EX-721, Denacol EX-731, YD-115, YD-115G, YD-115CA, YD-118T, YD-127, YD-128, YD-manufactured by Nippon Steel & Sumitomo Metal Corporation. 128G, YD-128S, YD-128CA, YD-134, YD-011, YD-012, YD-013, YD-014, YD-017, YD-019, YD-020G, YD-7011R, YD-901, YD-902, YD-903N, YD-904, YD-907, YD-6020, UDF-170, YDF-2001, YDF-2004, YDPN-638, YDCN-700-3, YDCN-700-5, YDCN- Examples thereof include 700-7, YDCN-700-10, YDCN-704, and YDCN-704A, but the present invention is not particularly limited, and one type or a combination of two or more types can be used.

From the viewpoint of impregnation property, the epoxy compound (A) is preferably liquid (viscosity is 20000 mPa · s or less) at 40 ° C. When it is not liquid, the impregnation property of the carbon fiber into the resin composition is remarkably lowered, and a carbon fiber reinforced composite material having high strength cannot be obtained. In addition to the impregnation property, the viscosity at 40 ° C. is more preferably 100 to 15000 mPa · s in order to prevent liquid dripping. When the aromatic ring-containing epoxy compound (A1) is larger than 20000 mPa · s at 40 ° C., or when the viscosity is adjusted in the range of 20000 mPa · s, the epoxy compound (A) is diluted with a solvent, a monomer, an oligomer, or the like. Can be used in a liquid state.

Solvents that can be used as the diluting solvent of the present invention are toluene, xylene, ethyl acetate, butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, propylene glycol 1-monomethyl ether 2-acetylate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether. Examples thereof include acetate and diethylene glycol monobutyl ether acetate, and one type or a combination of two or more types can be used.

It is preferable to dilute with a monomer or an oligomer in order to suppress the residue as a monomer component after curing. As the monomer and oligomer that can be used for dilution, any compound containing a photocurable functional group can be appropriately selected and used. For example, a (meth) acrylate group-containing compound, an epoxy group-containing compound, and an oxetane group can be used. Examples include a compound containing a compound and a compound containing a vinyl group, and one type or a combination of two or more types can be used. In particular, it is preferably an epoxy group-containing compound from the viewpoint of compatibility with the aromatic ring-containing epoxy compound (A1) and curability, and particularly from the glycidyl ether-based epoxy compound (A2) or the alicyclic epoxy compound (A3). It is preferably one or more epoxy compounds of choice. The glycidyl ether-based epoxy compound (A2) has excellent compatibility with the aromatic ring-containing epoxy compound (A1), and the alicyclic epoxy compound (A3) has an excellent curing rate. When used as a dilution, the compound is preferably 50 parts by weight or less, more preferably 40 parts by weight or less, based on 100 parts by weight of the epoxy compound (A) so as not to impair the strength after curing. If it is more than 50 parts by weight, the adhesion between the resin compound and the carbon fiber is lowered, and the strength of the carbon fiber reinforced composite material is lowered.

The compound that can be used as the glycidyl ether-based epoxy compound (A2) of the present invention is not particularly limited as long as it is a compound containing an ether bond and an epoxy group, and known compounds can be used. For example, ED manufactured by Adeca Co., Ltd. -502, ED-509E, ED-503, ED-503G, ED-506, ED-523T, ED-505, DY-BP, CY-BP, Epogose EN, Epogose AN, Epogose 2EH, manufactured by Yokkaichi Chemical Co., Ltd. Epogose HD (M), Epogose HD (D), Epolite M-1230, Epolite 40E, Epolite 100E, Epolite 200E, Epolite 400E, Epolite 70P, Epolite 200P, 400, Epolite 1500NP, Epolite 1600, Epolite 80MF, Epolite 100MF, Epolite 4000, Epool M manufactured by Nichiyu Co., Ltd., Epool EH, Epool L-41, Epool SK, Epool E-400, Epool E-1000, Epool P-200, Epool NPG-100, Nagasechem Denacol EX-611, Denacol EX-612, Denacol EX-614, Denacol EX-614B, Denacol EX-622, Denacol EX-411, Denacol EX-221, Denacol EX-212, Denacol EX-252, manufactured by Tex Co., Ltd. Denacol EX-810, Denacol EX-811, Denacol EX-850, Denacol EX-851, Denacol EX-821, Denacol EX-830, Denacol EX-832, Denacol EX-841, Denacol EX-861, Denacol EX-911, 941, 920, 931, Denacol EX-111, Denacol E
Examples thereof include X-121, Denacol EX-171, Denacol EX-192, and Denarex R-45EPT, which can be used alone or in combination of two or more.

The compound that can be used as the alicyclic epoxy compound (A3) of the present invention is not particularly limited as long as it is a compound containing an alicyclic epoxy group, and known ones can be used, for example, 3,4-epoxycyclo. Hexenylmethyl-3', 4'-epoxycyclohexene carboxylate, ε-caprolactone modified 3,4-epoxycyclohexylmethyl-3', 4'-epoxycyclohexanecarbochelate, vinylcyclohexene monooxide, 1,2-epoxy-4- Examples thereof include vinylcyclohexane, 1,2: 8,9 diepoxylimonene, 3,4-epoxycyclohexylmethylmethacrylate, and the like, and these compounds may be used alone or in combination of two or more. Examples of the alicyclic epoxy resin product include celloxide 2021, 2081, 2000, 3000 and cyclomer M100 manufactured by Daicel Chemical Industries, Ltd. The alicyclic epoxy resin (A1) is preferably bifunctional or higher from the viewpoint of curability. By increasing the number of functional groups, the curing rate is improved and the strength of the tank is increased. It can be used alone or in combination of two or more.

As the cationic photopolymerization initiator (B) of the present invention, any known compound having photosensitivity in the ultraviolet region to the near infrared region and generating a cation can be used. By polymerizing the epoxy compound (A) using the cationic photopolymerization initiator (B), curing is completed in a shorter time as compared with the thermosetting epoxy resin, so that the productivity is high, and for example, radicals. Compared with the polymerizable acrylate resin, it is not affected by the curing environment, and the curing proceeds with less curing shrinkage, so that a carbon fiber reinforced composite material having high strength can be obtained.
As the cationic polymerization initiator (B), for example, various compounds such as a diazonium compound, a sulfonium compound, an iodonium compound, and a metal complex compound are known, and "Functional Materials", October, 1985, Item 5. , "Applications and Markets of UV / EB Hardening Technology", CMC Co., Ltd., published in 1989, p. 78, etc., has a detailed description. Specific examples include triphenylsulfonium 6 fluorinated antimonate, triphenylsulfonium hexafluorophosphate, triphenyleudonium hexafluoroantimonate, diphenyl-4-thiophenoxyphenylhexafluoroantimonate, 4, 4'-bis (bis). (P-2-Hydroxyethoxyphenyl) Sulfonio) Phenylsulfide bishexafluoroantimonate and the like can be mentioned. Product names include, for example, CI-2855 manufactured by Nippon Soda Co., Ltd. and WPI-113 manufactured by Wako Pure Chemical Industries, Ltd. , WPI-116
, WPI-169, WPI-170, WPI-124, CPI-100P, CPI-101A, CPI-200K, CPI-210S, CPI-300PG, CPI-310B, CPI-400PG, BASF Co., Ltd. IRGACURE250, IRGACURE270, IRGACURE290 and the like can be mentioned, and one type or a combination of two or more types can be used.

The blending amount of the cationic photopolymerization initiator (B) is 0.1 to 20% by weight, preferably 0.5 to 15% by weight, based on 100% by weight of the resin composition for the carbon fiber reinforced composite material. If the blending amount of the cationic photopolymerization initiator (B) is less than 0.1% by weight, the polymerization tends to be insufficient. On the other hand, if the blending amount of the cationic photopolymerization initiator (B) exceeds 20% by weight, it is economically disadvantageous and the physical properties of the cured product are deteriorated.

The resin composition for a carbon fiber reinforced composite material of the present invention may contain a photosensitizer as long as the effect is not impaired. By containing the photosensitizer, the curing time can be shortened and the exposure amount can be reduced, so that the productivity is excellent and the effect of improving the physical properties after curing can be obtained. Known photosensitizers can be used, and for example, compounds such as anthracene, benzophenone, thioxanthone, perylene, phenothiazine, and rose bengal can be used. As the product name, for example, Kawasaki Kasei Chemicals Co., Ltd. Anthracene UVS-581, 1101, 1331 manufactured by the company, KAYACURE DETX-S manufactured by Nippon Kayaku Co., Ltd., KAYACURE EPA, etc. are mentioned, but are not particularly limited and can be used alone or in combination of two or more. .. The blending amount of the photosensitizer may be appropriately selected as long as it does not interfere with the effects of the present invention, but may be 0.1 to 10% by weight in 100% by weight of the resin composition for carbon fiber reinforced composite material. preferable.

The resin composition for a carbon fiber reinforced composite material of the present invention preferably contains a compound (C) containing at least one hydroxyl group in the molecule (however, excluding the epoxy compound (A)). By containing the compound (C) containing at least one hydroxyl group in the molecule, the photocurability is improved, and the carbon fiber and the resin are contained by the compound (C) containing at least one hydroxyl group in the molecule. Since the wettability with the composition is improved and the adhesion between the carbon fiber and the resin composition is also improved, the physical properties after curing are improved. The compound (C) containing at least one hydroxyl group in the molecule is preferably contained in an amount of 0.1 to 30% by weight, preferably 0.1 to 20% by weight, based on 100% by weight of the resin composition for a carbon fiber reinforced composite material. It is more preferably contained, and more preferably 0.1 to 15% by weight. If the content is less than 0.1% by weight, the above effect cannot be sufficiently obtained, and if it is more than 30% by weight, the function as a plasticizer becomes large and the material becomes brittle after curing.

Known compounds (C) containing at least one hydroxyl group in the molecule of the present invention can be used, for example, water, methanol, ethanol, propanol, iso-propanol, butanol, t-butanol, pentanol, hexanol. , Cyclohexanol, Heptanol, Octanol, Nonanol, Decanol, Dodecanol, Tetradecanol, Hexadecanol, Stearyl alcohol, Oleyl alcohol, Linolyl alcohol, Phenol, Diethylene glycol monomethyl ether, Diethylene glycol monobutyl ether, Dipropylene glycol monomethyl ether, Dipropylene Monovalent alcohols such as glycol monobutyl ether, 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol , 2,3-Butandiol, Diethylene Glycol, Catecol, Resolsinol, Divalent Alcohols such as Hydroquinone, 1,2,3-Propanetriol, 1,2,3-Butantriol, 1,2,4-Butantriol, 1, 2,3-Pentan Triol, 1,2,4-Pentan Triol, 1,2,5-Pentan Triol, 1,3,4-Pentan Triol, 1,3,5-Pentan Triol, 2,3,4-Pentan Triol, 1,2,3-benzenetriol, 1,3,5-benzenetriol, 1,2,4-benzenetriol and other trihydric alcohols can be mentioned, but are not particularly limited and one or more. Can be used in combination.

An oxetane group-containing compound may be added to the resin composition of the present invention. By adding an oxetane compound, improvement in curing speed can be expected. As the oxetane group-containing compound in the present invention, a compound containing one or more oxetane groups in the molecule, and known compounds can be used. Examples of the oxetane group-containing compound include OXT-101, OXT-212, OXT-121, and OXT-221 manufactured by Synthetic Co., Ltd., but the present invention is not particularly limited, and one type or a combination of two or more types may be used. Can be done. The oxetane group-containing compound is preferably contained in an amount of 0.1 to 30% by weight based on 100% by weight of the resin composition for a carbon fiber reinforced composite material. If it is less than 0.1% by weight, it is difficult to obtain the effect of improving the curing rate, and if it is more than 30% by weight, the adhesion to the carbon fiber is lowered and the strength after curing is lowered.

A vinyl group-containing compound may be added to the resin composition of the present invention. By adding a vinyl group-containing compound, improvement in curing speed can be expected. As the vinyl group-containing compound in the present invention, a compound containing one or more vinyl groups in the molecule and known can be used. Examples of the vinyl group-containing compound include vinyl ether, ethyl vinyl ether, ethylhexyl vinyl ether, propyl vinyl ether, isopropyl vinyl ether, butyl vinyl ether, cyclohexyl vinyl ether, 1,4-butanediol divinyl ether, cyclohexanedimethanol divinyl ether, diethylene glycol divinyl ether, and tri. Examples thereof include ethylene glycol divinyl ether, styrene, acrylamide, acrylate, ethyl acrylate, methyl acrylate, butyl acrylate, ethylhexyl acrylate and the like, and the present invention is not particularly limited and may be used alone or in combination of two or more. .. The vinyl group-containing compound is preferably contained in an amount of 0.1 to 10% by weight based on 100% by weight of the resin composition for a carbon fiber reinforced composite material. If it is less than 0.1% by weight, the effect of improving the curing rate is difficult to obtain, and if it is more than 10% by weight, the adhesion to the carbon fiber is lowered and the strength after curing is lowered.

<Carbon fiber>
Carbon fibers are generally classified into polyacrylonitrile (PAN) type and pitch type, but any carbon fiber can be used as the carbon fiber in the present invention, and any carbon fiber can be used, and it is appropriately selected and used according to the application. be able to. Further, in addition to carbon fiber, fiber materials such as glass fiber, aramid fiber, polyethylene terephthalate fiber, and vinylon fiber may be used in combination. Further, the shape of the fiber material is roving, knitting, cloth, matte or the like.

<Light irradiation>
The photocured product of the resin composition for a carbon fiber reinforced composite material of the present invention can be obtained by irradiating the resin composition for a carbon fiber reinforced composite material with light. As the light to irradiate the resin composition for the carbon fiber reinforced composite material, light in the ultraviolet to near infrared region is used. Ultraviolet rays refer to light rays in the wavelength range of 280 to 400 nm, visible light refers to light rays in the wavelength range of 400 to 800 nm, and near infrared rays refer to light rays in the wavelength range of 800 to 1200 nm. Among them, ultraviolet rays are preferable because the irradiation time of light is relatively short and the influence of air is relatively small.
The light source used in the present invention includes an LED lamp, a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a fluorescent lamp, natural light, sunlight, a metal halide lamp, a xenon lamp, a halogen lamp, a near infrared lamp, and red. Examples include outside lamps. Among these, the use of an LED lamp is preferable from the viewpoint of workability because heat generation from the light source can be suppressed.

The light irradiation time is the effective wavelength of the light source, the output of the light source, the distance from the light source to the carbon fiber reinforced composite material, the thickness of the carbon fiber reinforced composite material, the amount of the resin composition for the carbon fiber reinforced composite material, and the carbon fiber. It may be appropriately determined depending on the degree of thickening of the resin composition for the reinforced composite material, and is not particularly limited. Specifically, the carbon fiber material or the carbon fiber material so that the cationic polymer group such as the epoxy group in the curable resin composition partially reacts to appropriately thicken the resin composition for the carbon fiber reinforced composite material. It is preferable to irradiate the carbon fiber reinforced composite material with light so that the integrated light amount on the irradiation surface is 10 to 30,000 mJ / cm ² . Further, if necessary, heat treatment may be performed during light irradiation or before and after light irradiation.

<Carbon fiber material>
The carbon fiber material in the present invention is a carbon fiber-containing member in which a first carbon fiber and a second carbon fiber, or a metal, plastic, or glass are bonded to each other via a resin composition for a carbon fiber reinforced composite material. The resin composition for a carbon fiber reinforced composite material is used as a photocurable adhesive interposed between the first carbon fiber and the second carbon fiber, or between metal, plastic, and glass. By adhering the first and second carbon fibers to each other with a resin composition for a carbon fiber reinforced composite material, the carbon fiber raw fabrics are connected to each other to maintain the continuity of the carbon fibers when the carbon fiber reinforced composite material is produced. It is possible and productivity is improved. Further, since the resin composition for carbon fiber reinforced composite material of the present invention can bond carbon fiber to metal, plastic, and glass, when the carbon fiber is wound or laminated around metal, plastic, and glass. It can be used as a primer and can improve the strength of the carbon fiber reinforced composite material. Examples of the metal include stainless steel, aluminum, aluminum alloy, iron and the like, examples of the plastic include polyethylene and polypropylene, and examples of the glass include soda-lime glass, borosilicate glass and quartz glass. Not particularly limited, known ones can be used.

<Carbon fiber reinforced composite material>
The carbon fiber reinforced composite material in the present invention is a composite material in which the carbon fibers are impregnated with the resin composition for the carbon fiber reinforced composite material and then photocured under the light irradiation conditions. The amount of the fiber material used in the carbon fiber reinforced composite material is preferably 5 to 600 parts by weight, preferably 50 to 500 parts by weight, based on 100 parts by weight of the resin composition for the carbon fiber reinforced composite material. If the amount used is less than 5 parts by weight, the strength of the carbon fiber reinforced composite material is low, and if it is larger than 600 parts by weight, the fiber material is peeled off.
It can also be obtained by impregnating the carbon fiber material with at least one resin selected from a thermoplastic resin, a thermosetting resin, and a photocurable resin. By using the carbon fiber material, the strength of the joint portion after impregnation can be improved. The thermoplastic resin, thermosetting resin, and photocurable resin that can be used in the present invention are not particularly limited and known ones can be used. For example, in the case of a thermoplastic resin, polyethylene resin, polypropylene resin, polyamide resin, poly Butylene terephthalate resin, polyethylene terephthalate resin, ethylene-vinyl acetate resin, etc., thermosetting resin includes epoxy resin, polyester resin, phenol resin, acrylic resin, etc., and photocurable resin, epoxy. Examples thereof include resin, acrylic resin, oxetane resin, and vinyl resin.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples. In the examples, parts indicate parts by weight, and% indicates% by weight.

[Example 1]
<Adjustment of curable resin composition>
JER828 (Mitsubishi Chemical Corporation, bisphenol A type epoxy resin) 99.9 parts, CPI (San Apro Co., Ltd., p-phenylthiophenyldiphenylsulfonium PF ₆ salt) 0.01 part is stirred and the curable resin composition A-1 Got

<Evaluation of curing rate>
After applying the curable resin composition A-1 to a PET substrate so as to have a film thickness of 100 μm, an LED light source UV light (wavelength: 365 nm, irradiation intensity: 1000 mW / cm ² ) is applied from the coated surface to the curable resin. Irradiation was performed until the composition became less fluid. The irradiation time at this time was used as the curing time and evaluated according to the following criteria. The evaluation results are shown in Table 1.
◯: Curing time less than 15 seconds Δ: Curing time 15 seconds or more and less than 1 minute ×: Curing time 1 minute or more

<Evaluation of dimensional stability>
After measuring the specific gravity of the curable resin composition A-1 in the uncured state, the curable resin composition A-1 is coated on the PET substrate so as to have a film thickness of 100 μm, and the LED light source UV light (wavelength: A cured product was obtained by irradiating with 365 nm and irradiation intensity: 1000 mW / cm ² ) for 10 seconds to cure. The specific gravity of the cured product was measured, and the curing shrinkage rate was measured from the following formula. The specific gravity was measured at 23 ° C.
Curing shrinkage rate (%) = 100 × (cured product specific gravity-uncured product specific gravity) / cured product specific gravity Using the obtained curing shrinkage rate, dimensional stability was evaluated according to the following criteria. The evaluation results are shown in Table 1.
◯: Curing shrinkage rate less than 1% Δ: Curing shrinkage rate 1% or more and less than 3% ×: Curing shrinkage rate 3% or more

<Evaluation of heat resistance>
After coating the curable resin composition A-1 on the peel-treated PET substrate to a thickness of 100 μm, the coated surface is irradiated with an LED light source UV light (wavelength: 365 nm, irradiation intensity: 1000 mW / cm ² ) for 10 seconds. did. The obtained cured product is peeled off from the PET substrate, cut into a size of 10 mm × 20 mm, set in a tensile tester so that the distance between chucks is 10 mm, and a tensile test is performed at a speed of 1 mm / min at 25 ° C. went. The stress when the cured product broke was defined as T (25). Subsequently, the same test was carried out at 100 ° C., and the strength ratio was calculated from the following formula, with the stress when the cured product was broken as T (100).
Strength ratio = T (100) / T (25)
The heat resistance was evaluated according to the following criteria using the obtained strength ratio. The evaluation results are shown in Table 1.
◯: Intensity ratio 0.95 or more Δ: Intensity ratio 0.85 or more, less than 0.95 ×: Intensity ratio less than 0.85

<Evaluation of curability>
After the curable resin composition A-1 was applied to the PET substrate so as to have a film thickness of 100 μm, an LED light source UV light (wavelength: 365 nm, irradiation intensity: 1000 mW / cm ² ) was irradiated from the coated surface for 10 seconds. .. The resin composition after irradiation was peeled off from the PET substrate, and about 1 g was immersed in methyl ethyl ketone (MEK) and left at 40 ° C. for 24 hours. After leaving it to stand, it was placed in an oven at 100 ° C. for 1 minute to volatilize MEK, then the mass of the resin composition was measured, the weight loss of the resin composition before and after immersion was calculated, and the curability was evaluated according to the following criteria. .. The evaluation results are shown in Table 1.
5: Resin composition weight loss 0% or more and less than 5% 4: Resin composition weight loss 5% or more and less than 10% 3: Resin composition weight loss 10% or more and less than 20% 2: Resin composition weight loss 20% or more and less than 50% 1: Resin composition weight loss 50% or more

<Adhesion evaluation>
The adhesion was evaluated by the microdroplet method. The curable resin composition A-1 was dropped on the carbon monofilament and irradiated with an LED light source UV light (wavelength: 365 nm, irradiation intensity: 1000 mW / cm ² ) for 10 seconds to obtain a curable resin-adhered carbon monofilament. Then, it was sandwiched between blades so as to pull out the cured resin adhering matter from the cured resin-attached carbon monofiber, and the cured resin-attached carbon monofiber was pulled at 0.06 mm / min. The maximum load F at this time was measured, and the interfacial shear strength τ was obtained by the following formula.
Interfacial shear strength τ = F / (πdL)
However,
F: Maximum load at the time of test d: Carbon single fiber diameter L: Diameter in the drawing direction of the cured resin From the obtained interfacial shear strength, the adhesion was evaluated according to the following criteria. The evaluation results are shown in Table 1.
5: Interfacial shear strength 50 MPa or more 4: Interfacial shear strength 40 MPa or more and less than 50 MPa 3: Interfacial shear strength 30 MPa or more and less than 40 MPa 2: Interfacial shear strength 20 MPa or more and less than 30 MPa 1: Interfacial shear strength less than 20 MPa

<Evaluation of adhesiveness>
The carbon fiber was cut into 10 mm × 50 mm, and 0.05 g of the curable resin composition A-1 was applied to the terminal 10 mm. A carbon fiber was laminated therein, and an LED light source UV light (wavelength: 365 nm, irradiation intensity: 1000 mW / cm ² ) was irradiated for 10 seconds on each of the upper and lower surfaces to obtain a carbon fiber material. The tensile shear adhesive force of the obtained carbon fiber material was measured under the conditions of 25 ° C. and 10 mm / min, and the maximum load (N) at the time of fracture was divided by the adhesive area (1 cm ² ) to calculate the adhesive force. It was evaluated according to the criteria of. The evaluation results are shown in Table 1.
5: adhesive force 50 N / cm ² or more 4: adhesive strength 40N / cm ² or more, 50 N / cm ² less than 3: adhesion 30 N / cm ² or more, 40N / cm ² less than 2: adhesion 20 N / cm ² or more, 30 N / Cm less than ² 1: Adhesive strength less than 20 N / cm ²

<Making a pressure vessel>
Carbon fiber is impregnated with the curable resin composition A-1, and an aluminum liner (outer diameter: 100 mm, length: 400 mm, wall thickness: 5 mm) is fitted with an LED light source UV light (wavelength: 365 nm, irradiation intensity: 1000 mW / cm). While irradiating ² ), a hoop layer of 1.0 mm was wound around the first layer and a helical layer of 2.0 mm was wound around the second layer to obtain a pressure vessel T-1.

<Pressure resistance evaluation>
The pressure vessel T-1 was installed in a pressure fracture tester, a load was applied to the inside of the vessel until the pressure vessel burst, and the pressure at the time of burst was defined as the breaking pressure, and the pressure resistance was evaluated according to the following criteria. The results are shown in Table 1.
5: Breaking pressure 45MPa or more 4: Breaking pressure 41MPa or more and less than 45MPa 3: Breaking pressure 38MPa or more and less than 41MPa 2: Breaking pressure 35MPa or more and less than 38MPa 1: Breaking pressure less than 35MPa

<Manufacturing of carbon fiber reinforced composite material>
The carbon fiber woven fabric is impregnated with the curable resin composition A-1, and the LED light source UV light (wavelength: 365 nm, irradiation intensity: 1000 mW / cm ² ) is irradiated from both sides of the curable resin composition-impregnated carbon fiber for 10 seconds each. Then, a carbon fiber reinforced composite material C-1 was obtained.
<Durability evaluation>
Durability evaluation was performed by a 3-point bending test based on JIS K7074. The carbon fiber reinforced composite material C-1 was cut out to 100 × 15 × 2 mm, placed on a support fulcrum with a distance between fulcrums of 80 mm and R = 2 mm, and loaded with an indenter of R = 5 mm at a test speed of 5 mm / min. The maximum load was measured, and the durability was evaluated according to the following criteria. The results are shown in Table 1.
5: Bending strength 500 MPa or more 4: Bending strength 450 MPa or more and less than 500 MPa 3: Bending strength 400 MPa or more and less than 450 MPa 2: Bending strength 300 MPa or more and less than 400 MPa 1: Bending strength less than 300 MPa

[Examples 2 to 20]
In the same manner as in Example 1, the curable resin composition having the composition shown in Table 1 was prepared, followed by a pressure vessel.
A carbon fiber material and a carbon fiber reinforced composite material were prepared and evaluated in the same manner as in Example 1. The results are shown in Table 1.

[Example 21]
The carbon fiber was cut into 15 mm × 100 mm, and 0.07 g of the curable resin composition A-1 was applied to the terminal 10 mm. A carbon fiber was laminated therein, and an LED light source UV light (wavelength: 365 nm, irradiation intensity: 1000 mW / cm ² ) was irradiated for 10 seconds on each of the upper and lower surfaces to obtain a carbon fiber material. The obtained carbon fiber material is impregnated into the curable resin composition A-1, and an LED light source UV light (wavelength: 365 nm, irradiation intensity: 1000 mW / cm ² ) is impregnated with 10 each from both sides of the curable resin composition impregnated carbon fiber. The carbon fiber reinforced composite material D-1 was obtained by irradiation for seconds. Using the obtained carbon fiber reinforced composite material, a three-point bending test conforming to JIS K7074 was performed in the same manner as in the durability evaluation. The obtained carbon fiber reinforced composite material was cut out to 100 × 15 × 2 mm, placed on a support fulcrum with a distance between fulcrums of 80 mm and R = 2 mm, and loaded with an indenter of R = 5 mm at a test speed of 5 mm / min. It was given and the maximum load was measured. At this time, the carbon fiber adhesive portion was placed under the indenter portion. From the maximum load obtained, the durability was evaluated according to the following criteria. The results are shown in Table 3.
◯: Bending strength 400 MPa or more ×: Bending strength less than 400 MPa

[Example 22]
A carbon fiber material was obtained in the same manner as in Example 21, and the obtained carbon fiber material was impregnated with the resin composition shown in B-1 of Table 2, and then left at 120 ° C. for 24 hours to be cured to strengthen the carbon fiber. A composite material was obtained. Using the obtained carbon fiber reinforced composite material, durability evaluation was performed in the same manner as in Example 21. The results are shown in Table 3.

[Example 23]
A carbon fiber material was obtained in the same manner as in Example 21, and the obtained carbon fiber material was impregnated with the resin composition shown in B-2 of Table 2 at 200 ° C. and 10 MPa, and then cooled to room temperature to carbon. A fiber reinforced composite material was obtained. Using the obtained carbon fiber reinforced composite material, durability evaluation was performed in the same manner as in Example 21. The results are shown in Table 3.

[Comparative Example 1]
<Evaluation of curing rate>
The resin composition B-1 shown in Table 2 was applied to a PET substrate so as to have a film thickness of 100 μm, and then placed in an oven at 120 ° C. and heated until the resin composition lost its fluidity. The heating time at this time was used as the curing time and evaluated according to the following criteria. The evaluation results are shown in Table 2.
◯: Curing time less than 15 seconds Δ: Curing time 15 seconds or more and less than 1 minute ×: Curing time 1 minute or more

<Evaluation of dimensional stability>
After measuring the specific gravity of the resin composition B-1 in the uncured state, the resin composition B-1 is applied to a PET substrate so as to have a film thickness of 100 μm, and heated at 120 ° C. for 24 hours to cure the cured product. Obtained. The specific gravity of the cured product was measured, and the curing shrinkage rate was measured from the following formula. The specific gravity was measured at 23 ° C.
Curing shrinkage rate (%) = 100 × (cured product specific gravity-uncured product specific gravity) / cured product specific gravity Using the obtained curing shrinkage rate, dimensional stability was evaluated according to the following criteria. The evaluation results are shown in Table 2.
◯: Curing shrinkage rate less than 1% Δ: Curing shrinkage rate 1% or more and less than 3% ×: Curing shrinkage rate 3% or more

<Evaluation of heat resistance>
The resin composition B-1 was applied to a peel-treated PET substrate so as to have a film thickness of 100 μm, and then heated at 120 ° C. for 24 hours to obtain a cured product. The obtained cured product is peeled off from the PET substrate, cut into a size of 10 mm × 20 mm, set in a tensile tester so that the distance between chucks is 10 mm, and a tensile test is performed at a speed of 1 mm / min at 25 ° C. went. The stress when the cured product broke was defined as T (25). Subsequently, the same test was carried out at 100 ° C., and the strength ratio was calculated from the following formula, with the stress when the cured product was broken as T (100).
Strength ratio = T (100) / T (25)
The heat resistance was evaluated according to the following criteria using the obtained strength ratio. The evaluation results are shown in Table 2.
◯: Intensity ratio 0.95 or more Δ: Intensity ratio 0.85 or more, less than 0.95 ×: Intensity ratio less than 0.85

[Comparative Example 2]
<Evaluation of heat resistance>
The resin composition B-2 was cut into a size of 10 mm × 20 mm × 100 μm, set in a tensile tester so that the distance between chucks was 10 mm, and a tensile test was performed at a speed of 1 mm / min at 25 ° C. The stress when the cured product broke was defined as T (25). Subsequently, the same test was carried out at 100 ° C., and the strength ratio was calculated from the following formula, with the stress when the cured product was broken as T (100).
Strength ratio = T (100) / T (25)
The heat resistance was evaluated according to the following criteria using the obtained strength ratio. The evaluation results are shown in Table 2.
◯: Intensity ratio 0.95 or more Δ: Intensity ratio 0.85 or more, less than 0.95 ×: Intensity ratio less than 0.85

[Comparative Examples 3 to 6]
The curable resin composition having the composition shown in Table 2 was prepared by the same method as in Example 1, subsequently, a pressure vessel, a carbon fiber material, and a carbon fiber reinforced composite material were prepared, and the same evaluation as in Example 1 was performed. went. The results are shown in Table 2. The curability, adhesion, adhesiveness, pressure resistance, and durability were evaluated only when all the evaluation results of the curing speed, dimensional stability, and heat resistance test were "◯" or "Δ". The evaluation results are shown in Table 2.

[Comparative Example 7]
Durability was evaluated in the same manner as in Example 21 except that the carbon fibers were cut and then laminated without applying the curable resin composition. The results are shown in Table 3.

[Comparative Example 8]
Durability was evaluated in the same manner as in Example 22 except that the carbon fibers were cut and then laminated without applying the curable resin composition. The results are shown in Table 3.

[Comparative Example 9]
Durability was evaluated in the same manner as in Example 23, except that the carbon fibers were cut and then laminated without applying the curable resin composition. The results are shown in Table 3.

The compounds shown in Table 1 are as follows.
JER 828: Mitsubishi Chemical, bisphenol A type epoxy compound JER 806: Mitsubishi Chemical, bisphenol F type epoxy compound JER 152: Mitsubishi Chemical, phenol novolac type epoxy compound N-660: DIC Co., Ltd., cresol novolac Type Epoxy Compound EX-721: Nagase ChemteX Corporation, Phtalic Acid Type Epoxy Compound YX4000: Mitsubishi Chemical Co., Ltd., Biphenyl Type Epoxy Compound HP-4770: DIC Co., Ltd., Naphthalene Type Epoxy Compound EX-211: Nagase ChemteX Glysidyl ether type epoxy compound EX-411: Nagase ChemteX Co., Ltd., Glysidyl ether type epoxy compound Selokiside 2021P: Dycel Co., Ltd., Bifunctional alicyclic epoxy compound CPI: San Apro Co., Ltd., p-phenylthiophenyl Diphenylsulfonium PF _6- salt IRGACURE 250: BASF, iodonium, (4-methylphenyl) [4- (2-methylpropyl) phenyl] PF _6- salt DETX-S: Nippon Kayaku Co., Ltd., thioxanthone-based photosensitizer UVS-1331: Kawasaki Kasei Kogyo Co., Ltd., Anthracene-based photosensitizer OXT-121: Toa Synthetic Co., Ltd., Oxetane group-containing compound BDVE: Nippon Carbide Kogyo Co., Ltd., 1,4-butanediol divinyl ether

The compounds shown in Table 2 are as follows.
JER 828: Mitsubishi Chemical Co., Ltd., bisphenol A type epoxy compound EX-211: Nagasechemtex Co., Ltd., glycidyl ether type epoxy compound Serokiside 2021P: Daicel Co., Ltd., bifunctional alicyclic epoxy compound TMPTA: trimethylpropantriacrylate J106G: Prime Polymer Co., Ltd., Polypropylene compound CPI: San Apro Co., Ltd., p-phenylthiophenyldiphenylsulfonium PF ₆ salt ST11: Mitsubishi Chemical Co., Ltd., amine-based thermosetting agent TPO: 2,4,6-trimethylbenzoyl-diphenyl- Phosphine oxide

As shown in Table 1, the curable resin compositions used in Examples 1 to 20 contain an epoxy compound (A) and a cationic photopolymerization initiator (B), and the epoxy compound (A) is further contained. Since it contains an aromatic ring-containing epoxy compound (A-1), it is excellent in curing speed, dimensional stability, heat resistance, curability and adhesion. It also has excellent adhesiveness when laminated between carbon fibers. Furthermore, the burst pressure of the pressure vessel produced by impregnating the carbon fiber and winding it around the aluminum liner is high and the pressure resistance is excellent, and the durability of the carbon fiber reinforced composite material is also excellent. In particular, Examples 7 to 20 contain the compound (C) containing at least one hydroxyl group in the molecule, and further contain a photosensitizer, an oxetane group-containing compound, and a vinyl group-containing compound, and thus are curable. , Adhesion, pressure resistance, and durability are all excellent. Further, as shown in Examples 21 to 23 of Table 3, the carbon fiber reinforced composite material obtained by using the carbon fiber material obtained by using the resin composition of the present invention as an adhesive between carbon fibers is a carbon fiber. It also has excellent durability at the connection part.
On the other hand, in Comparative Examples 1 and 4 in Table 2, since the photocationic photopolymerization initiator is not contained, the curing rate is poor and the productivity is not excellent. Further, in Comparative Example 2, since the curable resin is not contained, the heat resistance is poor. In Comparative Example 3, since the acrylic compound is photoradically cured, the curing rate and heat resistance are excellent, but the dimensional stability is poor due to the influence of curing shrinkage. Further, in Comparative Examples 5 and 6, since the aromatic ring-containing epoxy compound (A1) is not contained, the adhesion to the carbon fiber is poor, and the pressure resistance and durability are also poor. Further, in Comparative Examples 7 to 9 in Table 3, since no adhesive is used for the carbon fiber connecting portion of the carbon fiber reinforced composite material, the durability is poor.

The resin composition for carbon fiber reinforced composite material and the carbon fiber reinforced composite material of the present invention can simultaneously satisfy high-speed curability, high heat resistance, high dust resistance and low curing shrinkage by using general-purpose materials. Pressure vessels such as hydrogen tanks, sports equipment such as golf shafts and rackets, protective equipment such as bulletproof waistcoats, helmets and gloves, transportation equipment such as automobiles, motorcycles, aircraft, rockets and railroad vehicles, residential doors, partitions, etc. It can be used for building materials such as wall materials, and can be said to have extremely high industrial utility value.

Claims (3)

A resin composition for a carbon fiber reinforced composite material containing an epoxy compound (A) and a cationic photopolymerization initiator (B), wherein the epoxy compound (A) contains an aromatic ring-containing epoxy compound (A1). A resin composition for a carbon fiber reinforced composite material. A carbon fiber material containing a photocured product and carbon fibers of the resin composition for a carbon fiber reinforced composite material according to claim 1. The carbon fiber reinforced resin composition according to claim 1 is impregnated into carbon fibers as a matrix resin, and the carbon fiber reinforced composite material resin composition is cured by light irradiation. Method for manufacturing composite materials.