JP2019157057A - Curable resin composition, and prepreg, film and fiber-reinforced plastic including the same - Google Patents

Abstract

To provide a curable resin composition that makes it possible to obtain a fiber-reinforced composite material having excellent strength and elastic moduli, and a film, molding, prepreg and fiber-reinforced plastic including the resin composition.SOLUTION: The present invention provides a curable resin composition containing the following components (A), (B) and (C), and a prepreg containing a reinforced fiber and a matrix resin, wherein the matrix resin is the curable resin composition containing the following components (A), (B) and (C): (A): oxazolidone-type epoxy resin; (B): meta-type triglycidyl amino phenol; and (C): curing agent.SELECTED DRAWING: None

Description

  The present invention relates to a curable resin composition, and a prepreg, film and fiber reinforced plastic using the same, and is suitably used for sports / leisure use, general industrial use, aircraft material use, and the like. .

Fiber reinforced plastics, which are one of fiber reinforced composite materials, are light in weight, high strength, and high rigidity, and thus are widely used from sports / leisure applications to industrial applications such as automobiles and aircraft.
As a method for producing a fiber reinforced plastic, there is a method of using an intermediate material obtained by impregnating a matrix resin into a reinforcing material composed of long fibers (continuous fibers) such as reinforcing fibers, that is, a prepreg. According to this method, there is an advantage that the content of the reinforcing fiber of the fiber reinforced plastic can be easily managed and the content can be designed to be higher. By stacking a plurality of prepregs and heat-curing, A molded product can be obtained.

  Specific methods for producing fiber reinforced plastic from prepreg include molding using an autoclave, press molding, internal pressure molding, oven molding, sheet wrap molding, and the like.

  Among fiber reinforced plastics, fiber reinforced plastic tubular bodies are widely used for sports and leisure applications such as fishing rods, golf club shafts, ski poles, bicycle frames and the like. By utilizing the high elastic modulus of fiber reinforced plastic, it becomes possible to fly a ball or a fishhook far away with a small force due to the bending and reaction that occurs when the tubular body is shaken. Moreover, it can reduce in weight and can improve a user's operational feeling by setting it as a tubular body.

  In recent years, the need for weight reduction is increasing, so that not only carbon fibers but also matrix resins are required to have higher physical properties.

  In order to solve the above-described problems, it has been proposed to use, for example, the epoxy resin compositions described in Patent Documents 1 and 2 as the matrix resin composition.

JP 2002-284852 A Japanese Patent Laid-Open No. 11-171972

  However, since the epoxy resin compositions described in Patent Document 1 and Patent Document 2 have not been sufficiently studied, the mechanical properties are not sufficient, and a fiber-reinforced plastic tubular body having sufficient breaking strength is obtained. I couldn't.

  The present invention has been made in view of the background described above, and by using a specific epoxy resin as a matrix resin, a cured resin having excellent strength, elastic modulus and toughness is formed, and has excellent mechanical properties. It has been found that a fiber reinforced plastic can be obtained. The present invention is formed using a curable resin composition capable of obtaining excellent breaking strength, a prepreg using the resin composition, and further using this prepreg, particularly when applied to a tubular composite material. It provides fiber reinforced plastic.

  As a result of intensive studies, the present inventors have found that by using an epoxy resin having a specific structure in combination, the above problems can be solved and a fiber-reinforced plastic having a desired performance can be provided, leading to the present invention. It was.

That is, the present invention relates to the following.
[1] A curable resin composition comprising the following components (A), (B) and (C).
Component (A): Oxazolidone type epoxy resin Component (B): Meta type triglycidylaminophenol Component (C): Curing agent [2] As the curing agent (C), at least one selected from dicyandiamide, ureas, and imidazoles Curable resin composition as described in said [1] containing a seed | species.
[3] The curable resin composition according to [1] or [2], further including a thermoplastic resin as the component (D).
[4] A film comprising the curable resin composition according to any one of [1] to [3].
[5] A prepreg comprising reinforcing fibers and a matrix resin, wherein the matrix resin is a curable resin composition comprising the following components (A), (B), and (C).
Component (A): Oxazolidone type epoxy resin Component (B): Meta type triglycidylaminophenol Component (C): Curing agent [6] As the curing agent (C), at least one selected from dicyandiamide, ureas, and imidazoles The prepreg according to [5] above, which contains seeds.
[7] The prepreg according to the above [5] or [6], which further contains a thermoplastic resin as the component (D).
[8] A fiber-reinforced plastic comprising a cured product of the curable resin composition according to any one of [1] to [3] and a reinforcing fiber.
[9] The fiber-reinforced plastic according to [8], wherein the shape is tubular.

  The curable resin composition of the present invention gives a cured resin having high strength, high elastic modulus and high toughness, and excellent mechanical properties are obtained by using the curable resin composition of the present invention as a matrix resin for fiber reinforced plastics. A fiber-reinforced plastic is obtained. In particular, by using the curable resin composition of the present invention, excellent fracture strength can be obtained in a fiber reinforced plastic of a tubular body.

Hereinafter, the present invention will be described in detail.
In the present invention, “epoxy resin” means a compound having two or more epoxy groups in one molecule.
The term “curable resin composition” means a resin composition containing an epoxy resin, a curing agent, a curing accelerator, and optionally a thermoplastic resin or an additive.
In the present invention, a cured product obtained by curing the curable resin composition is referred to as a “resin cured product”, and among them, a plate-like cured product is particularly referred to as a “resin plate”.
In the present invention, the softening point, epoxy equivalent, and active hydrogen equivalent are values measured under the following conditions.
1) Softening point: A value measured in accordance with JIS-K7234: 2008 (ring and ball method).
2) Epoxy equivalent: A value measured according to JIS K-7236: 2001.

[Curable resin composition]
The curable resin composition of the present invention (hereinafter also referred to as “the present resin composition”) includes a component (A), a component (B), and a component (C). Further, component (D), other epoxy resins, and additives as optional components may be included.

<Component (A)>
Component (A) is an oxazolidone type epoxy resin.
The oxazolidone-type epoxy resin is an epoxy resin having an oxazolidone ring structure, which improves the workability of the prepreg containing the epoxy resin composition containing the epoxy resin composition at room temperature, and the elastic modulus and heat resistance of the cured product of the epoxy resin composition. And adhesion with reinforcing fibers.

  The oxazolidone ring structure is formed by an addition reaction between an isocyanate group and an epoxy group. The production method of the oxazolidone skeleton-containing epoxy resin in the present invention is not particularly limited. For example, by reacting an isocyanate compound and an epoxy resin having a biphenyl skeleton in the presence of an oxazolidone ring-forming catalyst, it is almost the theoretical amount. Obtainable. It is preferable that the isocyanate compound and the epoxy resin are reacted in an equivalent ratio of 1: 2 to 1:10. When the ratio of the two is in the above range, the heat resistance and water resistance of the cured epoxy resin are better. There is a tendency. In the present invention, various isocyanate compounds can be used as raw materials, but in order to incorporate the oxazolidone ring structure into the skeleton of the epoxy resin, an isocyanate compound having a plurality of isocyanate groups is preferable. Moreover, in order for the hardened | cured material of the epoxy resin composition containing the said component (A) to have high heat resistance, the diisocyanate which has a rigid structure is preferable.

  Specific examples of the isocyanate compound used as the raw material include, for example, methane diisocyanate, butane-1,1-diisocyanate, ethane-1,2-diisocyanate, butane-1,2-diisocyanate, transvinylene diisocyanate, propane-1,3- Diisocyanate, butane-1,4-diisocyanate, 2-butene-1,4-diisocyanate, 2-methylbutene-1,4-diisocyanate, 2-methylbutane-1,4-diisocyanate, pentane-1,5-diisocyanate, 2, 2-dimethylpentane-1,5-diisocyanate, hexane-1,6-diisocyanate, heptane-1,7-diisocyanate, octane-1,8-diisocyanate, nonane-1,9-diisocyanate, decane-1,10- Isocyanate, dimethylsilane diisocyanate, diphenylsilane diisocyanate, ω, ω′-1,3-dimethylbenzene diisocyanate, ω, ω′-1,4-dimethylbenzene diisocyanate, ω, ω′-1,3-dimethylcyclohexane diisocyanate, ω , Ω′-1,4-dimethylcyclohexane diisocyanate, ω, ω′-1,4-dimethylnaphthalene diisocyanate, ω, ω′-1,5-dimethylnaphthalene diisocyanate, cyclohexane-1,3-diisocyanate, cyclohexane-1, 4-diisocyanate, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate, dicyclohexylmethane-4,4′-diisocyanate, 1,3-phenylene diisocyanate, 1,4-pheny Diisocyanate, 1-methylbenzene-2,4-diisocyanate, 1-methylbenzene-2,5-diisocyanate, 1-methylbenzene-2,6-diisocyanate, 1-methylbenzene-3,5-diisocyanate, diphenyl ether-4 , 4′-diisocyanate, diphenyl ether-2,4′-diisocyanate, naphthalene-1,4-diisocyanate, naphthalene-1,5-diisocyanate, biphenyl-4,4′-diisocyanate, 3,3′-dimethylbiphenyl- 4,4′-diisocyanate, 2,3′-dimethoxybisphenyl-4,4′-diisocyanate, diphenylmethane-4,4′-diisocyanate, 3,3′-dimethoxydiphenylmethane-4,4′-diisocyanate, 4,4 '-Dimet Bifunctional isocyanate compounds such as sidiphenylmethane-3,3′-diisocyanate, norbornene diisocyanate, diphenylsulfite-4,4′-diisocyanate, diphenylsulfone-4,4′-diisocyanate; polymethylene polyphenylisocyanate, triphenylmethanetri Polyfunctional isocyanate compounds such as isocyanate, tris (4-phenylisocyanatethiophosphate) -3,3 ′, 4,4′-diphenylmethanetetraisocyanate; multimers such as dimers and trimers of the isocyanate compounds, alcohols, Examples thereof include, but are not limited to, blocked isocyanates and bisurethane compounds masked with phenol. Two or more of these isocyanate compounds may be used in combination.

  Among the above isocyanate compounds, since heat resistance tends to be improved, a bifunctional or trifunctional isocyanate compound is preferable, a bifunctional isocyanate compound is more preferable, and isophorone, benzene, toluene, diphenylmethane, naphthalene, norbornene poly is more preferable. It is a bifunctional isocyanate compound having a skeleton selected from methylene polyphenylene polyphenyl and hexamethylene. When the number of functional groups of the isocyanate compound is too large, the storage stability of the epoxy resin composition tends to decrease, and when it is too small, the heat resistance of the cured product of the epoxy resin composition tends to decrease.

  In addition, various epoxy resins can be used as the epoxy resin as a raw material for the component (A). In order to efficiently incorporate the oxazolidone ring structure into the skeleton of the epoxy resin, epoxy groups are present at both ends of the molecule. An epoxy resin having is preferred. Specific examples of the epoxy resin used as a raw material for the component (A) include, for example, bisphenol A, bisphenol F, bisphenol AD, bisphenol S, tetramethylbisphenol A, tetramethylbisphenol F, tetramethylbisphenol AD, tetramethylbisphenol S, Epoxy resins derived from dihydric phenols such as tetrabromobisphenol A; 1,1,1-tris (4-hydroxyphenyl) methane, 1,1,1- (4-hydroxyphenyl) ethane, 4,4- [1 -Epoxy resins derived from tris (glycidyloxyphenyl) alkanes such as [4- [1- (4-hydroxyphenyl) -1-methylethyl] phenyl] ethylidene] bisphenol; phenol novolac, cresol novolac, bisphenol A Rack and epoxy resins derived from novolaks, and the like, but not particularly limited thereto. As the epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, biphenyl type epoxy resin and the like are particularly preferable because the viscosity of the component (A) is not excessively increased.

  As the isocyanate compound, a bifunctional isocyanate having a toluene skeleton such as tolylene diisocyanate (for example, 1-methylbenzene-2,4-diisocyanate, 1-methylbenzene-2,5-diisocyanate, 1-methylbenzene-2,6 -An addition reaction product obtained by mixing and reacting one molecule of diisocyanate, 1-methylbenzene-3,5-diisocyanate) and two molecules of bisphenol A diglycidyl ether as an epoxy resin is the workability of the prepreg at room temperature. It is particularly preferable for improving the heat resistance of the cured product of the epoxy resin composition.

  As commercially available epoxy resins having an oxazolidone ring structure (component (A)), AER4152, AER4151, LSA3301, LSA2102 (all trade names, manufactured by Asahi Kasei E-Materials Co., Ltd.) and ACR1348 (trade names, stocks) Company ADE KA), DER852, DER858 (trade name, manufactured by DOW), TSR-400 (trade name, manufactured by DIC), and the like, all of which are preferably used in the present invention, but AER4152 and TSR-400. Is particularly preferred. As said component (A), you may use together 2 or more types of above epoxy resins.

  It is preferable that content of a component (A) is 5 mass parts or more and 95 mass parts or less in 100 mass parts of all the epoxy resins contained in the epoxy resin composition of this invention. If content of a component (A) is 5 parts or more, it exists in the tendency which can obtain the resin cured material excellent in heat resistance, the adhesiveness to carbon fiber, and a mechanical physical property. More preferably, it is 10 mass parts or more, More preferably, it is 15 mass parts or more. On the other hand, if the content of the component (A) is 95 parts by mass or less, it is possible to obtain a prepreg excellent in tack and drapability and to obtain a cured resin product having high fracture toughness and no voids. is there. More preferably, it is 90 mass parts or less, More preferably, it is 85 mass parts or less. As for content of a component (A), it is more preferable that it is the range of 10-90 mass parts, and it is especially preferable that it is the range of 15-85 mass parts.

<Component (B)>
Component (B) is meta-type triglycidylaminophenol, and halogens, alkyl-substituted products, hydrogenated products, and the like can also be used. Component (B) mainly contributes to improving the strength, elastic modulus and heat resistance of the resin cured product of the present resin composition and improving adhesion to reinforcing fibers.

It is preferable that this resin composition contains 5 mass parts or more and 95 mass parts or less in 100 mass parts of all the epoxy resins contained in this resin composition.
The lower limit of the content of component (B) is more preferably 10 parts by mass or more, and still more preferably 15 parts by mass or more. Moreover, the upper limit of content of a component (B) becomes like this. More preferably, it is 90 mass parts or less, More preferably, it is 85 mass parts or less.
If the content of the component (B) in the resin composition is 5 parts by mass or more, a cured resin product having excellent strength, elastic modulus, and heat resistance and a resin composition having excellent adhesion to reinforcing fibers are obtained. Tend to be able to. On the other hand, if content of a component (B) is 95 mass parts or less, while it can obtain the resin cured material excellent in toughness, it exists in the tendency which can obtain the prepreg which has moderate tack.

A commercial item may be used for a component (B).
The meta-type triglycidylaminophenol (component (B)) available as a commercial product is not particularly limited, but MY0600 (epoxy equivalent 106 g / eq), MY0610 (epoxy equivalent 99 g / eq) (above, Huntsman Japan Co., Ltd.) Company-made).

<Ingredient (C)>
Component (C) is a curing agent. It does not specifically limit as a hardening | curing agent used as a component (C). As the component (C), dicyandiamide, ureas, imidazoles, aromatic amines, other amine-based curing agents, acid anhydrides, boron chloride amine complexes, and the like can be used. Particularly, dicyandiimide, ureas, imidazoles. It is preferable to use at least one curing agent selected from aromatic amines.

  Since dicyandiamide has a high melting point and can suppress compatibility with an epoxy resin in a low temperature region, it is preferable to use it as a curing agent (C) because a curable resin composition having an excellent pot life tends to be obtained. Further, it is preferable that the curable resin composition contains dicyandiamide as the curing agent (C) because the mechanical properties of the resin cured product tend to be improved.

  The content of dicyandiamide in the curable resin composition of the present invention is such that the number of moles of active hydrogen of dicyandiamide is 0.4 to the total number of epoxy groups of the epoxy resin contained in the curable resin composition. The amount is preferably set to 1 time. By setting the ratio to 0.4 times or more, a cured product having good heat resistance and good mechanical properties (that is, having high strength and elastic modulus) tends to be obtained. Moreover, by setting it as 1 times or less, it has the advantage that there exists a tendency for the hardened | cured material with favorable mechanical physical property (namely, excellent plastic deformation capability and impact resistance) to be obtained. Furthermore, by making the number of moles of active hydrogen of this dicyandiamide 0.5 to 0.8 times, the heat resistance of the resin cured product tends to be more excellent, which is more preferable.

  Examples of commercially available dicyandiamide include, but are not limited to, DICY7, DICY15 (manufactured by Mitsubishi Chemical Co., Ltd.), DICYANEX 1400F (manufactured by Air Products), and the like.

  The ureas used as the component (C) have a dimethylureido group in the molecule, and are heated at a high temperature to produce an isocyanate group and dimethylamine, which are the epoxy groups of the component (A) and the component (B). In addition, there is no particular limitation as long as it activates the epoxy resin used in combination, for example, aromatic dimethylurea in which a dimethylureido group is bonded to an aromatic ring, and aliphatic dimethylurea in which a dimethylureido group is bonded to an aliphatic compound Etc. Among these, aromatic dimethylurea is preferable in that the curing rate is high and the heat resistance and bending strength of the cured product tend to be high.

  As the aromatic dimethylurea, for example, phenyldimethylurea, methylenebis (phenyldimethylurea), tolylenebis (dimethylurea) and the like are preferably used. Specific examples include 4,4′-methylenebis (phenyldimethylurea) (MBPDMU), 3-phenyl-1,1-dimethylurea (PDMU), 3- (3,4-dichlorophenyl) -1,1-dimethylurea. (DCMU), 3- (3-chloro-4-methylphenyl) -1,1-dimethylurea, 2,4-bis (3,3-dimethylureido) toluene (TBDMU), m-xylylene diisocyanate and dimethylamine And dimethylurea obtained from the above. Among these, DCMU, MBPDMU, TBDMU, and PDMU are more preferable in terms of curing acceleration ability and imparting heat resistance to the cured resin. These may be used individually by 1 type and may be used in combination of 2 or more type.

  Examples of the aliphatic dimethylurea include dimethylurea obtained from isophorone diisocyanate and dimethylamine, and dimethylurea obtained from hexamethylene diisocyanate and dimethylamine. As ureas, commercially available products may be used.

As a commercial product of DCMU, for example, DCMU-99 (manufactured by Hodogaya Chemical Co., Ltd.) and the like can be mentioned, but not limited thereto.
Examples of commercially available products of MBPDMU include Technicure MDU-11 (above, manufactured by A & C Catalysts); Omicure 52 (above, manufactured by PTI Japan Ltd.), and the like. It is not something.
Examples of commercially available products of PDMU include, but are not limited to, Omicure 94 (manufactured by PTI Japan Ltd.).
Examples of commercially available products of TBDMU include Omicure 24 (above, manufactured by PTI Japan Ltd.), U-CAT 3512T (manufactured by Sun Apro Co., Ltd.), and the like. is not.
Examples of commercially available aliphatic dimethylurea include, but are not limited to, U-CAT 3513N (manufactured by San Apro Co., Ltd.).

  1-15 mass parts is preferable with respect to 100 mass parts of all the epoxy resins contained in the curable resin composition of this invention, and, as for content of urea, 2-10 mass parts is more preferable. When the urea content is 1 part by mass or more, the epoxy resin contained in the epoxy resin composition is sufficiently cured and cured to tend to increase mechanical properties and heat resistance. On the other hand, if the urea content is 15 parts by mass or less, the toughness of the cured resin product tends to be kept high.

  The imidazoles used as the component (C) may be imidazoles, and imidazole adducts, clathrate imidazoles, microcapsule imidazoles, imidazole compounds coordinated with stabilizers, and the like can also be used. These have nitrogen atoms with unshared electron pairs in their structure, which activates the epoxy groups of component (A) and component (B), and also activates other epoxy resins used in combination. And can promote curing and curing.

  Specific examples of imidazole include 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-phenylimidazole, 2-phenyl-4. -Methylimidazole, 1-benzyl-2-phenylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2- Undecylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazolium trimellitate, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2- Feni Imidazolium trimellitate, 2,4-diamino-6- (2′-methylimidazolyl- (1 ′))-ethyl-s-triazine, 2,4-diamino-6- (2′-undecylimidazolyl- ( 1 ′))-ethyl-s-triazine, 2,4-diamino-6- (2′-ethyl-4-methylimidazolyl- (1 ′))-ethyl-s-triazine, 2,4-diamino-6 (2′-methylimidazolyl- (1 ′))-ethyl-s-triazine / isocyanuric acid adduct, 2-phenylimidazole / isocyanuric acid adduct, 2-methylimidazole / isocyanuric acid adduct, 1-cyanoethyl-2- Phenyl-4,5-di (2-cyanoethoxy) methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl Such as-5-hydroxymethyl imidazole, and the like, but not limited thereto.

  Adduct treatment, inclusion treatment with different molecules, microcapsule treatment, or imidazole coordinated with a stabilizer is a modification of the imidazole. These are cured by adduct treatment with imidazole, inclusion treatment with different molecules, microcapsule treatment, or by degrading the activity by coordinating a stabilizer, while exhibiting excellent pot life in a low temperature region, and curing and hardening acceleration High ability.

  Moreover, you may use a commercial item as imidazoles. Examples of commercially available imidazoles include 2E4MZ, 2P4MZ, 2PZ-CN, C11Z-CNS, C11Z-A, 2MZA-PW, 2MA-OK, 2P4MHZ-PW, 2PHZ-PW (manufactured by Shikoku Kasei Kogyo Co., Ltd.). However, it is not limited to these.

  Examples of commercially available imidazole adducts include PN-50, PN-50J, PN-40, PN-40J, PN-31, and PN-23, which have a structure in which an imidazole compound is ring-opened and added to an epoxy group of an epoxy resin. , PN-H (manufactured by Ajinomoto Fine Techno Co., Ltd.) and the like, but are not limited thereto.

  Examples of the commercially available inclusion imidazole include TIC-188, KM-188, HIPA-2P4MHZ, NIPA-2P4MHZ, TEP-2E4MZ, HIPA-2E4MZ, NIPA-2E4MZ (manufactured by Nippon Soda Co., Ltd.) and the like. However, it is not limited to these.

  Examples of commercially available microcapsule type imidazole include NOVACURE HX3721, HX3722, HX3742, and HX3748 (above, manufactured by Asahi Kasei E-Materials Co., Ltd.); LC-80 (above, manufactured by A & C Catalysts), and the like. It is not limited.

  Moreover, the imidazole compound coordinated with the stabilizer is, for example, cure duct P-0505 (bisphenol A diglycidyl ether / 2-ethyl-4-methylimidazole adduct) which is an imidazole adduct manufactured by Shikoku Kasei Kogyo Co., Ltd. It can be prepared by combining L-07N (epoxy-phenol-borate ester compound) which is a stabilizer manufactured by Shikoku Kasei Kogyo Co., Ltd. The same effect can be obtained by using imidazole compounds such as various imidazoles and imidazole adducts mentioned above instead of the cure duct P-0505. As the imidazole compound before the stabilizer is coordinated, those having low solubility in an epoxy resin are preferably used, and in this respect, cure duct P-0505 is preferred.

  1-15 mass parts is preferable with respect to 100 mass parts of all the epoxy resins contained in curable resin composition of this invention, and, as for content of imidazoles, 2-10 mass parts is more preferable. If content of imidazole is 1 mass part or more, it exists in the tendency for the hardening of a epoxy resin contained in an epoxy resin composition, hardening acceleration | stimulation effect | action, and heat resistance to fully be acquired. On the other hand, if the content of imidazoles is 15 parts by mass or less, a cured resin having excellent mechanical properties tends to be obtained.

  Examples of aromatic amines used as the component (C) include 3,3′-diisopropyl-4,4′-diaminodiphenylmethane, 3,3′-di-t-butyl-4,4′-diaminodiphenylmethane, 3,3′-diethyl-5,5′-dimethyl-4,4′-diaminodiphenylmethane, 3,3′-diisopropyl-5,5′-dimethyl-4,4′-diaminodiphenylmethane, 3,3′-di -T-butyl-5,5'-dimethyl-4,4'-diaminodiphenylmethane, 3,3 ', 5,5'-tetraethyl-4,4'-diaminodiphenylmethane, 3,3'-diisopropyl-5,5 '-Diethyl-4,4'-diaminodiphenylmethane, 3,3'-di-t-butyl-5,5'-diethyl-4,4'-diaminodiphenylmethane, 3,3', , 5′-tetraisopropyl-4,4′-diaminodiphenylmethane, 3,3′-di-t-butyl-5,5′-diisopropyl-4,4′-diaminodiphenylmethane, 3,3 ′, 5,5 ′ -Tetra-t-butyl-4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, m-phenylenediamine, m-xylylene diene Examples include, but are not limited to, amine and diethyltoluenediamine. Among these, it is preferable to use 4,4′-diaminodiphenyl sulfone and 3,3′-diaminodiphenyl sulfone, which are excellent in heat resistance and elastic modulus, and are capable of obtaining a cured product in which the linear expansion coefficient and the decrease in heat resistance due to moisture absorption are small. . 4,4'-diaminodiphenylsulfone is also preferable in that the tack life of the prepreg can be maintained for a long period. Although 3,3′-diaminodiphenylsulfone is inferior to 4,4′-diaminodiphenylsulfone in the tack life of the prepreg and the heat resistance of the cured product, it is preferable because the elastic modulus and toughness of the cured product can be increased. . Further, it is preferable to add 4,4'-diaminodiphenylsulfone and 3,3'-diaminodiphenylsulfone at the same time because the heat resistance and elastic modulus of the cured product can be easily adjusted. These aromatic amines may be used singly or may be appropriately mixed and used.

  As for the compounding amount of the aromatic amines, particularly in diaminodiphenylsulfone, the number of active hydrogen equivalents of amino groups is 0.5 to 1 of the number of epoxy equivalents of all epoxy resins contained in the curable resin composition of the present invention. It is preferably 5 times, more preferably 0.6 to 1.4 times. By setting the blending amount of these epoxy resin curing agents to 0.5 to 1.5 times, the elastic modulus, toughness and heat resistance of the cured resin product tend to be in a favorable range. Moreover, a commercial item may be used for aromatic amines.

  Commercially available products of 4,4′-diaminodiphenylsulfone include Seika Cure S (active hydrogen equivalent 62 g / eq, manufactured by Wakayama Seika Kogyo Co., Ltd.), Sumicure S (active hydrogen equivalent 62 g / eq, manufactured by Sumitomo Chemical Co., Ltd.) As a commercial product of 3,3′-diaminodiphenylsulfone, 3,3′-DAS (active hydrogen equivalent 62 g / eq, manufactured by Mitsui Chemicals Fine Co., Ltd.) and the like can be mentioned, but are not limited thereto.

  Other commercially available aromatic amines include MDA-220 (active hydrogen equivalent 50 g / eq, manufactured by Mitsui Chemicals), “jER Cure (registered trademark)” W (active hydrogen equivalent 45 g / eq, Japan Epoxy). Resin Co., Ltd.), Lonacure (registered trademark) M-DEA (active hydrogen equivalent 78 g / eq), “Lonzacure (registered trademark)” M-DIPA (active hydrogen equivalent 92 g / eq), “Lonacure (registered trademark)” Examples include, but are not limited to, M-MIPA (active hydrogen equivalent: 78 g / eq) and “Lonzacure (registered trademark)” DETDA 80 (active hydrogen equivalent: 45 g / eq) (hereinafter, manufactured by Lonza).

  Examples of other amine curing agents that can be used as the component (C) include metaphenylenediamine, diaminodiphenylmethane, metaxylenediamine, isophoronediamine, and triethylenetetramine.

  Examples of the acid anhydride that can be used as the component (C) include hydrogenated methyl nadic acid anhydride and methyl hexahydrophthalic acid anhydride.

<Component (D)>
The thermoplastic resin is used as a component (D) in the curable resin composition of the present invention as necessary for the purpose of controlling the resin flow during molding of the curable resin composition of the present invention and imparting toughness to the cured resin. Can be blended. That is, it is preferable that this resin composition further contains a thermoplastic resin as the component (D).

  This resin composition preferably contains 1 part by mass or more and 15 parts by mass or less, preferably 2 parts by mass or more and 10 parts by mass or less, of component (D) with respect to 100 parts by mass of the total epoxy resin contained in the resin composition. It is more preferable. If content of a component (D) is 1 mass part or more, since it exists in the tendency for the resin flow control and a physical-property improvement effect to be exhibited favorably, it is preferable. On the other hand, if the content of component (D) is 15 parts by mass or less, the viscosity of the curable resin composition, the heat resistance and mechanical properties of the resin cured product, and the prepreg tack and drape properties tend to be easily maintained. Therefore, it is preferable.

  Examples of the thermoplastic resin include polyamide, polyester, polycarbonate, polyether sulfone, polyphenylene ether, polyphenylene sulfide, polyether ether ketone, polyether ketone, polyimide, polytetrafluoroethylene, polyether, polyolefin, liquid crystal polymer, polyarylate, Examples include, but are not limited to, polysulfone, polyacrylonitrile styrene, polystyrene, polyacrylonitrile, polymethyl methacrylate, ABS, AES, ASA, polyvinyl chloride, polyvinyl formal resin, phenoxy resin, and block polymer.

  Among these, phenoxy resin, polyethersulfone, and polyvinyl formal resin are preferable because of excellent resin flow controllability. Further, phenoxy resin and polyethersulfone are preferable from the viewpoint of further improving the heat resistance and flame retardancy of the cured resin, and the polyvinyl formal resin is suitable for tacking the prepreg obtained without impairing the heat resistance of the cured product. The range can be easily controlled, and is preferable from the viewpoint of improving the adhesion between the reinforcing fiber and the epoxy resin composition. A block polymer is preferable because it improves toughness and impact resistance.

  These thermoplastic resins may be used individually by 1 type, and may be used in combination of 2 or more type.

  Examples of the phenoxy resin include, but are not limited to, YP-50, YP-50S, YP70, ZX-1356-2, FX-316 (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.).

  As polyvinyl formal resin, vinylec (registered trademark) K (average molecular weight: 59,000), vinylec L (average molecular weight: 66,000), vinylec H (average molecular weight: 73,000), vinylec E (average molecular weight: 126) , 000) (manufactured by JNC Corporation) and the like.

  In addition, when the resin cured product requires heat resistance exceeding 180 ° C., polyethersulfone or polyetherimide is preferably used. Specifically, as polyether sulfone, SUMIKAEXCEL (registered trademark) 3600P (average molecular weight: 16,400), SUMIKAEXCEL 5003P (average molecular weight: 30,000), SUMIKAEXCEL 5200P (average molecular weight: 35,000), SUMIKAEXCEL 7600P (average molecular weight: 45,300) (manufactured by Sumitomo Chemical Co., Ltd.) and the like. Examples of the polyetherimide include ULTEM 1000 (average molecular weight: 32,000), ULTEM 1010 (average molecular weight: 32,000), ULTEM 1040 (average molecular weight: 20,000) (above, manufactured by SABIC Innovative Plastics Co., Ltd.) and the like. However, it is not limited to these.

  As block polymers, Nanostrength M52, Nanostrength M52N, Nanostrength M22, Nanostrength M22N, Nanostrength 123, Nanostrength 250, Nanostrength 012, Nanostrength 012, Nanostrength 012 , TPAE-23, TPAE-31, TPAE-38, TPAE-63, TPAE-100, PA-260 (manufactured by T & K TOKA), and the like, but are not limited thereto.

<Ingredient (E)>
The present resin composition, as component (E), improves workability by adjusting the viscoelasticity of the resin composition when it is uncured, and improves the strength, elastic modulus, toughness, and heat resistance of the cured resin. The epoxy resin described below may be included.

  Although it does not restrict | limit especially as a component (E), A bifunctional or more epoxy resin is used preferably. For example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol E type epoxy resin, bisphenol Z type epoxy resin, bisphenol AD type epoxy resin and other bisphenol type epoxy resins, biphenyl type epoxy resin, naphthalene Type epoxy resin, dicyclopentadiene type epoxy resin, phenol novolac type epoxy resin, cresol novolak type epoxy resin, trisphenolmethane type epoxy resin, glycidylamine type epoxy resin such as tetraglycidyldiaminodiphenylmethane, triglycidylaminophenol; Other glycidyl ether type epoxies such as glycidyloxyphenyl) ethane and tris (glycidyloxy) methane Resin, and their modified epoxy resins, phenol aralkyl type epoxy resins.

  Tri- or higher functional epoxy resins provide better strength, elastic modulus, and heat resistance, so para-type triglycidylaminophenol type epoxy resins, tetraglycidyldiaminodiphenylmethane type epoxy resins, phenol novolac type epoxy resins, cresols A novolac type epoxy resin is preferably used.

  Examples of commercially available epoxy resins used as the component (E) include jER1001, jER1002, jER1055, jER1004, jER1007, jER1009, jER4004P, jER4005P, jER4007P, jER4010P, jER1032H60, jER152, YER-4000, YX-7700, and YX-7700. , JER630, jER604 (above, manufactured by Mitsubishi Chemical Corporation); GAN, GOT, NC-2000, NC-3000 (above, manufactured by Nippon Kayaku Co., Ltd.); YDPN-638, TX-0911, YH-434, YH- 434L (above, manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), Epon165 (above, made by Momentive Specialty Chemicals); EPICLON2050, EPICLON3050, EP CLON 4050, EPICLON 7050, EPICLON HM-091, EPICLON HM-101, HP-4032, HP-4700, HP-7200 (manufactured by DIC Corporation), Sumiepoxy ELM434 (manufactured by Sumitomo Chemical Co., Ltd.), TEPIC-G, TEPIC-S, TEPIC-SP, TEPIC-SS, TEPIC-PAS B26L, TEPIC-PAS B22, TEPIC-VL, TEPIC-UC (manufactured by Nissan Chemical Industries, Ltd.), TETRAD-X, TETRAD-C (above, Mitsubishi Gas Chemical Co., Ltd.), MY0500, MY0510, MY0720, MY0721, MY0725, ECN-1299 (manufactured by Huntsman Japan Co., Ltd.), and the like, but are not limited thereto.

  As for content of a component (E), 5-35 mass parts is preferable in 100 mass parts of all the epoxy resins contained in the curable resin composition of this invention, and 10-30 mass parts is more preferable. If content of a component (E) is 5 mass parts or more, since it exists in the tendency for the physical-property improvement effect to be exhibited favorable, it is preferable. On the other hand, if the content of the component (E) is 35 parts by mass or less, it is preferable because the characteristics of the curable resin composition of the present invention tend to be maintained well.

<Optional component>
The resin composition may contain various known additives as long as it does not impair the effects of the present invention, improving the storage stability of the composition, and discoloration or alteration of the cured product layer. In order to avoid this, an antioxidant or a light stabilizer can be added.

Specific examples of this include, for example, various commercially available Sumitomo Chemical Co., Ltd., Sumitizer BHT, Sumilizer S, Summarizer BP-76, Summarizer MDP-S, Summarizer GM, Summarizer BBM-S, Summarizer WX-R, and Summarizer. NW, Sumilyzer BP-179, Sumilyzer BP-101, Sumilyzer GA-80, Sumilyzer TNP, Sumilyzer TPP-R, Sumilyzer P-16; ADK STAB AO-20, ADK STAB AO-30, ADK STAB AO- 40, ADK STAB AO-50, ADK STAB AO-60 AO-70, ADK STAB AO-80, ADK STAB AO-330, ADK STAB PEP-4C, ADK STAB PEP-8, ADK STAB PEP-24G,
ADK STAB PEP-36, ADK STAB HP-10, ADK STAB 2112, ADK STAB 260, ADK STAB 522A, ADK STAB 329K, ADK STAB 1500, ADK STAB C, ADK STAB 135A; ADK STAB 3010; , Tinuvin 622, Tinuvin 111, Tinuvin 123, Tinuvin 292; Funkrill FA-711M, FA-712HM manufactured by Hitachi Chemical Co., Ltd., and the like.

  The addition amount of these antioxidants and light stabilizers is not particularly limited, but may be added in the range of 0.001 to 5 parts by mass with respect to the total number of all epoxy resins and all (meth) acrylate compounds, respectively. Preferably, the range of 0.01-3 mass parts is more preferable.

  Other additives include elastomers, thermoplastic elastomers, flame retardants (eg, phosphorus-containing epoxy resins, red phosphorus, phosphazene compounds, phosphates, phosphate esters, etc.), silicone oils, wetting and dispersing agents, antifoaming agents, Foaming agents, natural waxes, synthetic waxes, metal salts of linear fatty acids, acid amides, esters, paraffins, release agents, crystalline silica, fused silica, calcium silicate, alumina, calcium carbonate, talc, Powders such as barium sulfate, metal oxides, metal hydroxides, inorganic fillers such as glass fibers, carbon nanotubes, fullerenes, organic fillers such as carbon fibers and cellulose nanofibers, inorganic fillers that have been surface-organized, etc., carbon black And known additives such as colorants such as Bengala, silane coupling agents, and conductive materials. Furthermore, if necessary, a slip agent, a leveling agent, a polymerization inhibitor such as hydroquinone monomethyl ether, an ultraviolet absorber, and the like can be blended. These may be used alone or in combination of two or more.

<Viscosity of curable resin composition>
The viscosity of the resin composition at 30 ° C. is preferably 100 Pa · s or more, more preferably 300 Pa · s or more, and 500 Pa · s or more, from the viewpoint of adjusting the tack of the obtained prepreg surface and workability. Is more preferable. The upper limit of the viscosity is preferably 1,000,000 Pa · s or less, more preferably 900,000 Pa · s or less, and further preferably 800,000 Pa · s or less.

  The viscosity of the resin composition at 60 ° C. is preferably 10 Pa · s or more, more preferably 20 Pa · s or more, and further preferably 30 Pa · s or more, from the viewpoint of the quality of the prepreg obtained. Further, from the viewpoint of impregnation into the reinforcing fiber aggregate and molding processability of the prepreg, 1,000 Pa · s or less is preferable, 900 Pa · s or less is more preferable, and 800 Pa · s or less is more preferable.

  The minimum viscosity of the present resin composition is preferably 0.05 Pa · s, and the lower limit of the minimum viscosity is 0.05 Pa · s, from the viewpoint of flow control of the resin during molding (suppression of disturbance of reinforcing fibers). s is more preferable, and 0.1 Pa · s is even more preferable. The upper limit of the minimum viscosity is preferably 50 Pa · s, more preferably 40 Pa · s, and further preferably 30 Pa · s.

The minimum viscosity is defined as the point at which the viscosity becomes the lowest in the viscosity curve obtained when the viscosity of the curable resin composition is measured in the temperature rising mode.
The viscosity of the curable resin composition is, for example, a plate gap of 500 μm, a temperature increase rate of 2 ° C./min using a 25 mmφ parallel plate with a rotational viscometer (TA Instruments, product name “AR-G2”). It is calculated | required by measuring with temperature rising, angular velocity 10rad / sec, and stress 300Pa.

<Physical properties of resin plate>
In the curable resin composition of the present invention, the resin cured product preferably has a flexural modulus of 3.5 to 5 GPa, and the resin cured product has a breaking elongation of 7 to 15%. Preferably there is. More preferably, the flexural modulus is 3.7 to 4.5 GPa and the elongation at break is 8 to 14%. When the elastic modulus is less than 3.5 GPa or when the elongation at break exceeds 15%, the static strength in the case of a fiber-reinforced composite material may be insufficient. If the flexural modulus exceeds 5 GPa or the elongation at break is less than 7%, the toughness of the fiber reinforced composite material tends to be insufficient, and the impact resistance of the fiber reinforced composite material may be insufficient. is there.

<Method and application of curable resin composition>
Although the curable resin composition of this invention is not limited to this, For example, it is obtained by mixing each component mentioned above. Examples of the method for mixing each component include a method using a mixer such as a three-roll mill, a planetary mixer, a kneader, a homogenizer, and a homodisper.

  The resin composition can be used, for example, in the production of a prepreg by impregnating a reinforcing fiber assembly as described later. In addition, a film of the resin composition can be obtained by applying the resin composition to a release paper or the like and curing it.

<Effect>
Since the present resin composition described above includes the component (A), the component (B), the component (C), and the component (D), other epoxy resins and other additives as necessary, the present resin composition. Can be used to obtain a fiber-reinforced composite material having excellent mechanical properties.

〔Molding〕
The molded article of the present invention comprises a cured product of the above-described curable resin composition of the present invention.
Examples of molding methods for the curable resin composition include injection molding methods (including insert molding of films, glass plates, etc.), injection compression molding methods, extrusion methods, blow molding methods, vacuum molding methods, pressure molding methods, and calendar moldings. Method, inflation molding method and the like. Among these, the injection molding method and the injection compression molding method are preferable because they are excellent in mass productivity and can obtain a molded product with high dimensional accuracy, but are not limited thereto.

  Since the molded product of the present invention is formed by molding the curable resin composition of the present invention, it is excellent in mechanical properties. For example, it is applied to a vehicle product, a casing of a mobile device, a furniture product, a building material product, etc. it can.

<Film made of curable resin composition>
One embodiment of the molded article of the present invention is the use as a film. This film is useful as an intermediate material for producing a prepreg, and also as a surface protective film or an adhesive film by being cured after being attached to a substrate.

  Moreover, although the usage method is not limited to this, It is preferable to apply | coat the curable resin composition of this invention to the surface of base materials, such as a release paper. The obtained coating layer may be used as a film by being stuck to another substrate while being uncured and cured, or may be used as a film by curing the coating layer itself.

[Prepreg]
The prepreg of the present invention is obtained by impregnating a reinforcing fiber assembly with the above-described curable resin composition of the present invention. The method of impregnating the reinforcing fiber assembly with the resin composition may be a known method, for example, a wet method in which the resin composition is dissolved in a solvent such as methyl ethyl ketone or methanol to reduce the viscosity and then impregnated. Examples thereof include, but are not limited to, a hot melt method (dry method) that is impregnated after the viscosity is reduced by heating.

  The wet method is a method in which a reinforcing fiber is immersed in a solution of a curable resin composition, then pulled up, and the solvent is evaporated using an oven or the like. On the other hand, in the hot melt method, a method of directly impregnating reinforcing fibers with a curable resin composition whose viscosity has been reduced by heating and a film in which a curable resin composition is once coated on release paper or the like are prepared. Then, there is a method of impregnating the reinforcing fibers with resin by overlapping the film from both sides or one side of the reinforcing fibers and heating and pressing.

  The hot melt method is preferable because there is substantially no solvent remaining in the prepreg.

  The content of the curable resin composition of the prepreg of the present invention (hereinafter referred to as “resin content”) is preferably 15 to 50% by mass when the total mass of the prepreg of the present invention is 100%. It is more preferably 20 to 45% by mass, and further preferably 25 to 40% by mass. If the resin content is 15% by mass or more, sufficient adhesion between the reinforcing fiber assembly and the curable resin composition can be secured, and if it is 50% by mass or less, the mechanical properties can be kept high.

  The reinforcing fiber constituting the reinforcing fiber assembly is not particularly limited, and may be appropriately selected from known reinforcing fibers constituting the fiber-reinforced composite material according to the use. Specific examples include various inorganic fibers or organic fibers such as carbon fiber, aramid fiber, nylon fiber, high-strength polyester fiber, glass fiber, boron fiber, alumina fiber, and silicon nitride fiber. Among these, carbon fiber, aramid fiber, glass fiber, boron fiber, alumina fiber, and silicon nitride fiber are preferable from the viewpoint of specific strength and specific elasticity, and carbon fiber is particularly preferable from the viewpoint of mechanical properties and weight reduction. When carbon fiber is used as the reinforcing fiber, surface treatment with metal may be performed. These reinforcing fibers may be used alone or in combination of two or more.

  From the viewpoint of the rigidity of the fiber-reinforced composite material obtained by curing the prepreg of the present invention, the strand tensile strength of the carbon fiber is preferably 1 to 9 GPa, more preferably 1.5 to 9 GPa, and the strand tensile elastic modulus of the carbon fiber. Is preferably 150 to 1,000 GPa, more preferably 200 to 1,000 GPa. The strand tensile strength and strand tensile elastic modulus of the carbon fiber are values measured in accordance with JIS R 7601: 1986.

  The form of the reinforcing fiber aggregate is not particularly limited, and a form used as a base material for a normal prepreg can be adopted. For example, the reinforcing fiber may be aligned in one direction. Or a non-crimp fabric.

  Since the prepreg of the present invention is formed by impregnating the reinforcing fiber assembly with the epoxy resin composition of the present invention, it can be used as a raw material for fiber reinforced plastic having excellent mechanical properties.

[Fiber reinforced plastic]
The fiber reinforced plastic of the present invention comprises a cured product of the above-described curable resin composition of the present invention and reinforced fibers. The fiber reinforced plastic of the present invention is not limited to this, but for example, it is obtained by laminating the above-described prepreg of the present invention and then molding it by a method of heat curing a curable resin while applying pressure to the laminate. It is done.
Since the fiber reinforced plastic of the present invention is excellent in mechanical properties, flame retardancy, heat resistance, electromagnetic wave shielding properties, and the like, it is preferable that carbon fibers are included as reinforcing fibers.

  The fiber-reinforced plastic molding method of the present invention includes a press molding method, an autoclave molding method, a bagging molding method, a wrapping tape method, an internal pressure molding method, a sheet wrap molding method, and a curable resin composition for filaments and preforms of reinforcing fibers. Examples include RTM (Resin Transfer Molding), VaRTM (Vacuum Assisted Resin Transfer Molding), filament winding, RFI (Resin Film Infusion), etc. The molding method is not limited.

  The wrapping tape method is a method in which a prepreg is wound around a mandrel or the like and a tubular body made of fiber reinforced plastic is formed, and is preferably used when producing a rod-like body such as a golf shaft or a fishing rod. More specifically, a prepreg is wound around a mandrel, a wrapping tape made of a thermoplastic film is wound around the outside of the prepreg for fixing and applying pressure, and the resin is heated and cured in an oven, and then a cored bar. This is a method for extracting a fiber and obtaining a fiber-reinforced plastic tubular body.

  Also, the internal pressure molding method is to set a preform in which a prepreg is wound on an internal pressure applying body such as a tube made of a thermoplastic resin in a mold, and then introduce a high pressure gas into the internal pressure applying body to apply pressure. At the same time, the mold is heated and molded. This method is preferably used when molding a complicated shape such as a golf shaft, a bat, a racket such as tennis or badminton.

  The fiber reinforced plastic using the cured product of the curable resin composition of the present invention as a matrix resin is suitably used for sports applications, general industrial applications, and aerospace applications. More specifically, in sports applications, it is suitably used for golf shafts, fishing rods, tennis and badminton racket applications, hockey stick applications, and ski pole applications. Furthermore, in general industrial applications, structural materials for moving bodies such as automobiles, ships, and railway vehicles, drive shafts, leaf springs, windmill blades, pressure vessels, flywheels, paper rollers, roofing materials, cables, and repair reinforcement materials, etc. Is preferably used.

[Fiber-reinforced plastic tubular body]
The fiber-reinforced plastic tubular body is the fiber-reinforced plastic of the present invention which is tubular. That is, it is a tubular fiber reinforced plastic obtained by laminating, curing and molding the above-described prepreg of the present invention by a known molding method such as a wrapping tape method. Since the fiber-reinforced plastic tubular body of the present invention has excellent breaking strength and elastic modulus, it can be suitably used for golf shafts, fishing rods and the like.

  The tubular body made of fiber reinforced plastic can be obtained from a unidirectional prepreg obtained by impregnating a reinforcing fiber aligned in one direction with the resin composition of the present invention. For example, 2 ply of prepreg is laminated so that the fiber direction of the unidirectional prepreg is −45 ° and + 45 ° with respect to the cylindrical axis direction, and the unidirectional prepreg is further parallel to the cylindrical axis direction. Thus, 1 ply of prepreg can be laminated to produce a composite material tubular body having an inner diameter of 6 mm. Here, the mandrel is a round bar made of stainless steel.

Specifically, for example, it can be produced by the method described in the following (I) to (V), but is not limited thereto.
(I) Two rectangular prepregs having a length of 200 mm and a width of 72 mm are cut out from the produced unidirectional prepreg so that the fiber axis direction is 45 degrees with respect to the long side direction. The two prepreg fibers are laminated so that the directions of the fibers intersect each other and are shifted by 9 mm in the short side direction.
(II) The bonded prepreg is wound on the mandrel subjected to the mold release treatment so that the long side and the mandrel axial direction are the same direction.
(III) On top of that, a rectangular prepreg 200 mm long × 153 mm wide cut from the produced unidirectional prepreg so that the long side direction is the fiber direction, the fiber direction is the same as the mandrel axis direction. Turn around the mandrel so that
(IV) Further, a heat-resistant film tape is wrapped as a wrapping tape to cover the wound product, and is heated and molded at 130 ° C. for 90 minutes in a curing furnace. The width of the wrapping tape is 15 mm, the tension is 3 N, the winding pitch (deviation amount at the time of winding) is 1 mm, and this is wrapped so as to have the same thickness as the laminated body.
(V) Thereafter, the mandrel is extracted and the wrapping tape is removed to obtain a fiber-reinforced plastic tubular body.

Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited thereto. The raw materials used in the examples and comparative examples are shown below.
The softening point and epoxy equivalent were measured under the following conditions.
1) Softening point: Measured according to JIS-K7234: 2008 (ring and ball method).
2) Epoxy equivalent: Measured according to JIS-K7236: 2001.

"material"
<Component (A)>
TSR-400: Oxazolidone type epoxy resin (epoxy equivalent 338 g / eq, manufactured by DIC Corporation, product name “TSR-400”).
<Component (B)>
MY0600: Meta-type triglycidylaminophenol (epoxy equivalent 105 g / eq, manufactured by Huntsman Japan KK, product name “MY0600”).
<Ingredient (C)>
1400F: Dicyandiamide (active hydrogen equivalent 21 g / eq, manufactured by Air Products, product name “DICYANEX 1400F”).
DCMU-99: 3- (3,4-dichlorophenyl) -1,1-dimethylurea (manufactured by Hodogaya Chemical Co., Ltd., product name “DCMU-99”).
<Component (D)>
Vinylec E: Polyvinyl formal resin (manufactured by JNC Corporation, product name “Vinylec E”).
YP70: Phenoxy resin (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., product name “YP70”).

<Ingredient (E)>
jER828: Liquid bisphenol F type epoxy resin (epoxy equivalent 189 g / eq, manufactured by Mitsubishi Chemical Corporation, product name “jER828”).
jER1002: Solid bisphenol A type epoxy resin (epoxy equivalent 650 g / eq, manufactured by Mitsubishi Chemical Corporation, product name “jER1002”).
jER1055: Solid bisphenol A type epoxy resin (epoxy equivalent 850 g / eq, manufactured by Mitsubishi Chemical Corporation, product name “jER1055”).
GAN: diglycidyl aniline (epoxy equivalent 125 g / eq, manufactured by Nippon Kayaku Co., Ltd., product name “GAN”).
jER630: para-type triglycidylaminophenol (epoxy equivalent 98 g / eq, manufactured by Mitsubishi Chemical Corporation, product name “jER630”).
<Carbon fiber>
HR: Product name “Pyrofil HR40” manufactured by Mitsubishi Chemical Corporation.

Example 1
TSR-400 as component (A), MY0600 as component (B), jER828 as component (E), 1400F and DCMU-99 as component (C), Vinylec E as component (D), and Thus, a curable resin composition was prepared.

  First, according to the composition described in Table 1, component (E) (liquid) and component (C) (solid) are weighed in a container so that the mass ratio of the solid component to the liquid component is 1: 1, and stirred. Mixed. This was further finely mixed with a three roll mill to obtain a master batch containing a curing agent.

  Subsequently, component (B) and component (D) in the composition shown in Table 1 were weighed into a flask, heated to 160 ° C. using an oil bath, and dissolved and mixed. Then, after cooling to about 120 ° C., the component (A) is added and dissolved and mixed, and then when cooled to about 65 ° C., the hardener-containing master batch is added and stirred to mix to obtain an uncured curable resin composition. Got.

"Production of resin plate"
An uncured curable resin composition is poured between two glass plates, molded into a plate shape, heated at 2 ° C./min, and kept at an oven atmosphere temperature of 135 ° C. for 90 minutes to be cured by heating. A resin plate having a thickness of 2 mm was produced.

"Preparation of prepreg"
The uncured curable resin composition was formed into a film using a comma coater (manufactured by Hirano Techseed Co., Ltd., “M-500”) to prepare a resin film having a resin basis weight of 16.7 g / m ² . This resin film is bonded to both surfaces of a carbon fiber sheet having a fiber basis weight of 100 g / m ² obtained by aligning carbon fibers, impregnated with a heating roll, and has a fiber basis weight of 133.4 g / m ² and a resin content of 25. A mass% uncured prepreg was obtained.

"Production of fiber-reinforced plastic plate"
The uncured prepreg having a resin content of 25% by mass obtained above was cut into 300 mm × 300 mm, and the fiber direction was [0 ° / 0 ° / 0 ° / 0 ° / 0 ° / 0 ° / 0 ° / 0. ° / 0 ° / 0 ° / 0 ° / 0 ° / 0 ° / 0 ° / 0 ° / 0 ° / 0 ° / 0 ° / 0 ° / 0 ° / 0 ° / 0 ° / 0 ° / 0 °] 24 sheets were stacked to obtain a laminate. The laminate was heated at 2 ° C./min under a pressure of 0.04 MPa in an autoclave, held at 80 ° C. for 60 minutes, then heated at 2 ° C./min under a pressure of 0.6 MPa, and held at 130 ° C. for 90 minutes. And cured by heating to obtain a 2.1 mm thick fiber reinforced plastic plate.

  About the produced resin board, prepreg, and fiber reinforced plastic, various measurements and evaluation were performed according to description of each following evaluation method. The results are shown in Table 1.

“Measurement of bending strength, flexural modulus, elongation at break (breaking strain) of resin plate”
The resin plate having a thickness of 2 mm obtained in the above-mentioned “Preparation of resin plate” was processed into a length of 60 mm × width of 8 mm to obtain a test piece. The test piece was universally equipped with a three-point bending jig (indenter R = 3.2 mm, support R = 3.2 mm, distance between supports (L) = 32 mm) in an environment of a temperature of 23 ° C. and a humidity of 50% RH. Using a testing machine (“INSTRON 5565” manufactured by INSTRON), the bending strength, bending elastic modulus, and elongation at break (breaking strain) of the resin plate were measured under conditions of a crosshead speed of 2 mm / min.

“Measurement of 90 ° bending strength, flexural modulus, elongation at break (break strain) of fiber reinforced plastic sheet”
The 2.1 mm thick fiber reinforced plastic plate obtained in the above-mentioned “Preparation of Fiber Reinforced Plastic Plate” was processed into a test piece by length 60 mm × width 12.7 mm. About this test piece, using a universal testing machine (“INSTRON 5565” manufactured by INSTRON) equipped with a three-point bending jig (indenter R = 5.0 mm, support R = 3.2 mm), the distance between supports (L ) And test piece thickness (d) ratio L / d = 16, crosshead speed (minute speed) = (L ² × 0.01) / (6 × d), The 90 ° bending strength, flexural modulus, and breaking elongation (breaking strain) were measured.

(Examples 2-3, Comparative Examples 1-3)
A curable resin composition was prepared in the same manner as in Example 1 except that the composition ratio was changed as shown in Table 1, and a resin plate, a prepreg, and a fiber reinforced plastic plate were prepared, and various measurements were performed. And evaluation. The evaluation results are shown in Table 1. In Comparative Example 2, the softening point of TSR-400 used as component (A) is 79 ° C., and if 100 parts by mass of epoxy resin is used, a curing agent master batch cannot be produced. JER828 liquid at room temperature was used.

  As shown in Table 1, each example was superior in strength and elastic modulus of the resin plate and the fiber reinforced plastic plate to Comparative Examples 1 to 4 in which the component (A) and the component (B) were not used in combination.

  By using the curable resin composition of the present invention, an excellent tubular fiber-reinforced plastic can be obtained. Therefore, according to the present invention, a wide range of fiber reinforced plastic molded articles having excellent mechanical properties, for example, molded articles for sports / leisure use such as shafts for golf clubs and industrial use such as aircraft can be provided.

Claims (9)

A curable resin composition comprising the following components (A), (B) and (C).
Component (A): Oxazolidone type epoxy resin Component (B): Meta type triglycidylaminophenol Component (C): Curing agent   The curable resin composition according to claim 1, comprising at least one selected from dicyandiamide, ureas, and imidazoles as the curing agent (C).   Furthermore, the curable resin composition of Claim 1 or 2 containing a thermoplastic resin as a component (D).   A film comprising the curable resin composition according to claim 1. A prepreg comprising reinforcing fibers and a matrix resin, wherein the matrix resin is a curable resin composition comprising the following components (A), (B) and (C).
Component (A): Oxazolidone type epoxy resin Component (B): Meta type triglycidylaminophenol Component (C): Curing agent   The prepreg according to claim 5, comprising at least one selected from dicyandiamide, ureas, and imidazoles as the curing agent (C).   Furthermore, the prepreg of Claim 5 or 6 containing a thermoplastic resin as a component (D).   A fiber reinforced plastic comprising a cured product of the curable resin composition according to claim 1 and reinforcing fibers.   The fiber-reinforced plastic according to claim 8, which has a tubular shape.