JP2014145018A - Epoxy resin composition, molding material and fiber-reinforced composite material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an epoxy resin composition that provides an epoxy resin cured product superior in heat resistance, elongation, and curability, and a molding material and a fiber-reinforced composite material using the same.SOLUTION: This invention provides an epoxy resin composition including the following [A]-[D]: [A] trifunctional or more binaphthalene type epoxy resin; [B] dicyandiamide or derivative thereof; [C] diaminodiphenyl sulfone or derivative thereof; and [D] urea compound.

Description

  The present invention relates to an epoxy resin composition that provides an epoxy resin cured product having excellent heat resistance, elongation, and curability, and a molding material and fiber-reinforced composite material using the same.

  Fiber reinforced composite materials using carbon fibers, aramid fibers, etc. as reinforcing fibers make use of their high specific strength and specific elastic modulus to make structural materials such as aircraft and automobiles, tennis rackets, golf shafts, fishing rods, bicycles, Widely used for sports such as housing, general industrial use. The fiber reinforced composite material can be produced by a method in which a plurality of prepregs, which are sheet-like molding materials in which reinforcing fibers are impregnated with an uncured matrix resin, are laminated and then heat-cured, or reinforcing fibers arranged in a mold. For example, a resin transfer molding method in which a liquid resin is poured and heated and cured is used. Among these production methods, the method using a prepreg has an advantage that it is easy to obtain a high-performance fiber-reinforced composite material because the orientation of the reinforcing fibers can be strictly controlled and the design freedom of the laminated structure is high. As the matrix resin used for the prepreg, a thermosetting resin is mainly used from the viewpoint of heat resistance and productivity, and an epoxy resin is preferably used from the viewpoint of mechanical properties such as adhesion to reinforcing fibers.

  In recent years, fiber reinforced composite materials have been required to be improved in various physical properties in order to meet the demands of golf shafts, fishing rods, bicycles, automobile members, industrial members, and the like that require further weight reduction. Further, in applications such as bicycle rims, automobile members, and industrial members, further improvement in heat resistance is required.

  As a method of improving the heat resistance of the fiber reinforced composite material, there is a method of applying a tetraglycidylamine type epoxy resin and dicyandiamide to a matrix resin. The epoxy resin composition prepared by this method is excellent in the heat resistance and curability of the cured resin, thus giving a fiber reinforced composite material having excellent heat resistance and curability, but the elongation of the cured resin is insufficient. Therefore, there is a problem that the tensile strength is insufficient (Patent Document 1).

  As a method for improving the heat resistance and tensile strength of the fiber reinforced composite material, there is a method in which an amine type epoxy resin, a bisphenol type epoxy resin, diaminodiphenyl sulfone, or dicyandiamide is applied as a matrix resin. The epoxy resin composition prepared by this method is excellent in elongation and curability, and thus provides a fiber-reinforced composite material having excellent tensile strength and curability, but does not satisfy the recently required heat resistance. (Patent Document 2).

  Furthermore, as a method for improving the heat resistance of the fiber reinforced composite material, there is a method using an epoxy resin having a rigid skeleton (Patent Document 3). In this method, a fiber-reinforced composite material having excellent heat resistance is obtained using an epoxy resin having a rigid skeleton such as a bifunctional naphthalene type epoxy resin. Since heat resistance and elongation were insufficient, heat resistance and tensile strength were not sufficient.

  Furthermore, as a method for improving the heat resistance of the fiber reinforced composite material, there is a method using a binaphthalene type epoxy resin (Patent Document 4). In this method, although a cured resin having heat resistance satisfying recent requirements can be obtained, the tensile strength of the obtained fiber-reinforced composite material is not sufficient because the elongation is not sufficient.

JP 2000-017090 A JP 2010-053278 A JP 2003-096158 A JP 2005-298815 A

  An object of the present invention is to provide an epoxy resin composition that gives an epoxy resin cured product having excellent heat resistance, elongation, and curability, and a molding material and a fiber-reinforced composite material using the same.

  As a result of intensive studies to solve the above problems, the present inventors have found that the above problems can be solved by combining a tri- or higher functional binaphthalene type epoxy resin with a specific curing agent and a curing accelerator. It came to complete. That is, this invention consists of the following structures.

(1) An epoxy resin composition comprising the following [A] to [D].
[A] Trifunctional or higher binaphthalene type epoxy resin [B] Dicyandiamide or a derivative thereof [C] Diaminodiphenylsulfone or a derivative thereof [D] A urea compound.

  (2) The epoxy resin composition according to the above (1), comprising 10 to 50 parts by mass of the constituent element [A] with respect to 100 parts by mass of all components of the epoxy resin.

(3) Constituent elements [B] and [C] are contained within the range satisfying the following conditions (I) and (II) with respect to 1 equivalent of the epoxy group of all epoxy resin components: Or the epoxy resin composition in any one of (2).
(I) The equivalent of active hydrogen group of component [B] is 0.3 to 0.8 equivalent (II) The equivalent of active hydrogen group of component [C] is 0.2 to 0.7 equivalent.

  (4) The epoxy resin composition according to any one of (1) to (3) above, containing 0.1 to 3 parts by mass of the constituent element [D] with respect to 100 parts by mass of all components of the epoxy resin.

  (5) The epoxy resin composition according to any one of (1) to (4), further including a biphenyl type epoxy resin.

  (6) The epoxy resin composition according to any one of (1) to (5), further including an aliphatic epoxy resin having more than two epoxy groups.

  (7) A molding material comprising the epoxy resin composition according to any one of (1) to (6) and a reinforcing fiber.

  (8) A fiber-reinforced composite material obtained by molding the molding material according to (7) above.

  According to the present invention, an epoxy resin composition that provides an epoxy resin excellent in heat resistance, elastic modulus, and elongation can be obtained. That is, the epoxy resin composition of the present invention can provide a fiber-reinforced composite material having excellent heat resistance and strength for bicycle rim materials, automotive members, and industrial members.

Hereinafter, the present invention will be described in more detail. The prepreg of the present invention is an epoxy resin composition containing the following components [A] to [D].
[A] Trifunctional or higher binaphthalene type epoxy resin [B] Dicyandiamide or a derivative thereof [C] Diaminodiphenylsulfone or a derivative thereof [D] A urea compound.

  The trifunctional or higher functional binaphthalene type epoxy resin of the component [A] is an element necessary for imparting excellent heat resistance to the cured resin, and is an epoxy resin represented by the following general formula (I).

(In the formula, X represents either an alkylene group having 1 to 8 carbon atoms or a group represented by the following general formula (II). R _{1 to} R ₅ are represented by the following general formula (III). Or a hydrogen atom, a halogen atom, a phenyl group, or an alkyl group having 1 to 4 carbon atoms, R _{1 to} R ₄ may be added to any ring of the naphthalene skeleton, and may be simultaneously added to both rings. R ₅ may be added to any position of the benzene skeleton, and among R _{1 to} R ₅ , an average of at least three groups represented by the following general formula (III) The other Rs may be the same or different from each other.

  The epoxy resin represented by the general formula (I) used in the present invention may be obtained by any production method, and can be obtained, for example, by reaction of hydroxynaphthalenes with epihalohydrin.

  Moreover, it is preferable that this structural element [A] contains 10-50 mass parts with respect to 100 mass parts of all the epoxy resins, More preferably, it is 15-30 mass parts. It is preferable for the component [A] to be 10 parts by mass or more because the heat resistance of the cured resin is excellent. On the other hand, it is preferable that the component [A] is 50 parts by mass or less because the elongation of the cured resin is excellent.

  As a commercial item of component [A], "Epiclon (trademark)" EXA-4701, HP-4700, HP-4710, EXA-4750 (above, DIC Corporation make) etc. are mentioned.

  In the epoxy resin composition of the present invention, an epoxy resin other than the constituent element [A] can be blended within a range not losing the effects of the present invention, and the preferred blending amount is 100 parts by mass of the total epoxy resin, It is 90 mass parts or less, More preferably, it is 70 mass parts or less. These may be added in combination of not only one type but also a plurality of types. Specifically, biphenyl type epoxy resin, aliphatic epoxy resin, bisphenol type epoxy resin, amine type epoxy resin, phenol novolac type epoxy resin, cresol novolac epoxy resin, phenol aralkyl type epoxy resin, biphenyl aralkyl type epoxy resin, naphthalene aralkyl Type epoxy resin, dicyclopentadiene type epoxy resin, urethane-modified epoxy resin, tetraphenylethane type epoxy resin, triphenylmethane type epoxy resin, fluorene type epoxy resin and the like.

  Among them, biphenyl type epoxy resins and aliphatic epoxy resins having more than two epoxy groups are preferable because they are excellent in the balance between heat resistance and elongation.

  Such a biphenyl type epoxy resin is an epoxy resin represented by the following formula (IV).

(In the formula, G is a group represented by the above general formula (III), and may be added at any position as long as one is added to each benzene ring. R ₆ and R ₇ are It represents an alkylene group having 1 to 4 carbon atoms, a phenyl group, or a halogen atom, and each R may be the same or different.
Moreover, it is preferable that this biphenyl type epoxy resin contains 5-35 mass parts with respect to 100 mass parts of all the epoxy resins, More preferably, it is 20-35 mass parts. When the biphenyl type epoxy resin is 5 parts by mass or more, it is preferable because the cured resin is excellent in heat resistance and elongation. On the other hand, when the biphenyl type epoxy resin is 35 parts by mass or less, it is preferable because the cured resin is excellent in elastic modulus and elongation.

  Examples of such commercially available biphenyl type epoxy resins include “jER (registered trademark)” YX4000H, YX4000, YL6616 (manufactured by Mitsubishi Chemical Corporation).

  Examples of the aliphatic epoxy resin having more than two epoxy groups include trimethylolpropane polyglycidyl ether, glycerol polyglycidyl ether, diglycerol polyglycidyl ether, polyglycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, sorbitol poly Glycidyl ether and the like can be used.

  Moreover, it is preferable that 3-20 mass parts is contained with respect to 100 mass parts of all the epoxy resins, and, more preferably, it is 5-15 mass parts with respect to 100 mass parts of all the epoxy resins. It is preferable that the aliphatic epoxy resin having more than two epoxy groups is 3 parts by mass or more because the elongation of the cured resin is excellent. On the other hand, when the amount of the aliphatic epoxy resin having more than two epoxy groups is 20 parts by mass or less, it is preferable because the cured resin has excellent heat resistance and elastic modulus.

  Examples of commercially available aliphatic epoxy resins having more than two epoxy groups include “Denacol (registered trademark)” EX-313, EX-314, EX-321, EX-411, EX-421, EX-512, EX-521, EX-611, EX-612, EX-614, EX-614B, EX-622 (manufactured by Nagase ChemteX Corporation) and the like.

  Specific examples of the bifunctional or lower aliphatic epoxy resin include “Denacol (registered trademark)” EX-111, 121, 141, 145, 146, 147, 171, 192, 201, 211, 212, 252, 810, 811. , 821, 830, 832, 841, 850, 851, 861, 911, 920, 931, 941 (manufactured by Nagase ChemteX Corporation).

  The bisphenol type epoxy resin is not particularly limited as long as the two phenolic hydroxyl groups of the bisphenol compound are reacted with epichlorohydrin and converted into a glycidyloxy group. The bisphenol A type, bisphenol F type, bisphenol AD type, Bisphenol S type or halogen, alkyl-substituted products, hydrogenated products, etc. of these bisphenols are used. Moreover, not only a monomer but the high molecular weight body which has a some repeating unit can also be used preferably.

  Commercially available bisphenol A type epoxy resins include “jER (registered trademark)” 825, 828, 834, 1001, 1002, 1003, 1003F, 1004, 1004AF, 1005F, 1006FS, 1007, 1009, 1010 (and above, Mitsubishi Chemical) Etc.). Examples of the brominated bisphenol A type epoxy resin include “jER (registered trademark)” 505, 5050, 5051, 5054, and 5057 (above, manufactured by Mitsubishi Chemical Corporation). Examples of commercially available hydrogenated bisphenol A type epoxy resins include ST5080, ST4000D, ST4100D, ST5100 (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.).

  Commercially available bisphenol F type epoxy resins include “jER (registered trademark)” 806, 807, 4002P, 4004P, 4007P, 4009P, 4010P (above, manufactured by Mitsubishi Chemical Corporation), “Epototo (registered trademark)” YDF2001. YDF2004 (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.) and the like. Examples of the tetramethylbisphenol F type epoxy resin include YSLV-80XY (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.).

  Examples of the bisphenol S-type epoxy resin include “Epiclon (registered trademark)” EXA-1514 (manufactured by DIC Corporation).

  Examples of commercially available amine type epoxy resins include tetraglycidyl diaminodiphenylmethane, tetraglycidyldiaminodiphenylsulfone, triglycidylaminophenol, triglycidylaminocresol, tetraglycidylxylylenediamine, glycidylaniline, diglycidyltoluidine, and halogens thereof. , Alkyl-substituted products, hydrogenated products, and the like can be used.

  Tetraglycidyldiaminodiphenylmethane includes “Sumiepoxy (registered trademark)” ELM434 (manufactured by Sumitomo Chemical Co., Ltd.), YH434L (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), and “jER (registered trademark)” 604 (manufactured by Mitsubishi Chemical Corporation). ), “Araldide (registered trademark)” MY720, MY721 (manufactured by Huntsman Co., Ltd.) and the like can be used. As tetraglycidyl diaminodiphenyl sulfone, TGDDS (manufactured by Konishi Chemical Co., Ltd.) or the like can be used. As triglycidylaminophenol or triglycidylaminocresol, "Sumiepoxy (registered trademark)" ELM100, ELM120 (manufactured by Sumitomo Chemical Co., Ltd.), "Araldide (registered trademark)" MY0500, MY0510, MY0600 (manufactured by Huntsman Corp.) "JER (registered trademark)" 630 (manufactured by Mitsubishi Chemical Corporation) or the like can be used. As tetraglycidylxylylenediamine and hydrogenated products thereof, “TETRAD (registered trademark)”-X, “TETRAD (registered trademark)”-C (manufactured by Mitsubishi Gas Chemical Co., Inc.) and the like can be used. As glycidyl aniline, GAN (made by Nippon Kayaku Co., Ltd.) etc. can be used. As diglycidyl toluidine, GOT (made by Nippon Kayaku Co., Ltd.) etc. can be used.

  Commercially available products of phenol novolac type epoxy resins include “Epicoat (registered trademark)” 152, 154 (manufactured by Mitsubishi Chemical Corporation), “Epicron (registered trademark)” N-740, N-770, N-775 ( As mentioned above, DIC Corporation) etc. are mentioned.

  As a commercial product of a cresol novolac type epoxy resin, “Epiclon (registered trademark)” N-660, N-665, N-670, N-673, N-695 (above, manufactured by DIC Corporation), EOCN-1020 , EOCN-102S, EOCN-104S (manufactured by Nippon Kayaku Co., Ltd.), and the like.

  NC-3000, 3000L (made by Nippon Kayaku Co., Ltd.) etc. are mentioned as a commercial item of a biphenyl aralkyl type epoxy resin.

  As the naphthalene aralkyl type epoxy resin, “Epototo (registered trademark)” ESN-155, ESN-355, ESN-375, ESN-475V, ESN-485, ESN-175 (above, manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), NC-7000, NC-7300, NC-7300L (Nippon Kayaku Co., Ltd. product) etc. are mentioned.

  Commercially available dicyclopentadiene type epoxy resins include “Epicron (registered trademark)” HP7200, HP-7200L, HP-7200H, HP-7200HH, HP-7200HHH (above, manufactured by DIC Corporation), Tactix558 (Huntsman Corporation) )), XD-1000-1L, XD-1000-2L (above, Nippon Kayaku Co., Ltd.).

  Examples of commercially available urethane-modified epoxy resins include AER4152 (produced by Asahi Kasei Epoxy Co., Ltd.) and ACR1348 (produced by ADEKA Co., Ltd.) having an oxazolidone ring.

  Examples of commercially available tetraphenylethane type epoxy resins include “jER (registered trademark)” 1031 (manufactured by Mitsubishi Chemical Corporation), GTR-1800 (manufactured by Nippon Kayaku Co., Ltd.), and the like.

  Commercially available products of triphenylmethane type epoxy resin include “jER (registered trademark)” 1032S50 (manufactured by Mitsubishi Chemical Corporation), “Tactics (registered trademark)” 742 (manufactured by Huntsman Corporation), EPPN-501H (Japan) Kayaku Co., Ltd.).

  As a commercial item of a fluorene type epoxy resin, PG-100, CG-200, EG-200 (made by Osaka Gas Chemical Co., Ltd.), LME10169 (made by Huntsman Co., Ltd.), etc. are mentioned.

  Dicyandiamide or a derivative thereof of this component [B] is necessary for curing the epoxy resin composition, and is excellent in curability and storage stability of the epoxy resin composition. The dicyandiamide derivative is obtained by bonding various compounds to dicyandiamide, and includes a reaction product with an epoxy resin, a reaction product with a vinyl compound or an acrylic compound.

  Examples of commercially available dicyandiamide include DICY-7 and DICY-15 (manufactured by Mitsubishi Chemical Corporation).

  The component [C], diaminodiphenylsulfone or a derivative thereof, is necessary for curing the epoxy resin composition, has an excellent balance between heat resistance and elongation, and is excellent in storage stability of the epoxy resin composition.

  Such component [C] is preferably in the form of fine particles. Diaminodiphenyl sulfone has structural isomers depending on the substitution position of the amino group on the aromatic ring. In the present invention, any isomer can be used, but the properties of the matrix resin and the resulting composite material can be controlled by selecting the type of isomer. For example, when 3,3′-diaminodiphenylsulfone is used, although the heat resistance is reduced as compared with the case where 4,4′-diaminodiphenylsulfone is used, the elastic modulus and elongation are improved.

  Commercially available products of 4,4′-diaminodiphenyl sulfone include “Seika Cuca (registered trademark)”-S (manufactured by Wakayama Seika Kogyo Co., Ltd.), “Sumi Cure (registered trademark)” S (manufactured by Sumitomo Chemical Co., Ltd.) Etc. Examples of commercially available 3,3'-diaminodiphenylsulfone include 3,3'-DAS (manufactured by Mitsui Chemicals Fine Co., Ltd.).

In addition, it is preferable that the constituent elements [B] and [C] are included within a range satisfying the following conditions (I) and (II) with respect to 1 equivalent of the epoxy group of all the epoxy resin components, and more preferably Is an amount that satisfies the following conditions (III) and (IV).
(I) The equivalent of active hydrogen group of component [B] is 0.3 to 0.8 equivalent (II) The equivalent of active hydrogen group of component [C] is 0.2 to 0.7 equivalent (III) The equivalent of active hydrogen group of element [B] is 0.4 to 0.7 equivalent (IV) The equivalent of active hydrogen group of component [C] is 0.3 to 0.6 equivalent.

  Here, the active hydrogen group means a functional group that can react with an epoxy group. Such an amount is such that the equivalent of the active hydrogen group of the constituent element [B] is 0.3 equivalent or more and the equivalent of the active hydrogen group of the constituent element [C] is 0.7 equivalent to 1 equivalent of the epoxy group of all the epoxy resin components. It is preferable that the amount satisfies the equivalent or less because it is excellent in heat resistance. On the other hand, such an amount is such that the equivalent of the active hydrogen group of the component [B] is 0.8 equivalent or less and the equivalent of the active hydrogen group of the component [C] is 0 with respect to 1 equivalent of the epoxy group of all the epoxy resin components. It is preferable that the amount satisfies 2 equivalents or more because the balance between heat resistance and elongation is excellent.

  Moreover, it is preferable that the total amount of component [B] and [C] contains the quantity used as the range of 0.5-1.0 equivalent with respect to 1 equivalent of epoxy groups of all the epoxy resin components. When the total amount is 0.5 equivalent or more with respect to 1 equivalent of the epoxy group of all the epoxy resin components, the heat resistance of the cured resin product tends to be improved. Further, when the total amount is such that the active hydrogen group is 1.0 equivalent or less with respect to 1 equivalent of the epoxy group of all the epoxy resin components, the components [B] and [C] that remain unreacted are small, There are fewer defects.

  In the epoxy resin composition of the present invention, a curing agent other than the constituent elements [B] and [C] can be blended as long as the effects of the present invention are not lost. These may be added in combination of not only one type but also a plurality of types. Specific examples include aromatic amines other than diaminodiphenyl sulfone or derivatives thereof, amines such as aliphatic amines, acid anhydrides, polyaminoamides, organic acid hydrazides, phenol resins, and isocyanates. .

The urea compound of component [D] is necessary because the resin composition is excellent in storage stability and curability and the heat resistance of the cured resin is improved.
The component [D] is preferably included in an amount of 0.1 to 3 parts by mass, more preferably 0.1 to 2 parts by mass, and still more preferably 0.2 to 100 parts by mass of the total epoxy resin component. -1 part by mass. When the blending amount of [D] is in the range of 0.1 to 3 parts by mass, the epoxy resin and the constituent elements [B] and [C] react efficiently while suppressing self-polymerization of the epoxy resin. The heat resistance and elongation of the cured resin product tend to be improved.

  Examples of the component [D] include N, N-dimethyl-N ′-(3,4-dichlorophenyl) urea, toluenebis (dimethylurea), 4,4′-methylenebis (phenyldimethylurea), 3- Phenyl-1,1-dimethylurea and the like can be used. Examples of commercially available urea compounds include DCMU99 (manufactured by Hodogaya Chemical Co., Ltd.), “Omicure (registered trademark)” 24, 52, 94 (manufactured by CVC Specialty Chemicals, Inc.) and the like.

  In the epoxy resin composition of the present invention, a curing agent accelerator other than the component [D] can be blended within a range not losing the effects of the present invention. These may be added in combination of not only one type but also a plurality of types. Specifically, at least one selected from tertiary amines and salts thereof, imidazoles and salts thereof, phosphorus curing accelerators, carboxylic acid metal salts, Lewis acids, Bronsted acids and salts thereof, and the like. Can be used.

  Examples of commercially available imidazoles include 2MZ, 2PZ, and 2E4MZ (manufactured by Shikoku Kasei Co., Ltd.). As the phosphorus curing accelerator, alkyl phosphine compounds, aryl phosphine compounds, phosphine oxide compounds, phosphonium salts and the like can be used. Lewis acid catalysts include boron trifluoride / piperidine complex, boron trifluoride / monoethylamine complex, boron trifluoride / triethanolamine complex, boron trichloride / octylamine complex, etc. Can be mentioned.

  The epoxy resin composition according to the present invention includes control of rheological properties, tack control of prepreg, which will be described later, improvement of elastic modulus and toughness of cured resin, and improvement of adhesion between reinforcing fiber and matrix resin in a fiber reinforced composite material. In order to have the improvement effect, a thermoplastic resin may be included. It is preferable that a thermoplastic resin contains 0.1-15 mass parts with respect to 100 mass parts of all the components of an epoxy resin. By blending the thermoplastic resin in such a range, the above effects tend to be sufficiently obtained.

As the thermoplastic resin, a thermoplastic resin soluble in an epoxy resin, organic particles such as rubber particles and thermoplastic resin particles, and the like can be blended. As the thermoplastic resin soluble in the epoxy resin, a thermoplastic resin having a hydrogen bonding functional group that can be expected to improve the adhesion between the epoxy resin composition and the reinforcing fiber is preferably used.
As the thermoplastic resin soluble in epoxy resin and having a hydrogen bonding functional group, a thermoplastic resin having an alcoholic hydroxyl group, a thermoplastic resin having an amide bond, or a thermoplastic resin having a sulfonyl group can be used.

  Examples of the thermoplastic resin having an alcoholic hydroxyl group include polyvinyl acetal resins such as polyvinyl formal and polyvinyl butyral, polyvinyl alcohol, and phenoxy resins. In addition, examples of the thermoplastic resin having an amide bond include polyamide, polyimide, and polyvinylpyrrolidone. Furthermore, polysulfone can be mentioned as a thermoplastic resin which has a sulfonyl group. Polyamide, polyimide and polysulfone may have a functional group such as an ether bond and a carbonyl group in the main chain. The polyamide may have a substituent on the nitrogen atom of the amide group.

  Commercially available thermoplastic resins soluble in epoxy resins and having hydrogen bonding functional groups include polyvinyl acetal resins such as Denkabutyral and “Denka Formal (registered trademark)” (manufactured by Denki Kagaku Kogyo Co., Ltd.), “Vinylec”. (Registered trademark) "(manufactured by jNC Corporation)," UCAR (registered trademark) "PKHP (manufactured by Union Carbide) as a phenoxy resin, and" Macromelt (registered trademark) "(manufactured by Henkel Japan Co., Ltd.) as a polyamide resin ), “Amilan (registered trademark)” (manufactured by Toray Industries, Inc.), “Ultem (registered trademark)” (manufactured by General Electric Co., Ltd.) as polyimide, and “Victrex (registered trademark)” (manufactured by Mitsui Chemicals, Inc.) as polysulfone ), “UDEL (registered trademark)” (manufactured by Union Carbide), polyethersulfone, Excel (registered trademark) "(manufactured by Sumitomo Chemical Co.), as polyvinylpyrrolidone," Luviskol (registered trademark) "can be exemplified (BASF Japan Ltd.).

  Acrylic resins are highly compatible with epoxy resins and are preferably used for controlling viscoelasticity. Examples of commercially available acrylic resins include “Dianal (registered trademark)” BR series (manufactured by Mitsubishi Rayon Co., Ltd.), “Matsumoto Microsphere (registered trademark)” M, M100, M500 (above, Matsumoto Yushi Seiyaku ( Product)).

  As the rubber particles, cross-linked rubber particles, and core-shell rubber particles obtained by graft polymerization of a different polymer on the surface of the cross-linked rubber particles are preferably used from the viewpoint of handleability and the like.

  As commercial products of crosslinked rubber particles, FX501P (manufactured by JSR Co., Ltd.) composed of a crosslinked product of carboxyl-modified butadiene-acrylonitrile copolymer, CX-MN series (manufactured by Nippon Shokubai Co., Ltd.) composed of acrylic rubber fine particles, YR-500 series (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.) and the like can be used.

  Commercially available core-shell rubber particles include, for example, “Paraloid (registered trademark)” EXL-2655 (manufactured by Kureha Co., Ltd.), acrylate / methacrylate ester copolymer made of butadiene / alkyl methacrylate / styrene copolymer. “STAPHYLOID (registered trademark)” AC-3355, TR-2122 (manufactured by Takeda Pharmaceutical Co., Ltd.), “PARALOID (registered trademark)” EXL-2611 composed of butyl acrylate / methyl methacrylate copolymer EXL-3387 (manufactured by Rohm & Haas), “Kane Ace (registered trademark)” MX series (manufactured by Kaneka Corporation) and the like can be used.

  As the thermoplastic resin particles, polyamide particles and polyimide particles are preferably used, and as commercially available products of polyamide particles, SP-500 (manufactured by Toray Industries, Inc.), “Orgasol (registered trademark)” (manufactured by Arkema), etc. Can be used.

  Furthermore, the epoxy resin composition of the present invention can be blended with inorganic particles as long as the effects of the present invention are not lost. Examples of the inorganic particles include metal oxides, metals, and minerals, and these may be used alone or in combination of two or more. Inorganic particles are used to improve the function and impart functions of the resulting cured product. Specific functions include surface hardness, anti-blocking, heat resistance, barrier properties, electrical conductivity, antistatic properties, electromagnetic wave absorption, ultraviolet cut, Examples include toughening, impact resistance, and low thermal linear expansion. Metal oxides include silicon oxide, titanium oxide, zirconium oxide, zinc oxide, tin oxide, indium oxide, aluminum oxide, antimony oxide, cerium oxide, magnesium oxide, iron oxide, tin-doped indium oxide (ITO), antimony-doped tin oxide. , Fluorine-doped tin oxide, and the like. Examples of the metal include gold, silver, copper, aluminum, nickel, iron, zinc, and stainless steel. Examples of the mineral include clay minerals such as montmorillonite, talc, mica, boehmite, kaolin, smectite, zonolite, verculite, and sericite. Others include carbon compounds such as carbon black, acetylene black, ketjen black, carbon nanotubes, metal hydroxides such as aluminum hydroxide and magnesium hydroxide, various glasses such as glass beads, glass flakes, and glass balloons. A filler can be mentioned. There are no particular restrictions on the size of the inorganic particles to be used, and for example, particles having a size of about 1 nm to 10 μm can be used. May be. The inorganic particles may be used as they are, or those dispersed in a solvent like sol or colloid may be used.

  Furthermore, for the purpose of improving dispersibility and interface affinity, a filler surface whose surface is treated with a coupling agent or the like may be used.

  The epoxy resin composition of the present invention may contain other components in addition to the above-described components as long as the effects of the present invention are not impaired. Other components include, for example, mold release agents, surface treatment agents, flame retardants, antibacterial agents, leveling agents, antifoaming agents, thixotropic agents, heat stabilizers, light stabilizers, UV absorbers, colorants, and couplings. Agents, metal alkoxides and the like.

  As a numerical value representing heat resistance, the glass transition temperature is generally used, but the glass transition temperature of the cured resin obtained by curing the epoxy resin composition of the present invention is preferably 140 to 230 ° C. More preferably, it is 160-230 degreeC, More preferably, it is 170-230 degreeC, Most preferably, it is 180-230 degreeC. When the glass transition temperature of the cured resin is 140 ° C. or higher, the resulting fiber-reinforced composite material has sufficient heat resistance when used for bicycle rim materials, automotive members, and industrial members. Moreover, if glass transition temperature is 230 degrees C or less, there exists a tendency which is excellent in the elongation of resin cured material, and excellent in the tensile strength of the fiber reinforced composite material obtained.

  When the glass transition temperature is less than 140 ° C., the amount of the component [A] or the component [C] is increased or the component [B] is decreased within the scope of the present invention. The transition temperature can be improved. On the other hand, when the glass transition temperature exceeds 230 ° C., within the scope of the present invention, by reducing the component [A] and the component [C] or increasing the component [B], The glass transition temperature can be lowered.

  Furthermore, the amount of bending deflection of the cured resin product is preferably 4 to 15 mm, more preferably 6 to 15 mm, still more preferably 8 to 15 mm, and most preferably 10 to 15 mm. If the amount of bending deflection is 4 mm or more, the resulting fiber-reinforced composite material has sufficient tensile strength when used for bicycle rim materials, automobile members, and industrial members. Moreover, if the amount of bending deflection is 15 mm or less, it exists in the heat resistance of resin cured material, and there exists a tendency which is excellent in the heat resistance of the fiber reinforced composite material obtained.

When the amount of bending deflection is less than 4 mm, the amount of deflection can be reduced by decreasing the component [A] or the component [B] or increasing the component [C] within the scope of the present invention. Can be improved. On the other hand, when the amount of deflection exceeds 15 mm, the amount of deflection can be increased by increasing the component [A] or the component [B] or decreasing the component [C] within the scope of the present invention. Can be reduced.
As a numerical value representing the curability of the cured resin of the present invention, a reaction rate when cured at 200 ° C. for 30 minutes (hereinafter simply referred to as a reaction rate) is used. Such a reaction rate is preferably 90% or more, and more preferably 95% or more. When such a reaction rate is 90% or more, the cured product has excellent heat resistance and elongation, and even when the cured resin is exposed to heat or light, it tends to be difficult to deform.
This reaction rate refers to the reaction rate of glycidyl groups in the epoxy resin component, and can be determined as follows. That is, it calculates from the area ratio of the absorbance of the benzene ring peak and the oxirane ring peak of the epoxy resin composition and the cured resin using an infrared spectrum. Specifically, using a Fourier transform infrared spectrophotometer and measuring the area of the absorbance of the epoxy resin composition and cured resin respective benzene ring peak (1510 cm ^-1) and oxirane ring peak (910 cm ^-1), For each, the area ratio of the oxirane ring to the benzene ring {(area of the oxirane ring peak) / (area of the peak of the benzene ring)} is obtained, and the reaction rate of the cured resin is obtained by the following formula.

Reaction rate = (1− (area ratio of cured resin) / (area ratio of epoxy resin composition)) × 100
When the reaction rate is less than 90%, the reaction rate can be improved by increasing any of the constituent elements [B] to [D].

  For preparing the epoxy resin composition of the present invention, a kneader, a planetary mixer, a three-roll extruder, a twin-screw extruder, or the like is preferably used. After adding other than the constituent elements [B] to [D], the temperature of the epoxy resin composition is raised to an arbitrary temperature of 100 to 180 ° C. while stirring, whereby the constituent elements [B] to [D] The method of dissolving the resin other than the above and then lowering the temperature to 100 ° C. or lower, more preferably 80 ° C. or lower with stirring, and adding and kneading the constituent elements [B] to [D] is an epoxy Since it is excellent in the storage stability of a resin composition, it is used preferably.

  The cured resin is produced as follows. After defoaming the epoxy resin composition at a pressure of 0.3 kPa or less and a temperature of 80 ° C. or less, in a mold set to a thickness of 2 mm with a 2 mm-thick “Teflon (registered trademark)” spacer, a range of 200 ° C. By curing at a temperature of 30 minutes, a cured resinous plate-like resin can be obtained.

  The epoxy resin composition of the present invention can be used as a molding material in combination with reinforcing fibers. Such reinforcing fibers are not particularly limited, and glass fibers, carbon fibers, aramid fibers, boron fibers, alumina fibers, silicon carbide fibers, and the like are used. Two or more of these fibers may be mixed and used. Among these, it is preferable to use carbon fibers from which a lightweight and highly rigid fiber-reinforced composite material can be obtained.

  The carbon fiber preferably has a surface oxygen concentration O / C measured by X-ray photoelectron spectroscopy of 0.02 to 0.20, more preferably 0.04 to 0.15, still more preferably 0.8. It is 06-0.10. When the O / C is 0.02 or more, the chemical bond between the epoxy resin composition, the coupling agent or sizing agent described later, and the carbon fiber outermost surface becomes strong, and the reduction of the residual stress of the present invention is reduced. It becomes easy to contribute greatly to the improvement of the strength of the material. Moreover, since the O / C is 0.20 or less, the chemical bond between the functional group of the epoxy resin composition and the outermost surface of the carbon fiber can be strengthened while maintaining the strength of the carbon fiber substrate itself, The reduction of the residual stress of the present invention easily contributes greatly to improving the strength of the molding material.

  The surface nitrogen concentration N / C measured by X-ray photoelectron spectroscopy is preferably 0.02 to 0.30, preferably 0.03 to 0.25, and more preferably 0.10 to 0.00. Is 20. When N / C is 0.02 or more, the chemical bond between the epoxy resin composition, the coupling agent or sizing agent described later, and the outermost surface of the carbon fiber becomes strong, and the reduction of the residual stress of the present invention reduces the molding material. It becomes easy to contribute greatly to the improvement of strength. Further, when N / C is 0.30 or less, the chemical bond between the functional group of the epoxy resin composition and the outermost surface of the carbon fiber can be strengthened while maintaining the strength inherent in the carbon fiber substrate itself. The reduction of the residual stress of the invention easily contributes greatly to improving the strength of the molding material.

Here, the surface oxygen concentration O / C refers to a value obtained by X-ray photoelectron spectroscopy according to the following procedure. First, after cutting the carbon fiber bundle from which the sizing agent and the like have been removed with a solvent and spreading and arranging on a stainless steel sample support base, the photoemission angle is 90 degrees, and MgK _α1,2 is used as the X-ray source. The inside of the sample chamber is kept at a vacuum of 1 × 10 ⁻⁸ Torr. As correction of the peak accompanying charging during measurement, first, the binding energy value of the main peak of C1S is adjusted to 284.6 eV. The C _1S peak area was obtained by drawing a straight base line in the range of 282 to 296 eV, and the O _1S peak area was obtained by drawing a straight base line in the range of 528 to 540 eV. The surface oxygen concentration O / C was expressed as an atomic ratio calculated by dividing the ratio of the O _1S peak area to the C _1S peak area by the sensitivity correction value unique to the apparatus. In the examples of the present invention, ESCA-750 manufactured by Shimadzu Corporation was used, and the sensitivity correction value unique to the apparatus was 2.85.

The surface oxygen concentration N / C refers to a value obtained by X-ray photoelectron spectroscopy according to the following procedure. First, after cutting the carbon fiber bundle from which the sizing agent and the like have been removed with a solvent and spreading and arranging on a stainless steel sample support base, the photoemission angle is 90 degrees, and MgK _α1,2 is used as the X-ray source. The inside of the sample chamber is kept at a vacuum of 1 × 10 ⁻⁸ Torr. As correction of the peak accompanying charging during measurement, first, the binding energy value of the main peak of C _1S is adjusted to 284.6 eV. The C _1S peak area was determined by drawing a straight base line in the range of 282 to 296 eV, and the N _1S peak area was determined by drawing a straight base line in the range of 398 to 410 eV. The surface nitrogen concentration N / C was expressed as an atomic ratio calculated by dividing the ratio of the N _1S peak area to the C _1S peak area by the sensitivity correction value unique to the apparatus. In the examples of the present invention, ESCA-750 manufactured by Shimadzu Corporation was used, and the sensitivity correction value unique to the apparatus was 1.7.

  Further, the surface of the carbon fiber can be given a known surface treatment, a coupling agent or a sizing agent, but a divalent or higher epoxy resin, a resin having an alkoxysilyl group, polyurethane, polyamide, polyvinyl acetate, Any one or more of ethylene ionomer and unsaturated polyester is preferably attached.

  As the carbon fiber surface treatment, electrolytic treatment is preferable. Examples of the electrolytic solution used for the electrolytic treatment include acids such as sulfuric acid, nitric acid, and hydrochloric acid, hydroxides such as sodium hydroxide, potassium hydroxide, and barium hydroxide, ammonia, and inorganic substances such as sodium carbonate and sodium bicarbonate. Examples include salts, aqueous solutions of organic salts such as sodium acetate and sodium benzoate, and potassium, barium or other metal salts thereof, ammonium salts, and organic compounds such as hydrazine.

  The form of the reinforcing fibers is not particularly limited, and for example, long fibers aligned in one direction, tows, woven fabrics, mats, knits, braids, braids, short fibers chopped to a length of less than 10 mm, and the like are used. It is done. As used herein, long fibers refer to single fibers or fiber bundles that are substantially continuous for 10 mm or more. The short fiber is a single fiber or fiber bundle cut to a length of less than 10 mm. Among these, long fiber, tow, woven fabric, mat, knit and braid arranged in one direction are preferable for applications where a fiber reinforced composite material having high specific strength and high specific modulus is required, and more preferably in one direction. Long fibers, tows and woven fabrics.

  As a method of molding into a fiber reinforced composite material using a molding material in which the epoxy resin composition and reinforcing fibers of the present invention are combined, a method of molding after combining the epoxy resin composition and reinforcing fibers in advance, or an epoxy resin at the time of molding The method etc. which shape | mold combining a composition and a reinforced fiber are mentioned. As a method of combining the epoxy resin composition and the reinforcing fiber in advance, a method of molding using a sheet molding compound (SMC), a method of molding using a prepreg, a method of molding using a filament winding method (dry method), etc. Is mentioned. Methods of molding by combining the epoxy resin composition and the reinforcing fiber during molding include hand lay-up method, spray-up method, resin transfer molding method, resin film infusion method, filament winding method (wet method), pultrusion method, etc. Is mentioned.

  In particular, for applications where lightweight and highly rigid fiber reinforced composite materials are required, a method of molding using prepreg is preferable. From the viewpoint of balance of strength, shape flexibility, and molding cost of fiber reinforced composite materials, yarn prepreg is preferable. A method of molding using a resin, a resin transfer molding method, a resin film infusion method, a filament winding method, and a pultrusion method are preferably used.

  SMC is composed of a reinforcing fiber made of short fibers and a resin, and a B-stage formed by impregnating a reinforcing fiber made of short fibers with a resin composition into a sheet form. And SMC mainly gives the fiber reinforced composite material of this invention by heat-pressing and hardening in a metal mold | die.

  The prepreg is a sheet formed by impregnating a fiber base material such as long fiber, woven fabric, mat, etc., made of the reinforcing fibers in one direction with a resin composition. Examples of the impregnation method include a wet method in which the resin composition is reduced in viscosity by dissolving in a solvent such as methyl ethyl ketone and methanol, and a hot melt method (dry method) in which the viscosity is reduced by heating and impregnation. Can do.

  The wet method is a method in which a reinforcing fiber is immersed in a solution of a resin composition and then lifted and the solvent is evaporated using an oven or the like. The hot melt method is a method in which a resin composition whose viscosity has been reduced by heating is directly impregnated into a fiber substrate made of reinforcing fibers, or a film in which a resin composition is once coated on release paper or the like is prepared. Next, the fiber base material made of the reinforcing fibers is impregnated with resin by overlapping the film from both sides or one side of the fiber base material made of the reinforcing fibers and heating and pressing. The hot melt method is preferable because substantially no solvent remains in the prepreg.

  After shaping and / or laminating the prepreg, the fiber-reinforced composite material of the present invention is produced by a method of heat-curing the epoxy resin composition of the present invention while applying pressure to the shaped product and / or laminate. .

  As a method for applying heat and pressure, a press molding method, an autoclave molding method, a bagging molding method, a wrapping tape method, an internal pressure molding method, or the like can be appropriately used.

  The wrapping tape method is a method of winding a prepreg around a mandrel or other core metal to form a tubular body made of a fiber-reinforced composite material, and is a method suitable for producing a rod-shaped body such as a golf shaft or fishing rod. . More specifically, the prepreg is wound around a mandrel, a wrapping tape made of a thermoplastic film is wound outside the prepreg for fixing and applying pressure, and the resin is heated and cured in an oven, and then the core metal This is a method for extracting a tube to obtain a 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 bad, a racket such as tennis or badminton, or a bicycle wheel.

The prepreg preferably has a reinforcing fiber amount per unit area of 50 to 300 g / m ² . It is preferable that the amount of the reinforcing fibers is 50 g / m ² or more because the number of laminated layers is small in order to obtain a predetermined thickness at the time of forming the fiber-reinforced composite material and the working efficiency is good. On the other hand, it is preferable that the amount of reinforcing fibers is 300 g / m ² or less because the prepreg drape tends to be good. The fiber weight content is preferably 60 to 90% by mass, more preferably 65 to 85% by mass, and further preferably 70 to 80% by mass. When the fiber mass content is 60% by mass or more, since the reinforcing fiber content is large, the advantage of the prepreg that a fiber-reinforced composite material excellent in specific strength and specific elastic modulus can be obtained is easily obtained. Moreover, it is preferable for the fiber weight content to be 90% by mass or less because poor impregnation of the epoxy resin composition hardly occurs and the obtained composite material tends to have less voids.

  As a manufacturing method of the fiber reinforced composite material of this invention, it is preferable to include the process of hardening an epoxy resin composition within 150-200 degreeC and 2 hours. It is preferable for the curing temperature to be 150 ° C. or higher because the production time tends to be short. On the other hand, when the curing temperature is 200 ° C. or lower, the residual stress of the epoxy resin composition tends to be small, which is preferable. Furthermore, when the curing time is within 2 hours, it is preferable because the amount of energy used is small and high-speed production is easy.

  The filament winding method is a method in which a continuous fiber bundle in which reinforcing fibers are arranged in one direction is impregnated with a resin, and the resin is cured after being wound in a desired shape. The dry method is a method in which the continuous fiber bundle is previously impregnated into a B-stage and molded, and the wet method is a method in which the continuous fiber bundle is impregnated with the resin and formed into a desired shape. It is a method of winding and curing.

  The hand lay-up method is a method in which a reinforcing fiber substrate is pre-shaped in a mold, impregnated with a brush or roller, laminated to a predetermined thickness while defoaming, and then cured.

  The spray-up method is a method of using a spray-up machine to cut the reinforcing fibers to an appropriate length and simultaneously spraying the resin onto the mold to obtain a predetermined thickness and then curing the resin. .

  With the resin transfer molding (RTM) method, a reinforcing fiber base is pre-shaped in a mold, and after mold clamping, a resin is injected into the sealed system to impregnate the reinforcing fiber base with the resin, and the resin is cured. This is a method of molding. The mold and the resin are preferably preheated. The temperature for heating the mold and the resin is determined from the relationship between the initial viscosity of the resin and the increase in viscosity from the viewpoint of impregnation into the reinforcing fiber base, and is preferably 40 to 70 ° C, more preferably 50 to 60 ° C. It is.

  In the RTM method, a reinforcing fiber substrate obtained by processing reinforcing fibers into a form such as a mat, a woven fabric, a knit, a blade, or a long fiber aligned in one direction is preferably used. Among them, a woven fabric that is easy to obtain a fiber-reinforced composite material having a high fiber content and excellent in handleability is preferably used.

  In addition, in the RTM method, depending on the fiber reinforced composite material to be obtained, such as using a molding die having a plurality of injection ports and injecting resin from a plurality of injection ports simultaneously or sequentially with a time difference. It is preferable to select an appropriate condition because a degree of freedom that can cope with molded bodies of various shapes and sizes can be obtained. The number and shape of such injection ports are not limited, but in order to enable injection in a short time, it is better that there are more injection ports, and the arrangement is a position where the flow length of the resin can be shortened according to the shape of the molded product. Is preferred.

  The resin used in the RTM method is prepared by separately heating the liquid a containing the epoxy resin and the liquid b containing the constituent elements [B] to [D] and mixing them using a mixer immediately before injection. It is preferable to inject from the viewpoint of the pot life of the resin. Ingredients of the curing accelerator or other, a liquid may be blended in either b solution, it can be used as a mixture in either or both advance.

  In the RTM method, the injection pressure of the resin composition is usually 0.1 to 1.0 MPa, and a VaRTM (vacuum assist resin transfer molding) method in which the resin is injected by vacuum suction inside the mold can be used. From the point of time and economical efficiency of equipment, 0.1 to 0.6 MPa is preferable. Even when pressure injection is performed, it is preferable to suck the inside of the mold in vacuum before injecting the resin composition, because generation of voids is suppressed.

  In the resin film infusion method, a reinforcing fiber base and an uncured resin film are placed in a closed mold, the whole is heated to melt the resin, and then the pressure in the mold and external pressure are applied. In this method, the reinforcing fiber base material is impregnated with the above and further heated to be cured.

  The pultrusion method is a method of continuously forming a fiber reinforced composite material by impregnating a continuous reinforcing fiber bundle with resin, introducing it into a mold, heat-curing it, and drawing it with a drawing device. is there.

  The fiber-reinforced composite material of the present invention is suitably used for sports applications, general industrial applications, and aerospace applications. More specifically, in sports applications, it is used for golf shafts, fishing rods, tennis and badminton rackets, hockey sticks, and ski poles. 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. Used for. Further, in aerospace applications, it is used for fuselage, main wing, tail wing, moving wing, fairing, cowl, door, seat, interior material, motor case, antenna and the like.

  Hereinafter, the effects of the present invention will be described more specifically with reference to examples. In addition, this invention is not limited to the following Example. The unit “part” of the composition ratio means part by mass unless otherwise specified. Various characteristics (physical properties) were measured in an environment of a temperature of 23 ° C. and a relative humidity of 50% unless otherwise specified.

  The thermosetting resin, the thermoplastic resin, and the reinforcing fiber used in this example and the comparative example are as follows.

<Epoxy resin>
Component [A]
・ Binaphthalene type epoxy resin (“Epiclon (registered trademark)” EXA-4701, DIC Corporation, 5-functional, epoxy equivalent: 167)
Binaphthalene type epoxy resin (“Epiclon (registered trademark)” HP-4700, manufactured by DIC Corporation, tetrafunctional, epoxy equivalent: 165)
・ Binaphthalene type epoxy resin (“Epiclon (registered trademark)” HP-4710, manufactured by DIC Corporation, tetrafunctional, epoxy equivalent: 171)
-Binaphthalene type epoxy resin ("Epiclon (registered trademark)" EXA-4750, manufactured by DIC Corporation, trifunctional, epoxy equivalent: 185).

Other epoxy resins / biphenyl type epoxy resins (“jER (registered trademark)” YX4000, manufactured by Mitsubishi Chemical Corporation, bifunctional, epoxy equivalent: 186)
Aliphatic epoxy resin (“Denacol (registered trademark)” EX-321, manufactured by Nagase ChemteX Corporation, functional group number: more than 2 and 3 or less, epoxy equivalent: 140)
Aliphatic epoxy resin (“Denacol (registered trademark)” EX-313, manufactured by Nagase ChemteX Corporation, functional group number: more than 2 and 3 or less, epoxy equivalent: 141)
Aliphatic epoxy resin (“Denacol (registered trademark)” EX-314, manufactured by Nagase ChemteX Corporation, trifunctional, epoxy equivalent: 144)
Aliphatic epoxy resin (“Denacol (registered trademark)” EX-421, manufactured by Nagase ChemteX Corporation, trifunctional, epoxy equivalent: 159)
Aliphatic epoxy resin ("Denacol (registered trademark)" EX-521, manufactured by Nagase ChemteX Corporation, trifunctional, epoxy equivalent: 183)
Aliphatic epoxy resin (“Denacol (registered trademark)” EX-411, manufactured by Nagase ChemteX Corp., tetrafunctional, epoxy equivalent: 229)
Aliphatic epoxy resin (“Denacol (registered trademark)” EX-614B, manufactured by Nagase ChemteX Corporation, tetrafunctional or higher, epoxy equivalent: 173).
・ Binaphthalene type epoxy resin ("Epiclon (registered trademark)" HP-4770, manufactured by DIC Corporation, bifunctional, epoxy equivalent: 204)
Naphthalene type epoxy resin (“Epiclon (registered trademark)” HP-4032D, manufactured by DIC Corporation, bifunctional, epoxy equivalent: 140)
Aliphatic epoxy resin ("Denacol (registered trademark)" EX-211, manufactured by Nagase ChemteX Corporation, bifunctional, epoxy equivalent: 138)
Bisphenol A type epoxy resin (“jER (registered trademark)” 825, manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 175)
Tetraglycidyl diaminodiphenyl methane (“Sumiepoxy (registered trademark)” ELM434, manufactured by Sumitomo Chemical Co., Ltd., epoxy equivalent: 125)
Biphenyl aralkyl type epoxy resin (NC-3000L, Nippon Kayaku Co., Ltd., epoxy equivalent: 269)
-Naphthalene aralkyl type epoxy resin (NC-7000, Nippon Kayaku Co., Ltd., epoxy equivalent: 230).

<Curing agent>
Component [B]
Dicyandiamide (DICY7, manufactured by Mitsubishi Chemical Corporation, active hydrogen equivalent: 12).

Component [C]
-4,4'-diaminodiphenyl sulfone ("Seika Cuca (registered trademark)"-S, manufactured by Wakayama Seika Kogyo Co., Ltd., active hydrogen group equivalent: 62).

Other curing agent, methyltetrahydrophthalic anhydride (HN-2200, manufactured by Hitachi Chemical Co., Ltd., active hydrogen equivalent: 151).
-Phenolic resin (H-4, manufactured by Meiwa Kasei Co., Ltd., active hydrogen equivalent: 105).

<Curing accelerator>
Component [D]
・ 3- (3,4-Dichlorophenyl) 1,1-dimethylurea (DCMU99, manufactured by Hodogaya Chemical Co., Ltd.)
2,4-Toluenebis (dimethylurea) (“Omicure®” 24, manufactured by Emerald Performance Materials, LLC).

Other curing accelerator, 2-methylimidazole (2MZ, manufactured by Shikoku Chemicals Co., Ltd.)
Tetraphenylphosphonium tetraphenylborate (TPP-K (registered trademark), manufactured by Hokuko Chemical Co., Ltd.).

<Thermoplastic resin>
-Polyethersulfone ("Sumika Excel (registered trademark)" PES5003P, manufactured by Sumitomo Chemical Co., Ltd.).

<Reinforcing fiber>
Carbon fiber (“Torayca (registered trademark)” T700S, manufactured by Toray Industries, Inc., tensile elastic modulus: 230 GPa, tensile strength: 4900 MPa).

(1) Preparation of Epoxy Resin Composition In a kneader, a predetermined amount of components other than [B] to [D] are added, the temperature is raised to 170 ° C. while kneading, and the mixture is kneaded at 170 ° C. for 1 hour. A liquid was obtained. The temperature was lowered while kneading to 80 ° C., [B] to [D] were added at 80 ° C. or lower, and further kneaded to obtain an epoxy resin composition.

(2) Preparation method of cured resin The epoxy resin composition obtained in (1) above was defoamed in a vacuum and then set to a thickness of 2 mm with a 2 mm thick “Teflon (registered trademark)” spacer. It was poured into the molded mold, heated from room temperature to 200 ° C. at a rate of 1.5 ° C./min, and then kept at 200 ° C. for 30 minutes to obtain a 2 mm thick plate-shaped resin cured product.
(3) Measuring method of bending elastic modulus and bending deflection of cured resin material Using a diamond cutter, a test piece having a width of 10 mm and a length of 60 mm was cut out from the cured resin material obtained in (2) above, and Instron Universal Using a testing machine (manufactured by Instron), the span length was 32 mm, the crosshead speed was 100 mm / min, three-point bending was performed according to JIS K7171 (1994), and the bending elastic modulus and bending deflection were measured. .

(4) Method for measuring glass transition temperature of cured resin product A sample having a width of 13 mm and a length of 50 mm was cut out from the cured resin product produced by the method of (2) above using a diamond cutter. Using a dynamic viscoelasticity measuring device (Rheometer RDA2: manufactured by Rheometrics), the sample was heated at a rate of temperature increase of 5 ° C./min, and the storage elastic modulus was measured in a torsion mode with a frequency of 1.0 Hz. It was. The onset temperature of the storage elastic modulus at this time was defined as the glass transition temperature.

(5) Method for measuring reaction rate of cured resin product Using a Fourier transform infrared spectrophotometer (IR Prestige-21: manufactured by Shimadzu Corporation), the epoxy resin composition produced by the method of (1) above and the above ( The area of the absorbance of the benzene ring peak (1510 cm-1) and the oxirane ring peak (910 cm-1) of the cured resin produced by the method 2) was measured to obtain the area ratio of the oxirane ring to the benzene ring. The area ratio of the oxirane ring to the benzene ring was determined from (the area of the oxirane ring peak) / (the area of the benzene ring peak). The reaction rate of the cured resin was calculated from (1- (area ratio of cured resin) / (area ratio of epoxy resin composition)) × 100.

(6) Preparation method of unidirectional prepreg The epoxy resin composition prepared by the method of (1) above was applied to a release paper using a reverse roll coater to prepare a resin film. Next, two resin films are overlapped on both sides of the carbon fiber on the carbon fiber aligned in one direction in the form of a sheet, heated and pressed to impregnate the resin composition, and the weight of the carbon fiber per unit area is 125 g / m ² , A T700S unidirectional prepreg with a fiber weight content of 68% was produced.

(7) Manufacturing method of fiber reinforced composite material by autoclave method After unidirectional prepreg produced according to (5) above is laminated in one direction so as to have a desired thickness, the autoclave is 200 ° C, 0.3 MPa. And cured by heating and pressing for 30 minutes to prepare a fiber-reinforced composite material.

(8) Tensile test method for fiber reinforced composite material A sample having a width of 12.5 mm and a length of 200 mm was cut out from a fiber reinforced composite material having a thickness of 1 mm produced by the method of (7) above using a diamond cutter. This sample was subjected to a 0 ° tensile test of the fiber reinforced composite material according to JIS K7073 (1988) using an Instron universal testing machine (manufactured by Instron), and the tensile strength was measured.

(9) Compression Test Method for Fiber Reinforced Composite Material A sample with a width of 12.5 mm and a length of 78 mm was cut out from the fiber reinforced composite material with a thickness of 1 mm produced by the method of (7) above using a diamond cutter. This sample was subjected to JIS K7076 (1991) using an Instron universal tester (Instron). The fiber reinforced composite material was subjected to a 0 ° compression test, and the compressive strength was measured. Moreover, after calculating | requiring real Vf based on the combustion method as described in JIS7075 (1991) from the test piece, the obtained bending strength was converted into Vf60%.

(10) Measurement of glass transition temperature of fiber reinforced composite material A sample having a width of 13 mm and a length of 50 mm was cut out from the fiber reinforced composite material prepared according to (7) above using a diamond cutter. Using a dynamic viscoelasticity measuring device (Rheometer RDA2: manufactured by Rheometrics), the sample was heated at a rate of temperature increase of 5 ° C./min, and the storage elastic modulus was measured in a torsion mode with a frequency of 1.0 Hz. It was. The onset temperature of the storage elastic modulus at this time was defined as the glass transition temperature.

  The epoxy resin composition, the prepreg, and the fiber reinforced composite material were prepared for each of the examples and comparative examples by the above method, and the results of measuring the characteristics are summarized in Tables 1 to 4.

Example 1
The component [A] is 50 parts by mass of HP-4700, the other epoxy resin is 50 parts by mass of jER825, the component [B] is 0.9 equivalent of DICY7, and the component [C] is 0.0% Seikacure-S. An epoxy resin composition was prepared using 1 equivalent and 3 parts by mass of DCMU99 as component [D]. The obtained resin composition was cured to obtain a cured resin. The obtained cured resin had good bending elastic modulus, bending deflection, glass transition temperature, and reaction rate. Moreover, a prepreg was produced using the obtained epoxy resin composition and reinforcing fibers, and this prepreg was laminated and cured to obtain a fiber-reinforced composite material. The obtained fiber reinforced composite material had good 0 degree tensile strength and 0 degree compressive strength.

(Examples 2 to 4)
An epoxy resin composition, a cured resin, and a fiber reinforced composite material were obtained in the same manner as in Example 1 except that the constituent element [A] was changed to EXA-4701, HP-4710, and EXA-4750, respectively. The physical properties of the obtained cured resin and fiber-reinforced composite material were good.

(Example 5)
5 parts by mass of HP-4700 as component [A], 70 parts by mass of jER825, 25 parts by mass of ELM434, 0.5 equivalent of DICY7 as component [B], and as component [C] An epoxy resin composition was prepared using 0.5 equivalent of Seikacure-S, 3 parts by mass of DCMU99 as the component [D], and 7 parts by mass of PES5003P as the thermoplastic resin. A resin cured product and a fiber reinforced composite material were obtained in the same manner as in Example 1 using the obtained resin composition. The physical properties of the cured resin and the fiber reinforced composite material were good.

(Example 6)
The epoxy resin composition, the cured resin, and the fiber reinforced composite material were the same as in Example 5, except that HP-4700 was 10 parts by mass as the component [A] and jER825 was 65 parts by mass as the other epoxy resin. Obtained. By making the compounding quantity of component [A] into the preferable range, the glass transition temperature of resin cured material and a fiber reinforced composite material improved compared with Example 5, and it became a more preferable range.

(Example 7)
As in Example 6, an epoxy resin composition, a cured resin, and a fiber reinforced composite material were prepared in the same manner as in Example 6 except that HP-4700 was 15 parts by mass as component [A] and jER825 was 60 parts by mass as the other epoxy resin. Obtained. By making the compounding quantity of component [A] into the more preferable range, the glass transition temperature of resin hardened | cured material and a fiber reinforced composite material improved compared with Example 6, and also became the preferable range.

(Example 8)
55 parts by mass of HP-4700 as component [A], 45 parts by mass of jER825 as other epoxy resin, 0.9 equivalent of DICY7 as component [B], and 0.1% of Seikacure-S as component [C]. An epoxy resin composition was prepared using 1 equivalent of 1 part by mass of DCMU99 as component [D]. A resin cured product and a fiber reinforced composite material were obtained in the same manner as in Example 1 using the obtained resin composition. The physical properties of the cured resin and the fiber reinforced composite material were good.

Example 9
The epoxy resin composition, the cured resin, and the fiber reinforced composite material were the same as in Example 8 except that HP-4700 was 50 parts by mass as component [A] and jER825 was 50 parts by mass as the other epoxy resin. Obtained. By making the compounding quantity of component [A] into a preferable range, the bending deflection amount of the resin cured product compared with Example 8 was improved, and it became a more preferable range. As a result, the tensile strength of the fiber reinforced composite material was improved as compared with Example 8.

(Example 10)
The epoxy resin composition was the same as in Example 9, except that 30 parts by mass of HP-4700 as component [A], 70 parts by mass of jER825 as the other epoxy resin, and 4 parts by mass of PES5003P as the thermoplastic resin were used. A cured resin and a fiber reinforced composite material were obtained. By making the compounding quantity of component [A] into a more preferable range, the bending deflection amount of the resin cured product was improved as compared with Example 9, and it became a more preferable range. As a result, the tensile strength of the fiber reinforced composite material was improved as compared with Example 8.

(Example 11)
25 parts by mass of HP-4700 as component [A], 75 parts by mass of jER825 as other epoxy resin, 0.9 equivalent of DICY7 as component [B], and Seikacure-S as 0.0 as component [C]. An epoxy resin composition was prepared using 1 equivalent, 1.5 parts by mass of DCMU99 as component [D], and 4 parts by mass of PES5003P as a thermoplastic resin. A resin cured product and a fiber reinforced composite material were obtained in the same manner as in Example 1 using the obtained resin composition. The physical properties of the cured resin and the fiber reinforced composite material were good.

(Example 12)
The epoxy resin composition, the cured resin, and the fiber reinforced composite were the same as in Example 11, except that the compounding amounts of the component [B] and the component [C] were 0.8 equivalent and 0.2 equivalent, respectively. Obtained material. By making the compounding amounts of the constituent element [B] and the constituent element [C] into a more preferable range, the glass transition temperature of the resin cured product and the fiber reinforced composite material is improved as compared with Example 11, and is further in the preferable range. .

(Example 13)
The epoxy resin composition, the cured resin, and the fiber reinforced composite were the same as in Example 12, except that the blending amounts of the component [B] and the component [C] were 0.7 equivalent and 0.3 equivalent, respectively. Obtained material. By making the blending amounts of the constituent element [B] and the constituent element [C] into a more preferable range, the glass transition temperature of the resin cured product and the fiber reinforced composite material was improved as compared with Example 12, and became the most preferable range. .

(Example 14)
20 parts by mass of HP-4700 as component [A], 80 parts by mass of jER825 as other epoxy resin, 0.2 equivalent of DICY7 as component [B], and Seikacure-S as 0. An epoxy resin composition was prepared using 8 equivalents, 1.5 parts by mass of DCMU99 as component [D], and 5 parts by mass of PES5003P as a thermoplastic resin. A resin cured product and a fiber reinforced composite material were obtained in the same manner as in Example 1 using the obtained resin composition. The physical properties of the cured resin and the fiber reinforced composite material were good.

(Example 15)
The epoxy resin composition, the cured resin, and the fiber reinforced composite were the same as in Example 14 except that the compounding amounts of the component [B] and the component [C] were 0.3 equivalent and 0.7 equivalent, respectively. Obtained material. By setting the blending amounts of the constituent element [B] and the constituent element [C] in a more preferable range, the resin cured product and the amount of bending deflection were improved as compared with Example 14, and the more preferable range was achieved. As a result, the tensile strength of the fiber-reinforced composite material was improved as compared with Example 14.

(Example 16)
The epoxy resin composition, the cured resin, and the fiber reinforced composite were the same as in Example 14 except that the blending amounts of the component [B] and the component [C] were 0.4 equivalent and 0.6 equivalent, respectively. Obtained material. By making the blending amounts of the constituent element [B] and the constituent element [C] into a more preferable range, the resin cured product and the amount of bending deflection were improved as compared with Example 15, and the most preferable range was obtained. As a result, the tensile strength of the fiber reinforced composite material was improved as compared with Example 15.

(Example 17)
25 parts by mass of HP-4700 as component [A], 75 parts by mass of jER825 as other epoxy resin, 0.9 equivalent of DICY7 as component [B], and Seikacure-S as 0.0 as component [C]. An epoxy resin composition was prepared using 1 equivalent, 1.5 parts by mass of DCMU99 as component [D], and 4 parts by mass of PES5003P as a thermoplastic resin. A resin cured product and a fiber reinforced composite material were obtained in the same manner as in Example 1 using the obtained resin composition. The physical properties of the cured resin and the fiber reinforced composite material were good.

(Example 18)
25 parts by mass of HP-4700 as component [A], 75 parts by mass of jER825 as other epoxy resin, 0.9 equivalent of DICY7 as component [B], and Seikacure-S as 0.0 as component [C]. An epoxy resin composition was prepared using 1 equivalent, 3 parts by mass of DCMU99 as component [D], and 4 parts by mass of PES5003P as a thermoplastic resin. A resin cured product and a fiber reinforced composite material were obtained in the same manner as in Example 1 using the obtained resin composition. The physical properties of the cured resin and the fiber reinforced composite material were good.

(Example 19)
An epoxy resin composition, a cured resin, and a fiber-reinforced composite material were obtained in the same manner as in Example 18 except that the amount of component [D] was 2 parts by mass. By making the compounding quantity of component [D] into the more preferable range, the glass transition temperature of resin hardened | cured material and a fiber reinforced composite material improved compared with Example 18. FIG.

(Example 20)
An epoxy resin composition, a cured resin, and a fiber-reinforced composite material were obtained in the same manner as in Example 18 except that the amount of component [D] was 0.1 parts by mass. The physical properties of the cured resin and the fiber reinforced composite material were good.

(Example 21)
An epoxy resin composition, a cured resin, and a fiber-reinforced composite material were obtained in the same manner as in Example 20 except that the amount of component [D] was 0.2 parts by mass. By making the compounding quantity of component [D] into the more preferable range, the reaction rate of the resin cured material compared with Example 20 improved.

(Example 22)
An epoxy resin composition, a cured resin, and a fiber-reinforced composite material were obtained in the same manner as in Example 19 except that the amount of component [D] was 1 part by mass. By making the compounding quantity of component [D] into a more preferable range, the glass transition temperature of resin hardened | cured material and a fiber reinforced composite material improved compared with Example 19. FIG.

(Example 23)
25 parts by mass of HP-4700 as component [A], 75 parts by mass of jER825 as other epoxy resin, 0.5 equivalent of DICY7 as component [B], and Seikacure-S as 0.0 as component [C]. An epoxy resin composition was prepared using 5 equivalents, 0.5 part by mass of DCMU99 as component [D], and 4 parts by mass of PES5003P as the thermoplastic resin. A resin cured product and a fiber reinforced composite material were obtained in the same manner as in Example 1 using the obtained resin composition. The physical properties of the cured resin and the fiber reinforced composite material were good.

(Example 24)
An epoxy resin composition, a cured resin, and a fiber-reinforced composite material were obtained in the same manner as in Example 23 except that the component [D] was changed to Omicure 24. The physical properties of the cured resin and the fiber reinforced composite material were good.

(Example 25)
10 parts by mass of HP-4700 as component [A], 85 parts by mass of jER825 as other epoxy resin, 5 parts by mass of ELM434, 0.5 equivalent of DICY7 as component [B], and as component [C] An epoxy resin composition was prepared using 0.5 equivalents of Seikacure-S, 0.5 parts by mass of DCMU99 as component [D], and 7 parts by mass of PES5003P as a thermoplastic resin. A resin cured product and a fiber reinforced composite material were obtained in the same manner as in Example 1 using the obtained resin composition. The physical properties of the cured resin and the fiber reinforced composite material were good.

(Example 26)
As other epoxy resins, an epoxy resin composition, a cured resin, and a fiber reinforced composite material were obtained in the same manner as in Example 25 except that 80 parts by mass of jER825 and 5 parts by mass of YX-4000 were blended. By blending YX-4000 within a preferable range, the glass transition temperature of the resin cured product and the fiber reinforced composite material was improved as compared with Example 25.

(Example 27)
As other epoxy resins, similar to Example 26, except that 65 parts by mass of jER825, 20 parts by mass of YX-4000, and 5 parts by mass of PES5003P as a thermoplastic resin were blended, an epoxy resin composition, a cured resin, A fiber reinforced composite material was obtained. By blending YX-4000 within a more preferable range, the glass transition temperature of the resin cured product and the fiber-reinforced composite material was improved as compared with Example 26.

(Example 28)
As other epoxy resins, except that 50 parts by mass of jER825, 35 parts by mass of YX-4000, and 5 parts by mass of PES5003P as a thermoplastic resin were blended, an epoxy resin composition, a cured resin, A fiber reinforced composite material was obtained. By blending YX-4000 within a more preferable range, the glass transition temperature of the resin cured product and the fiber-reinforced composite material was improved as compared with Example 26.

(Example 29)
As component [A], HP-4700 is 15 parts by mass, as other epoxy resin is jER825 is 70 parts by mass, ELM434 is 15 parts by mass, component [B] is DICY7 as 0.2 equivalent, and component [C] is An epoxy resin composition was prepared using 0.8 equivalent of Seikacure-S, 1.5 parts by mass of DCMU99 as the component [D], and 6 parts by mass of PES5003P as the thermoplastic resin. A resin cured product and a fiber reinforced composite material were obtained in the same manner as in Example 1 using the obtained resin composition. The physical properties of the cured resin and the fiber reinforced composite material were good.

(Example 30)
An epoxy resin composition, a cured resin, and a fiber-reinforced composite material were obtained in the same manner as in Example 29 except that EX-411 was 25 parts by mass and jER825 was 45 parts by mass as other epoxy resins. The physical properties of the cured resin and the fiber reinforced composite material were good.

(Example 31)
An epoxy resin composition, a cured resin, and a fiber-reinforced composite material were obtained in the same manner as in Example 29 except that EX-411 was 3 parts by mass and jER825 was 67 parts by mass as other epoxy resins. By blending an aliphatic epoxy resin having more than two epoxy groups in a preferred range, the amount of bending deflection of the cured resin was improved compared to Example 29, and it was further in a preferred range. As a result, the tensile strength of the fiber reinforced composite material was improved as compared with Example 29.

(Example 32)
An epoxy resin composition, a cured resin, and a fiber-reinforced composite material were obtained in the same manner as in Example 30, except that EX-411 was 20 parts by mass and jER825 was 50 parts by mass as other epoxy resins. By blending an aliphatic epoxy resin having more than two epoxy groups within a preferable range, the glass transition temperature of the cured resin and the fiber-reinforced composite material was improved as compared with Example 30.

(Example 33)
An epoxy resin composition, a cured resin, and a fiber-reinforced composite material were obtained in the same manner as in Example 31 except that EX-411 was 5 parts by mass and jER825 was 65 parts by mass as other epoxy resins. By blending an aliphatic epoxy resin having more than two epoxy groups in a more preferable range, the bending deflection amount of the cured resin was improved compared with Example 31, and the most preferable range was obtained. As a result, the tensile strength of the fiber reinforced composite material was improved as compared with Example 31.

(Example 34)
An epoxy resin composition, a cured resin, and a fiber-reinforced composite material were obtained in the same manner as in Example 32 except that EX-411 was 15 parts by mass and jER825 was 55 parts by mass as other epoxy resins. By blending an aliphatic epoxy resin having more than two epoxy groups in a more preferable range, the glass transition temperature of the cured resin and the fiber-reinforced composite material was improved as compared with Example 32.

(Example 35)
20 parts by mass of HP-4700 as component [A], 25 parts by mass of EX-321 as other epoxy resins, 45 parts by mass of jER825, 15 parts by mass of ELM434, 0.5% of DICY7 as component [B] An epoxy resin composition was prepared using 0.5 equivalent of Seikacure-S as the component [C], 0.5 part by mass of DCMU99 as the component [D], and 5 parts by mass of PES5003P as the thermoplastic resin. . A resin cured product and a fiber reinforced composite material were obtained in the same manner as in Example 1 using the obtained resin composition. The physical properties of the cured resin and the fiber reinforced composite material were good.

(Examples 36 to 41)
As other epoxy resins, except that EX-313, EX-314, EX-421, EX-521, EX-411, and EX-614B were used instead of EX-321, respectively, the same as in Example 35 An epoxy tree composition was prepared. A resin cured product and a fiber reinforced composite material were obtained in the same manner as in Example 1 using the obtained resin composition. The physical properties of the cured resin and the fiber reinforced composite material were good.

(Example 42)
20 parts by mass of HP-4700 as component [A], 20 parts by mass of YX-4000, 10 parts by mass of EX-411, 50 parts by mass of jER825, and 0 of DICY7 as component [B] .5 equivalents, 0.5 equivalents of Seikacure-S as component [C], 0.5 parts by mass of DCMU99 as component [D], and 5 parts by mass of PES5003P as thermoplastic resin, Prepared. A resin cured product and a fiber reinforced composite material were obtained in the same manner as in Example 1 using the obtained resin composition. The physical properties of the cured resin and the fiber reinforced composite material were good.

(Example 43)
An epoxy resin composition was prepared in the same manner as in Example 28 except that NC-3000L was used instead of YX-4000 as the other epoxy resin. Compared with Example 28, although the glass transition temperature of the resin cured product and the fiber-reinforced composite material was lowered, it was within the preferred range and was good. Moreover, the physical properties of the other cured resin and fiber reinforced composite material were also good.

(Example 44)
An epoxy resin composition was prepared in the same manner as in Example 40 except that EX-211 was used instead of EX-411 as the other epoxy resin. Compared to Example 40, although the glass transition temperature of the resin cured product and the fiber-reinforced composite material was lowered, it was within the preferred range and was good. Moreover, the physical properties of the other cured resin and fiber reinforced composite material were also good.

(Comparative Example 1)
An epoxy resin composition was prepared in the same manner as in Example 1 except that 100 parts by mass of jER825 was used as the other epoxy resin and 10 parts by mass of PES5003P was used as the thermoplastic resin without using the component [A]. Since component [A] was not used, the heat resistance was remarkably lowered as compared with Example 1, which was not preferable.

(Comparative Example 2)
An epoxy resin composition was prepared in the same manner as in Example 5 except that the component [B] was not used and the component [C] was changed to 1 equivalent. Since component [B] was not used, the amount of bending deflection and the reaction rate of the cured resin were greatly reduced compared to Example 5, which was not preferable. As a result, the tensile strength of the fiber reinforced composite material also decreased, which was not preferable. Moreover, since the glass transition temperature of the resin cured product and the fiber reinforced composite material was also lowered, it was not preferable.

(Comparative Example 3)
An epoxy resin composition was prepared in the same manner as in Example 5, except that the component [C] was not used and the component [B] was 1 equivalent. Since component [C] was not used, compared with Example 5, the glass transition temperature of the resin cured product and the fiber-reinforced composite material was lowered, which was not preferable.

(Comparative Example 4)
An epoxy resin composition was prepared in the same manner as in Example 5 except that the component [D] was not used. Since component [D] was not used, the amount of bending deflection and the reaction rate of the cured resin were greatly reduced compared to Example 5, which was not preferable. As a result, the tensile strength of the fiber reinforced composite material also decreased, which was not preferable. Moreover, since the glass transition temperature of the resin cured product and the fiber reinforced composite material was also lowered, it was not preferable.

(Comparative Example 5)
An epoxy resin composition was prepared in the same manner as in Example 18 except that HP-4770, which is a bifunctional binaphthalene type epoxy resin, was used instead of HP-4700 of the component [A]. Since bifunctional binaphthalene epoxy resin was used in place of component [A], the glass transition temperature of the cured resin and the fiber-reinforced composite material was lowered compared to Example 18, which was not preferable.

(Comparative Example 6)
An epoxy resin composition was prepared in the same manner as in Example 18 except that HP-4032D, which is a bifunctional naphthalene type epoxy resin, was used instead of HP-4700 of the component [A]. Since a bifunctional naphthalene epoxy resin was used instead of component [A], the glass transition temperature of the resin cured product and the fiber-reinforced composite material was lowered compared to Example 18, which was not preferable.

(Comparative Example 7)
An epoxy resin composition was prepared in the same manner as in Example 18 except that NC-7000, which is a naphthalene aralkyl type epoxy resin, was used instead of HP-4700 of component [A]. Since naphthalene aralkyl type epoxy resin was used instead of component [A], the glass transition temperature of the cured resin and the fiber-reinforced composite material was lower than that of Example 18, which was not preferable.

(Comparative Example 8)
The epoxy resin composition was the same as in Example 5, except that 1 equivalent of HN-2200 was used in place of components [B] and [C], and 0.5 parts by mass of 2MZ was used in place of component [D]. A product was prepared. As a result, the bending deflection amount of the cured resin was greatly reduced compared with Example 5, which was not preferable.

(Comparative Example 9)
Epoxy resin composition as in Example 5, except that 1 equivalent of H-4 was used instead of components [B] and [C], and 5 parts by mass of TPP-K was used instead of component [D]. Was prepared. As a result, the amount of bending deflection of the cured resin and the glass transition temperature were greatly reduced as compared with Example 5, which was not preferable.

(Comparative Example 10)
An epoxy resin composition was prepared in the same manner as in Example 11 except that 3 parts by mass of 2MZ was used instead of the component [D]. As a result, compared with Example 11, the glass transition temperature of the cured resin was lowered, which was not preferable.

(Comparative Example 11)
An epoxy resin composition was prepared in the same manner as in Example 11 except that 5 parts by mass of TPP-K was used instead of the component [D]. As a result, compared with Example 11, the glass transition temperature of the cured resin was lowered, which was not preferable.

Claims (8)

An epoxy resin composition comprising the following [A] to [D].
[A] Trifunctional or higher binaphthalene type epoxy resin [B] Dicyandiamide or its derivative [C] Diaminodiphenylsulfone or its derivative [D] Urea compound The epoxy resin composition of Claim 1 which contains 10-50 mass parts of component [A] with respect to 100 mass parts of all the components of an epoxy resin. The constituent elements [B] and [C] are included in a range satisfying the following conditions (I) and (II) with respect to 1 equivalent of the epoxy group of all the epoxy resin components: An epoxy resin composition according to claim 1.
(I) The equivalent of active hydrogen group of component [B] is 0.3 to 0.8 equivalent (II) The equivalent of active hydrogen group of component [C] is 0.2 to 0.7 equivalent The epoxy resin composition in any one of Claims 1-3 containing 0.1-3 mass parts of component [D] with respect to 100 mass parts of all the components of an epoxy resin. Furthermore, the epoxy resin composition in any one of Claims 1-4 containing a biphenyl type epoxy resin. Furthermore, the epoxy resin composition in any one of Claims 1-5 containing the aliphatic epoxy resin which has more than two epoxy groups. The molding material containing the epoxy resin composition and reinforcement fiber in any one of Claims 1-6. A fiber-reinforced composite material obtained by molding the molding material according to claim 7.