JP2000355630A - Member made from fiber-reinforced plastic - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a member free from delamination and excellent in dimensional stability by using an epoxy resin composition containing reinforcing fibers having specified physical properties, a curing agent, an epoxy resin or a component of a compound having a functional group reactive with the curing agent and an amide bond and a polyester polyurethane component. SOLUTION: This member is made from reinforcing fibers having a tensile modulus of at least 290 GPa, such as modified carbon fibers, a curing agent such as 4,4'-diaminodiphenylmethane, and an epoxy resin composition comprising an epoxy resin or a component comprising a compound having one functional group reactive with the curing agent and at least one amido bond and an aromatic-ring-containing polyester polyurethane in amounts of 0.5-15 wt.% and 1-15 wt.% based on the entire epoxy resin. The member has a cutting loss of at most 1 wt.% wet cut by a wet process. The modified carbon fibers have a surface carboxyl concentration COOH/C of 0.002-0.03 and a surface oxygen concentration O/C of 0.02-0.3 as measured by (modified) X-ray photoelectron spectroscopy.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fiber-reinforced plastic member which can be suitably used for general industrial use, sports and leisure use, and the like.

[0002]

2. Description of the Related Art Fiber-reinforced plastic members having a prepreg composed of a reinforcing fiber and a matrix resin as an intermediate base material have excellent mechanical strength, so that they are used for sports, aerospace, and general industrial applications. Widely used in Particularly in sports applications, golf shafts, fishing rods, rackets for tennis and badminton, sticks for hockey, and the like can be cited as main applications.

[0003] In these applications, a product is completed by combining various metals and plastics in addition to a fiber reinforced plastic member. At this time, a cutting process is performed on the bonding portion in order to increase the bonding strength of the various members. May be required.

In a conventional fiber reinforced plastic member,
In such a cutting process, there is a problem that the material is easily cut more than necessary, and the reinforcing fibers and the matrix resin fall off due to phase separation, and the dimensional stability of the fiber reinforced plastic member is reduced. This phase separation, when the content of the reinforcing fibers used is high, or when the absolute amount of the matrix resin is small, or when using a prepreg as an intermediate substrate,
When the unit weight of the prepreg was small, it became remarkable in some cases.

[0005] Since such a fiber-reinforced plastic member may have a reduced mechanical strength, the fiber-reinforced plastic member is reinforced by using a metal, or the outer layer portion is reinforced by increasing the content of a matrix resin. According to this, however, the response to the weight reduction generally required for the above-mentioned applications has been extremely insufficient.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to prevent unnecessary cutting during cutting, and to reduce flakes due to phase separation between the reinforcing fiber and the matrix resin, and to reduce dimensional stability. It is an object of the present invention to provide a fiber-reinforced plastic member which is excellent in the mechanical strength and has little decrease in mechanical strength.

[0007]

The present invention has the following configuration to achieve the above object. That is, the tensile modulus is 2
A fiber-reinforced plastic member comprising a reinforcing fiber having a strength of 90 Gpa or more, and a curing agent and an epoxy resin composition containing the following component (A) and / or component (B). The fiber reinforced plastic member has a cut amount of 1% by weight or less by wet cutting of the reinforced plastic member. (A) a compound having one functional group and one or more amide bonds capable of reacting with an epoxy resin or a curing agent in the molecule (B) a polyester polyurethane having an aromatic ring in the molecule

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The present inventors have conducted intensive studies on the above-mentioned problems, and heated an epoxy resin composition comprising a reinforcing fiber having a tensile elastic modulus of a specific value or more, a curing agent and a specific compound. Then, by curing the matrix resin, the amount of cutting of the fiber reinforced plastic member by the cutting process becomes smaller than before, and the fiber reinforced plastic member falls off due to the separation of the reinforcing fiber and the matrix resin. Have been found to effectively deter the present invention, and have reached the present invention.

[0009] The fiber-reinforced plastic member of the present invention comprises:
It is composed of a reinforcing fiber having a tensile modulus of at least 290 Gpa and a matrix resin obtained by heating and curing the epoxy resin composition. Here, the epoxy resin is used because it is excellent in heat resistance, water resistance, and adhesion, but other thermosetting resins such as an unsaturated polyester resin may be used.

In the present invention, carbon fiber is preferably used as the reinforcing fiber because of its excellent mechanical strength represented by tensile modulus and durability, but other reinforcing fibers are used in order to appropriately increase the adhesiveness. Glass fibers, aramid fibers, boron fibers, alumina fibers, silicon carbide fibers, etc., which have been subjected to a surface treatment, can also be used as long as their tensile modulus of elasticity can be sufficiently ensured. It can also be used. Also, carbon fiber
So-called graphite fibers are included, and specifically,
Various materials such as polyacrylonitrile, pitch, rayon and the like can be used. Among them, polyacrylonitrile-based ones from which high-strength carbon fibers can be easily obtained are preferably used.

The reinforced fiber may be a twisted yarn, untwisted yarn, or non-twisted yarn, but untwisted yarn or non-twisted yarn is preferable because it achieves both moldability and mechanical strength of a fiber-reinforced plastic member. Further, as the form of the reinforcing fiber, one in which the fiber directions are aligned in one direction or a woven fabric can be used.
The woven fabric can be freely selected from plain weave, satin weave, and the like according to the site to be used and the application.

In the present invention, it is necessary that the tensile modulus of the reinforcing fiber is 290 Gpa or more, and preferably 330 Gpa or more. If the tensile modulus is less than 290 Gpa, the amount of the fiber-reinforced plastic member cut by the cutting process may be excessive, and as a result, particularly when manufacturing sporting goods such as lightweight fishing rods and golf shafts. For example, the mechanical strength of the obtained finished product may decrease. Here, a tensile modulus of about 800 GPa, preferably about 500 GPa, and more preferably about 400 GPa is sufficient for achieving the effects of the present invention.

The cutting property of a fiber-reinforced plastic member, that is, the difficulty of cutting, is improved by increasing the adhesion between the reinforcing fiber and the matrix resin (hereinafter simply referred to as adhesiveness) together with the tensile modulus of the reinforcing fiber. , Can be improved.

In order to enhance the adhesiveness, the surface of the reinforcing fiber is modified by some treatment, or the epoxy resin composition is improved to increase the affinity with the surface of the reinforcing fiber. A method in which the used reinforcing fiber and the epoxy resin composition are used in combination can be adopted.

For the modification of the carbon fiber surface as a reinforcing fiber, the following method (1) or (2) can be employed. (1) Adjusting the functional group concentration on the carbon fiber surface. That is, surface specific oxygen concentration (hereinafter abbreviated as O / C) measured by X-ray photoelectron spectroscopy, surface carboxyl group concentration (hereinafter COO) measured by chemically modified X-ray photoelectron spectroscopy.
H / C) is a specific range.

Specifically, the O / C of the carbon fiber surface is
It is preferably 0.02 or more, preferably 0.04 or more, and more preferably 0.06 or more. O /
When C is less than 0.02, the affinity for a polar group in the matrix resin described below decreases, and the 90 ° tensile strength of the fiber reinforced plastic member may not be improved.
Further, the upper limit of O / C is 0.3 or less, preferably 0.25 or less. If the O / C exceeds 0.3, the affinity between the carbon fiber and the polar group in the matrix resin becomes stronger, but the oxide layer having a strength considerably lower than the strength originally possessed by the carbon fiber itself is formed by the carbon fiber. Therefore, the resulting fiber-reinforced plastic member has low mechanical strength.

On the other hand, the COOH / C of the carbon fiber is preferably at least 0.002, more preferably at least 0.005. When COOH / C is less than 0.002, the affinity for the polar group in the matrix resin is reduced, and the 90 ° tensile strength of the fiber reinforced plastic member may not be improved. Further, the upper limit of COOH / C is 0.03 or less, preferably 0.02 or less. C
When OOH / C exceeds 0.03, although the affinity between the carbon fiber and the polar group in the matrix resin becomes strong, the oxide layer having much lower strength than the carbon fiber itself originally has is formed by the carbon fiber. Therefore, the resulting fiber-reinforced plastic member has low mechanical strength. Further, the curing speed of the matrix resin may be delayed.

The carbon fiber having the above-specified O / C and COOH / C ranges can be obtained by performing an electrolytic oxidation treatment or an oxidation treatment in a gas phase or a liquid phase. Among them, it is preferable to perform the electrolytic oxidation treatment because the oxidation treatment can be performed in a short time and the oxidation treatment can be easily controlled.

The electrolytic solution used for the electrolytic oxidation treatment may be either acidic or alkaline. Specific examples of the electrolyte dissolved in the acidic electrolyte include inorganic acids such as sulfuric acid and nitric acid, organic acids such as acetic acid and butyric acid, and salts such as ammonium sulfate and ammonium hydrogen sulfate. Among them, sulfuric acid and nitric acid showing strong acidity can be preferably used. Specific examples of the electrolyte dissolved in the alkaline electrolyte include hydroxides such as sodium hydroxide and potassium hydroxide, ammonia, inorganic salts such as sodium carbonate and sodium hydrogen carbonate, and organic salts such as sodium acetate and sodium benzoate. And further potassium salts, barium salts or other metal salts thereof, and ammonium salts,
An organic compound such as tetraethylammonium hydroxide or hydrazine may be mentioned, but from the viewpoint of preventing curing failure of the resin, ammonium carbonate, ammonium hydrogencarbonate and tetraalkylammonium hydroxide containing no alkali metal can be preferably used.

The amount of electricity to be supplied can be optimized according to the degree of carbonization of the carbon fibers. From the viewpoint of appropriately suppressing the decrease in the crystallinity of the surface layer, the amount of electricity is 3 to 500.
Coulomb / g range is preferred, preferably 5-2.
It is better to be in the range of 00 coulomb / g.

After the electrolytic oxidation treatment, the yarn is preferably washed with water and dried. At the time of drying, if the temperature is too high, the functional group present on the outermost surface of the carbon fiber is easily lost by thermal decomposition, so it is desirable to set the drying temperature as low as possible,
Drying at 250 ° C. or less, preferably 210 ° C. or less is good.

In addition, by such a treatment, the roughness of the carbon fiber surface can be increased at the same time, whereby the above-mentioned adhesiveness can be enhanced. (2) To reduce the crystal size of the carbon fiber. That is,
The purpose is to make the crystal size Lc of the carbon fiber measured by the wide-angle X-ray diffraction method a specific range and increase the number of active sites.

Specifically, the crystal size Lc of the carbon fiber is preferably 15 to 70 ng straws, and more preferably 20 to 70 ng straws.
It is preferably 35 angstroms, more preferably 20 to 30 angstroms.

According to the present invention, in order to enhance the affinity with the reinforcing fiber surface, an epoxy resin composition containing a specific compound is heated and cured to form a matrix resin, so that a great effect can be obtained. They have found what they can get.

In the present invention, the epoxy resin constituting the matrix resin is a compound having two or more epoxy groups in a molecule.

In the present invention, in order to improve the machinability of the fiber reinforced plastic member, the adhesiveness is increased and the matrix resin is JIS K7203.
High flexural modulus as measured by JIS K71
Since it is preferable that the tensile elongation as measured at 13 is large, the epoxy resin having two epoxy groups in the molecule is used in an amount of 70 to 100% by weight based on 100% by weight of the total epoxy resin in the epoxy resin composition. % Is preferred.

Specific examples of the epoxy resin in the present invention include glycidyl ether obtained from a polyol, glycidylamine obtained from an amine having a plurality of active hydrogens, glycidyl ester obtained from a polycarboxylic acid, and a plurality of glycidyl esters in a molecule. A polyepoxide obtained by oxidizing a compound having a heavy bond is exemplified.

Specific examples of glycidyl ether include bisphenol A epoxy resin obtained from bisphenol A, bisphenol F epoxy resin obtained from bisphenol F, bisphenol S epoxy resin obtained from bisphenol S, and tetrabromobisphenol A. Bisphenol type epoxy resin such as tetrabromobisphenol A type epoxy resin.

Specific examples of the glycidyl ether include a novolak type epoxy resin which is a glycidyl ester of novolak obtained from a phenol derivative such as phenol, alkylphenol, or halogenated phenol.

Specific examples of glycidyl esters include diglycidyl phthalate, diglycidyl terephthalate, and diglycidyl dimer.

Further, other epoxy resins having a glycidyl group include triglycidyl isocyanurate.

In the present invention, a curing agent is added to the epoxy resin composition. As a specific example of the curing agent, 4,4'-
Aromatic amines having active hydrogen such as diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, m-phenylenediamine, m-xylylenediamine, diethylenetriamine, triethylenetetramine, isophoronediamine Aliphatic amines having active hydrogens such as bis (aminomethyl) norbornane, bis (4-aminocyclohexyl) methane, dimer acid ester of polyethyleneimine, epoxy compounds, acrylonitrile, phenol and formaldehyde Thiourea and other modified amines obtained by reacting them, dimethylaniline, dimethylbenzylamine, 2,4,6-tris (dimethylaminomethyl) phenol and third compounds having no active hydrogen such as 1-substituted imidazole Amines, dicyandiamide, tetramethylguanidine, carboxylic anhydrides such as hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, adipic hydrazide or naphthalenedicarboxylic hydrazide And polyphenol compounds such as novolak resins, polymercaptans such as esters of thioglycolic acid and polyol, Lewis acid complexes such as boron trifluoride ethylamine complex, and aromatic sulfonium salts.

It is preferable to combine an appropriate curing aid with these curing agents in order to enhance the curing activity. Specifically, 3-phenyl-1,1-dimethylurea, 3- (3,4-dichlorophenyl) -1,1-dimethylurea (DCMU), and 3- (3-chloro-4-methylphenyl) are added to dicyandiamide. ) -1,1-Dimethylurea, 2,4-bis (3,
Examples include a combination of a urea derivative such as (3-dimethylureido) toluene as a curing aid, and a combination of a carboxylic acid anhydride or a novolak resin with a tertiary amine as a curing aid.

By making the epoxy resin composition as described above, the flexural modulus of the matrix resin in the fiber reinforced plastic member can be at least 3.1.
GPa or more, preferably 3.3 GPa or more. Also, the tensile elongation of the matrix resin can be 8% or more, preferably 10% or more. Furthermore, in the present invention, it is necessary to blend the constituent (A) and / or the constituent (B) described in detail below, whereby the fiber obtained in combination with the above-mentioned properties is obtained. In a reinforced plastic member, performance such as machinability can be further improved.

In the present invention, the constituent element (A) is a compound having one functional group capable of reacting with an epoxy resin or a curing agent and one or more amide bonds in the molecule. This compound is blended as a highly polar compound for increasing the adhesiveness.

The term "amide bond" as used herein means a partial structure comprising a group selected from a carbonyl group, a thiocarbonyl group, a sulfonyl group, and a phosphoryl group, and a nitrogen atom bonded to the carbon by a single bond. A typical compound having an amide bond is a carboxylic acid amide, but may have an amide bond in a part of the ring, or may have a more complex structure such as imide, urethane, urea, or the like.
It may have a structure such as biuret, hydantoin, carboxylic acid hydrazide, hydroxamic acid, semicarbazide, semicarbazone and the like.

The carbonyl oxygen of the amide bond forms a strong hydrogen bond with a hydrogen atom bonded to oxygen or nitrogen. Therefore,
A hydrogen bond with a hydrogen atom such as a carboxyl group or a hydroxyl group present on the surface layer of the reinforcing fiber is generated, thereby increasing the adhesiveness.

Further, since the carbonyl group of the amide bond is a strong permanent dipole, an organic dipole is formed on a reinforcing fiber having a high polarizability such as a carbon fiber, and the adhesive property is improved by an electric attractive force of the dipole-dipole. Enhance.

If the compound having an amide bond does not have a functional group capable of reacting with the epoxy resin or the curing agent in the molecule, the adhesion between the reinforcing fiber and the matrix resin may be insufficient due to phase separation. The compound having an amide bond may have a functional group capable of reacting with an epoxy resin or a curing agent in a molecule, but such a compound may have a resin composition. As the material is cured, it becomes a part of the matrix resin network, and there is no fear that such an adverse effect will occur.

It is known that an epoxy resin composition containing a compound having two or more functional groups capable of reacting with an epoxy resin or a curing agent and one or more amide bonds in the molecule is used for a fiber-reinforced plastic member. However, no remarkable improvement in adhesiveness has been confirmed with these known techniques.
However, the epoxy resin composition containing a compound having one functional group and one or more amide bonds capable of reacting with an epoxy resin or a curing agent in the molecule, which the present inventors have found, has a remarkable effect. You.

The reason for this is that a compound having two or more functional groups capable of reacting with an epoxy resin or a curing agent in a molecule is chemically bonded to an epoxy resin network at two or more locations, so that an oxygen atom of an amide bond is not bonded. A compound having one functional group that can react with an epoxy resin or a curing agent in a molecule, while not being sufficiently close to the surface of the reinforcing fiber, is chemically bonded to the epoxy resin network at only one place. The present inventors presume that the degree of freedom is large, and the oxygen atom of the carbonyl group is likely to come into contact with the surface of the reinforcing fiber.

Further, the component (A) has an effect of increasing not only the adhesiveness but also the bending elastic modulus of the matrix resin. This is considered to be because the oxygen of the hydroxyl group and the carbonyl group present in the epoxy resin forms a strong hydrogen bond and restricts the molecular motion.

The functional groups capable of reacting with the epoxy resin include carboxyl groups, phenolic hydroxyl groups, amino groups,
Examples include a secondary amine structure and a mercapto group. Examples of the functional group which can react with the curing agent include an epoxy group, a double bond conjugated to a carbonyl group, and the like. The double bond conjugated with the carbonyl group performs a Michael addition reaction with an amino group or a mercapto group in the curing agent.

Specific examples of the compound having one carboxyl group and having an amide bond include succinamic acid, oxamic acid, N-acetylglycine, N-acetylalanine, 4-acetamidobenzoic acid, N-acetylanthranilic acid, 4-acetamidobutyric acid, 6-acetamidohexanoic acid,
Hippuric acid, 5-hydantoin acetic acid, pyroglutamic acid, 2-
(Phenylcarbamoyloxy) propionic acid and the like.

Specific examples of the compound having one phenolic hydroxyl group and having an amide bond include salicylamide,
4-hydroxybenzamide, 4-hydroxyphenylacetamide, 4-hydroxyacetanilide, 3-hydroxyacetanilide and the like.

Specific examples of the compound having one amino group and having an amide bond include 4-aminobenzamide, 3-aminobenzamide, 4'-aminoacetanilide, 4-aminobutylamide, 6-aminohexanamide, Examples include 3-aminophthalimide, 4-aminophthalimide and the like.

Specific examples of the compound having one secondary amine structure and having an amide bond include nipecotamide, N, N-diethylnipecotamide, isonipecotamide, 1-acetylpiperazine and the like.

Specific examples of the compound having one mercapto group and having an amide bond include 4-acetamidothiophenol, N- (2-mercaptoethyl) acetamide and the like.

Specific examples of the compound having one epoxy group and having an amide bond include glycidamide, N-phenylglycidamide, N, N-diethylglycidamide, N-methoxymethylglycidamide, N-hydroxymethylglycidamide. Damide, 2,3-epoxy-3-methylbutylamide, 2,3-epoxy-2-methylpropionamide, 9,10-epoxystearamide, N-glycidylphthalimide and the like.

In a compound having one double bond conjugated to a carbonyl group and having an amide bond, the carbonyl group conjugated to the double bond may be the same as or different from the carbonyl group of the amide bond. . Compounds in which the carbonyl group conjugated to the double bond is the same as the carbonyl group of the amide bond include amides of α, β-unsaturated carboxylic acids and derivatives thereof having a substituent on the nitrogen atom. Specific examples of such compounds include acrylamide, methacrylamide, N, N-dimethylacrylamide, N, N-diethylacrylamide, N-tert-butylacrylamide, N-isopropylacrylamide, N-butylacrylamide, N-
Hydroxymethylacrylamide, N-methoxymethylacrylamide, N-ethoxymethylacrylamide, Nn-
Examples include propoxymethylacrylamide, Nn-butoxymethylacrylamide, N-isobutoxymethylacrylamide, N-benzyloxymethylacrylamide, diacetoneacrylamide, 1-acryloylmorpholine, 1-acryloylpiperidine and the like. In addition, imides of unsaturated dicarboxylic acids such as maleimide, N-ethylmaleimide, and N-phenylmaleimide are also applicable. Examples of the compound in which the carbonyl group conjugated to the double bond is not the same as the carbonyl group of the amide bond include 2- (phenylcarbamoyloxy) ethyl methacrylate.

The component (A) may be blended in the epoxy resin composition alone or in combination of two or more.

The component (A) (when a plurality of types are used, the total thereof) is preferably used in an amount of 0.5 to 15% by weight, preferably 100% by weight of the total epoxy resin in the epoxy resin composition. It is good to mix 1 to 10% by weight, more preferably 2 to 5% by weight. If it is less than 0.5% by weight, the effect of improving the adhesiveness is not sufficiently exhibited, and if it is more than 15% by weight, the heat resistance may be reduced.

The component (A) may be a liquid or a solid at room temperature. When a solid component is used as the component (A), it may be mixed with the epoxy resin composition and then dissolved by means such as heating and stirring, or may be mixed without being dissolved. When the solid component (A) is blended without dissolving, it is preferable to use the solid component (A) by pulverizing it to a particle size of 10 μm or less.

In the present invention, the component (B) is a polyester polyurethane having an aromatic ring in the molecule.
This compound is blended as a compound for increasing the elastic modulus without lowering the tensile elongation of the cured product.

That is, since the urethane structure present in the molecule of the component (B) forms a strong hydrogen bond with the hydroxyl group present in the epoxy resin and restrains the molecular movement, the elastic modulus of the cured resin is increased. It is estimated that

In the constituent element (B), the ester structure in the molecule reacts with the amino group, mercapto group, phenolic hydroxyl group and the like in the curing agent by a nucleophilic substitution reaction to form a part of the network of the epoxy resin cured product. Therefore, there is also a feature that phase separation does not occur and the elastic modulus of the cured resin is hardly reduced.

In the present invention, the constituent component (B) includes, for example, a polyisocyanate having two or more isocyanate groups in a polyester polyol obtained by polycondensation of a polyhydric carboxylic acid and a polyhydric alcohol, and optionally a chain extension. Polyester polyurethane obtained by applying a conventionally known method such as a one-shot method or a prepolymer method using an agent can be used. In the present invention, one or more components (B) can be blended in the resin composition.

Examples of polycarboxylic acids include malonic acid, succinic acid, succinic anhydride, glutaric acid, adipic acid, azelaic acid, sebacic acid, phthalic acid, phthalic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, and isophthalic acid. Acid, terephthalic acid, nadic acid anhydride, maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, trimellitic acid, trimellitic anhydride, pyromellitic acid, pyromellitic anhydride, etc., among which succinic acid And aliphatic polycarboxylic acids such as adipic acid.

Examples of polyhydric alcohols include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,3-butylene glycol, 1,4
-Butylene glycol, 1,5-butylene glycol,
1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, diethylene glycol,
Dipropylene glycol, 2,2,4-trimethyl-
1,3-pentanediol, cyclohexanediol,
Bisphenol A ethylene oxide adduct, bisphenol A propylene oxide adduct, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, glycerin, trimethylolpropane, trimethylolethane, pentaerythritol and the like, among which 1,2-propylene glycol, 1,
4-butylene glycol, 1,6-hexanediol and the like are preferably used.

As the polyisocyanate, an aromatic polyurethane can be used since the synthesized polyurethane has an aromatic ring in the molecule, and the elasticity of the cured product obtained by heating and curing the epoxy resin composition is further increased. Isocyanates are preferably used. For example, 2,4
-Tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, tolidine diisocyanate, 1,5-naphthalene diisocyanate, isophorone diisocyanate, p-
Examples include phenylene diisocyanate, m-phenylene diisocyanate, xylylene diisocyanate, tetramethyl xylene diisocyanate, triphenylmethane triisocyanate, tris (isocyanate phenyl) thiophosphate, and oligomers thereof. 6-tolylene diisocyanate and 4,4'-diphenylmethane diisocyanate are preferably used.

As the chain extender, 1,2-propylene glycol, 1,4-butanediol, 1,6-hexanediol, polyethylene glycol, polypropylene glycol or a mixture thereof is used.

In the present invention, the component (B) is blended in an amount of 1 to 15% by weight, preferably 1 to 10% by weight, more preferably 1 to 5% by weight based on 100% by weight of the total epoxy resin. . If the amount is less than 1% by weight, the effect of improving the elastic modulus of the cured resin becomes insufficient, and if it exceeds 15% by weight, the heat resistance of the cured resin may decrease.

The component (A) and the component (B)
Can, of course, be simultaneously compounded. In this case, in order to secure the heat resistance and the like of the cured resin, the total amount of the components (A) and (B) is determined by adding It is good to be 1 to 15% by weight, preferably 1 to 10% by weight based on the weight%.

In the present invention, in addition to the above-mentioned constituents (A) and (B), other components such as a polymer compound and organic or inorganic particles are appropriately added to the epoxy resin composition according to the purpose. Can be blended.

As the polymer compound, a thermoplastic resin is preferably used. By blending a thermoplastic resin,
Optimizing the viscosity of the resin composition and the handling of the prepreg,
Alternatively, the effect of improving the adhesion is enhanced.

The thermoplastic resin used here is preferably a thermoplastic resin having a hydrogen-bonding functional group which can be expected to have a synergistic effect of improving the adhesiveness which is the object of the present invention.

Examples of the hydrogen bonding functional group include an alcoholic hydroxyl group, an amide bond and a sulfonyl group.

Examples of the thermoplastic resin having an alcoholic hydroxyl group include polyvinyl acetal resins such as polyvinyl formal and polyvinyl butyral, polyvinyl alcohol, phenoxy resins, and thermoplastic resins having an amide bond include polyamide, polyimide, and thermoplastic resins having a sulfonyl group. Examples of the plastic resin include polysulfone. Polyamide, polyimide and polysulfone may have a functional group such as an ether bond or a carbonyl group in the main chain. The polyamide may have a substituent on the nitrogen atom of the amide group.

Examples of commercially available thermoplastic resins having a hydrogen-bonding functional group that are soluble in an epoxy resin include, as polyvinyl acetal resins, denkabutyral and denkaformal (registered trademark, manufactured by Denki Kagaku Kogyo KK), Vinylek (registered trademark, manufactured by Chisso Corporation), UCARPKHP (model number, manufactured by Union Carbide) as a phenoxy resin, Macromelt (registered trademark, manufactured by Henkel Hakusui Corporation) as a polyamide resin, Amilan CM4000
(Registered trademark, manufactured by Toray Industries, Inc.), Ultem (registered trademark, manufactured by General Electric) as polyimide, M
atrimid 5218 (registered trademark, manufactured by Ciba Co., Ltd.), and polysulfone such as Victrex (registered trademark, manufactured by Mitsui Chemicals, Inc.) and UDEL (registered trademark, manufactured by Union Carbide Co., Ltd.).

When a thermoplastic resin is blended, the thermoplastic resin is used as the total epoxy resin 1 in the epoxy resin composition.
It is preferable to mix 1 to 20% by weight with respect to 00% by weight in order to impart appropriate viscoelasticity to the epoxy resin composition and increase the mechanical strength of the resulting fiber-reinforced plastic member.

Rubber particles and thermoplastic resin particles are used as the organic particles to be added to the epoxy resin composition.
These particles have the effect of improving the toughness of the resin and the impact resistance of the fiber reinforced plastic member.

Further, as the rubber particles, crosslinked rubber particles and core-shell rubber particles obtained by graft-polymerizing a different polymer on the surface of the crosslinked rubber particles are preferably used.

Commercially available crosslinked rubber particles include XER-91 (Nippon Synthetic Rubber Industry Co., Ltd.) comprising a crosslinked product of a carboxyl-modified butadiene-acrylonitrile copolymer.
CX-MN series (manufactured by Nippon Shokubai Co., Ltd.) composed of fine particles of acrylic rubber, YR-500 series (manufactured by Toto Kasei Co., Ltd.) and the like can be used.

As commercially available core-shell rubber particles, a paraloid EXL-2655 made of butadiene / alkyl methacrylate / styrene copolymer (Kureha Chemical Industry Co., Ltd.)
Co., Ltd.), staphyloid AC-3355 comprising an acrylate-methacrylate copolymer, TR-2
122 (manufactured by Takeda Pharmaceutical Co., Ltd.), butyl acrylate
PARALOID comprising a methyl methacrylate copolymer
EXL-2611, EXL-3387 (registered trademark, model number, manufactured by Rohm & Haas) or the like can be used.

As the thermoplastic resin particles, polyamide or polyimide particles are preferably used.
As commercially available polyamide particles, Toray Industries, Ltd.
P-500, manufactured by ATOCHEM, orgasol (registered trademark) or the like can be used.

As the inorganic particles to be added to the epoxy resin composition, silica, alumina, smectite, synthetic mica and the like can be added. These inorganic particles are blended into the epoxy resin composition mainly for rheological control, that is, for increasing viscosity and imparting thixotropic properties.

Various known methods are used for producing the fiber-reinforced plastic member of the present invention. For producing sports goods such as golf shafts, fishing rods and rackets, the epoxy resin composition as described above is used. The method of preparing a prepreg impregnated with reinforcing fibers such as carbon fiber, laminating, heating and curing to make a fiber reinforced plastic member is adopted, such as ease of handling, convenience in molding, etc. It is preferable from the viewpoint of.

The prepreg is produced by a method such as a wet method in which a matrix resin is dissolved in methyl ethyl ketone, methanol or a solvent to reduce the viscosity and impregnated into reinforcing fibers, or a hot melt method in which the viscosity is reduced by heating and impregnated into the reinforcing fibers. be able to.

The wet method is a method in which a reinforcing fiber is immersed in a solution comprising a resin composition, then pulled up, and the solvent is evaporated while heating using an oven or the like to obtain a prepreg.

The hot melt method is a method of directly impregnating a reinforcing fiber with a resin composition whose viscosity has been reduced by heating, or a method of preparing a film in which the resin composition is once coated on release paper or the like, and then reinforcing the fiber. There is a method in which such a film is overlaid on both sides or one side of the fiber and heated to impregnate the resin composition into a prepreg. The hot melt method is preferred because the solvent does not substantially remain in the prepreg.

The fiber reinforced plastic member can be produced by a conventionally known method in which after laminating such prepregs, the resin composition is heated and cured while applying pressure to the laminate.

Methods for applying heat and pressure include a press molding method, an autoclave molding method, a bagging molding method, a wrapping tape method, and an internal pressure molding method. Particularly, for sports goods, the wrapping tape method and the internal pressure molding method are used. It is preferably adopted.

The wrapping tape method is a method of wrapping a prepreg around a core metal such as a mandrel to obtain a cylindrical molded body, and is suitable for producing a rod-shaped body such as a golf shaft and a fishing rod. Specifically, a prepreg is wound around a mandrel, and a wrapping tape made of a thermoplastic resin film is wound around the outside of the prepreg for fixing the prepreg and applying pressure, and after heating and curing the resin in an oven, a core metal is formed. Is obtained to obtain a cylindrical molded body.

In the internal pressure forming method, a preform in which a prepreg is wound around an internal pressure applying body such as a tube made of a thermoplastic resin is placed in a mold, and then a high-pressure gas is introduced into the internal pressure applying body to form a pressure. And molding by heating the mold. The method includes a golf shaft, a bat,
It is suitably used when obtaining a molded article having a complicated shape such as a tennis or badminton racket.

[0085]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail with reference to embodiments. The preparation amount of the prepreg and the cutting amount as an index of the cutting property of the fiber reinforced plastic member were measured by the following method. Table 1 or Table 2 shows the raw materials used in each of the examples and comparative examples, and the cutting amounts of the fiber-reinforced plastic members obtained by heating and curing the obtained prepreg. (1) Preparation of prepreg The resin composition was applied on release paper using a reverse roll coater to prepare a resin film. Next, the two resin films are overlapped so as to be sandwiched from both sides of carbon fibers aligned in one direction in a sheet shape, and heated under pressure to impregnate the carbon fibers with the resin.
A prepreg of 25 g / m ² was obtained. (2) Cutting amount of fiber reinforced plastic member The unidirectional prepreg is formed by reinforcing fibers in the same direction with a thickness of 2
mm to obtain a unidirectional composite material. From this unidirectional composite material, a temperature of 135
11. A sample prepared by heating and curing at 290 Pa and a pressure of 290 Pa for 2 hours so that the weight becomes 4 g.
After processing into a rectangular parallelepiped shape of 5 mm, length of 100 mm, and height, the same sample was fixed. Next, using a micro grinder having a cylindrical grindstone attached to a rotating shaft having a roughness of # 240, a diameter of 10 mm and a length of 15 mm, while applying a load of 200 g in the pressing direction, make sure that the grindstone is not clogged. While the grindstone was wet with 100 cc of supply water per minute, wet cutting was performed at 10,000 rpm for 1 minute. Regarding the weight loss ratio of the same sample before and after cutting, n = 1
The average value of 0 was defined as the cutting amount. (3) Tensile strength and tensile modulus of carbon fiber The carbon fiber to be measured is manufactured by Union Carbide Co., Ltd.
Bakelite (registered trademark) ERL-4221 1000
g (100% by weight), a resin composition obtained by mixing 30 g (3% by weight) of boron trifluoride monoethylamine (BF ₃ .MEA) and 40 g (4% by weight) of acetone,
Next, the mixture was heated at 130 ° C. for 30 minutes and cured to obtain a resin-impregnated strand. Resin-impregnated strand test method (JIS
R7601), the tensile strength and the tensile modulus were determined. (4) Tensile elongation of carbon fiber Measured according to JIS R7601. (5) Concentration of functional group on carbon fiber surface Surface specific oxygen concentration O / C Surface specific oxygen concentration O / C was determined by X-ray photoelectron spectroscopy according to the following procedure.

First, a sizing agent or the like was removed from the carbon fiber bundle to be measured with a solvent, cut into a suitable length, spread on a stainless steel sample support, and measured under the following conditions.

Photoelectron escape angle: 90 degrees X-ray source: MgKα1,2 Vacuum inside the sample chamber: 1 × 10 ⁻⁸ Torr Next, the main component of C _1S was used to correct the peak accompanying the charging during measurement. B. Peak binding energy value E. FIG. 284.6 eV
I adjusted to.

Next, the C _1s peak area [O _1s ] is 28
Obtained by drawing a linear base line in the range of 2 to 296 eV, the O _1s peak area [C _1s ] is 528 to 54
It was determined by drawing a straight base line in the range of 0 eV.

The surface specific oxygen concentration O / C was determined by the following equation from the ratio of the O _1s peak area [O _1s ], the C _1s peak area [C _1s ], and the sensitivity correction value unique to the apparatus.

O / C = ([O _1s ] / [C _1s ]) / (sensitivity correction value) In this case, as a measuring device, Shimadzu Corp.
Using ESCA-750, the sensitivity correction value unique to the device was set to 2.85. B. Surface carboxyl group concentration COOH / C Surface carboxyl group concentration COOH / C was determined by chemically modified X-ray photoelectron spectroscopy according to the following procedure.

First, a sizing agent or the like is removed from a carbon fiber bundle to be measured with a solvent, cut to an appropriate length, spread on a platinum sample support, and then arranged at 0.02 mol / L.
Was exposed to air containing 60% of dicyclohexylcarbodiimide gas and 0.04 mol / L of pyridine gas at 60 ° C. for 8 hours for chemical modification treatment, and then measured under the following conditions.

Photoelectron escape angle: 35 degrees X-ray source: AlKα1,2 Vacuum in sample chamber: 1 × 10 ⁻⁸ Torr Next, the main component of C _1S was used to correct peaks due to charging during measurement. B. Peak binding energy value E. FIG. 284.6 eV
I adjusted to.

Next, the C _1s peak area [C _1s ] is 28
It is obtained by drawing a linear base line in the range of 2 to 296 eV, and the F _1s peak area [F _1s ] is 682 to 69
It was determined by drawing a straight base line in the range of 5 eV.

Further, as a comparative sample, the reaction rate r was determined by dividing the C _1s peak of chemically modified polyacrylic acid.
And the residual ratio m of the dicyclohexylcarbodiimide derivative was determined from the O _1s peak splitting. Next, the surface carboxyl group concentration COOH / C was determined by the following equation.

COOH / C = [[F _1s ] / [(3k [C _1s ]-(2 + 13
m) [F _1s ]) r]] × 100 (%) Here, model SSX-100-206 manufactured by US SSI was used.
The sensitivity correction value k of the F _1s peak area with respect to the C _1s peak area unique to this apparatus was 3.919. (6) Crystal size Lc of carbon network plane by wide-angle X-ray diffraction Preparation of measurement sample From the cured resin plate prepared in the same manner as in A of the above (1), a test piece of 4 cm in length is cut out and solidified using a mold and a collodion-alcohol solution to form a prism and a measurement sample. did. B. Measurement conditions X-ray source: CuKα (using Ni filter) Output: 40 kV, 20 mA Measurement of crystal size Lc The crystal size Lc was calculated from the half width of the peak of the plane index (002) obtained by the transmission method using the following Scherrer equation.

[0096] Lc (hkl) = Kλ / β 0 cosθ B However, Lc (hkl): average direction perpendicular to the (hkl) plane of the crystallite size K: 1.0, λ: X-ray wavelength of, β ₀ : (β _E2 −β ₁₂ ) _1/2 β _E : Apparent half width (measured value), β ₁₂ : 1.05 × 1
0 ^-2 rad. θ _B : Bragg angle (Example 1) The following materials were mixed in a kneader to obtain a resin composition. Bisphenol A type epoxy resin 40% by weight (Epicoat 828, registered trademark, Yuka Shell Epoxy Co., Ltd.) Bisphenol A type epoxy resin 50% by weight (Epicoat 1001, registered name, Yuka Shell Epoxy Co., Ltd.) Phenol novolak Type epoxy resin 10% by weight (Epicoat 154, registered trademark, Yuka Shell Epoxy Co., Ltd.) Dicyandiamide 5% by weight (DICY7, model number, Yuka Shell Epoxy Co., Ltd.) 3- (3,4-dichlorophenyl)- 1,1-dimethylurea 3% by weight (DCMU99, model number, manufactured by Hodogaya Chemical Industry Co., Ltd.) N-n-butoxymethylacrylamide 5% by weight (manufactured by Kasano Kosan Co., Ltd.) Polyvinyl formal 7% by weight (vinylek K, Chisso Using this resin composition, according to the method described above, Wei direction tensile modulus using a carbon fiber 294 GPa, the matrix resin content to prepare a 24% by weight of the prepreg. (Example 2) The same method as described in Example 1, except that Nn-dimethylacrylamide (produced by Kojin Co., Ltd.) was used as the component (A) to be blended. According to the above, a prepreg having a matrix resin content of 24% by weight was prepared using carbon fibers having a tensile elastic modulus in the fiber direction of 343 GPa. (Example 3) The same resin composition as in Example 1 was used according to the method described above, except that N-isopropylacrylamide (produced by Kojin Co., Ltd.) was used as the component (A) to be blended. A prepreg having a matrix resin content of 24% by weight was prepared using carbon fibers having a tensile modulus in the fiber direction of 392 GPa. Example 4 The following materials were mixed in a kneader to obtain a resin composition. Bisphenol A type epoxy resin 40% by weight (Epicoat 828, registered trademark, Yuka Shell Epoxy Co., Ltd.) Bisphenol A type epoxy resin 30% by weight (Epicoat 1001, registered trademark, Yuka Shell Epoxy Co., Ltd.) Phenol novolak Type epoxy resin 30% by weight (Epicoat 154, registered trademark, Yuka Shell Epoxy Co., Ltd.) Dicyandiamide 5% by weight (DICY7, model number, Yuka Shell Epoxy Co., Ltd.) 3- (3,4-dichlorophenyl)- 1,1-Dimethylurea 3% by weight (DCMU99, model number, manufactured by Hodogaya Chemical Industry Co., Ltd.) Nn-butoxymethylacrylamide 5% by weight (manufactured by Kasano Kosan Co., Ltd.) Polyvinylformal 7% by weight (Vinylek K, registered (Trademark, manufactured by Chisso Corporation) According, the fiber direction of the tensile modulus using a carbon fiber 294 GPa, the matrix resin content to prepare a 24% by weight of the prepreg. (Example 5) The same method as in Example 4 except that Nn-dimethylacrylamide (produced by Kojin Co., Ltd.) was used as the component (A) to be blended. According to the above, a prepreg having a matrix resin content of 24% by weight was prepared using carbon fibers having a tensile elastic modulus in the fiber direction of 343 GPa. (Example 6) The same resin composition as in Example 4 was used, except that N-isopropylacrylamide (produced by Kojin Co., Ltd.) was used as the component (A) to be blended, according to the method described above. A prepreg having a matrix resin content of 24% by weight was prepared using carbon fibers having a tensile modulus in the fiber direction of 392 GPa. Example 7 The following materials were mixed in a kneader to obtain a resin composition. Bisphenol A type epoxy resin 30% by weight (Epicoat 828, registered trademark, manufactured by Yuka Shell Epoxy Co., Ltd.) Bisphenol A type epoxy resin 45% by weight (Epicoat 1001, registered name, Yuka Shell Epoxy Co., Ltd.) Phenol novolak Type epoxy resin 25% by weight (Epicoat 154, registered trademark, Yuka Shell Epoxy Co., Ltd.) Dicyandiamide 5% by weight (DICY7, model number, Yuka Shell Epoxy Co., Ltd.) 3- (3,4-dichlorophenyl)- 1,1-dimethylurea 4% by weight (DCMU99, model number, manufactured by Hodogaya Chemical Industry Co., Ltd.) 5% by weight of polyester polyurethane (“PANDEX” T-5205, registered trademark, manufactured by Dainippon Ink Industries, Ltd.) Polyvinyl formal 5 % By weight (Vinilec K, registered trademark, manufactured by Chisso Corporation) Using the resin composition according to the method described above, the fiber direction of the tensile modulus using a carbon fiber 294 GPa, the matrix resin content to prepare a 24% by weight of the prepreg. Example 8 The following raw materials were mixed in a kneader to obtain a resin composition. Bisphenol A type epoxy resin 30% by weight (Epicoat 828, registered trademark, manufactured by Yuka Shell Epoxy Co., Ltd.) Bisphenol A type epoxy resin 45% by weight (Epicoat 1001, registered name, Yuka Shell Epoxy Co., Ltd.) Phenol novolak Type epoxy resin 25% by weight (Epicoat 154, registered trademark, Yuka Shell Epoxy Co., Ltd.) Dicyandiamide 5% by weight (DICY7, model number, Yuka Shell Epoxy Co., Ltd.) 3- (3,4-dichlorophenyl)- 1,1-dimethylurea 4% by weight (DCMU99, model number, manufactured by Hodogaya Chemical Industry Co., Ltd.) Nn-butoxymethylacrylamide 3% by weight (manufactured by Kasano Kosan Co., Ltd.) Polyester polyurethane 5% by weight (“PANDEX” T -5205, registered trademark, Dainippon Ink and Chemicals, Inc.) Ruformal 5% by weight (Vinilec K, registered trademark, manufactured by Chisso Corporation) Using this resin composition, according to the method described above, using carbon fibers having a tensile elastic modulus in the fiber direction of 294 GPa and a matrix resin content of 24 A weight% prepreg was prepared. Comparative Example 1 A resin composition was obtained by mixing the following raw materials with a kneader. Bisphenol A type epoxy resin 10% by weight (Epicoat 828, registered trademark, Yuka Shell Epoxy Co., Ltd.) Bisphenol A type epoxy resin 40% by weight (Epicoat 1001, registered trademark, Yuka Shell Epoxy Co., Ltd.) Phenol novolak Epoxy resin 10% by weight (Epicoat 154, registered trademark, manufactured by Yuka Shell Epoxy Co., Ltd.) Resorcin diglycidyl ether type epoxy resin 20% by weight (Denacol EX201, registered trademark, manufactured by Nagase Kasei Kogyo Co., Ltd.) Brominated bisphenol A-type epoxy resin 10% by weight (Epiclon 152, registered trademark, manufactured by Dainippon Ink & Chemicals, Inc.) Dicyandiamide 5% by weight (DICY7, model number, Yuka Shell Epoxy Co., Ltd.) 3- (3,4-dichlorophenyl) -1,1-dimethylurea 3% by weight ( CMU99, model number, Hodogaya Chemical Industry Co., Ltd.) Polyvinyl formal 7% by weight (Vinilec K, registered trademark, manufactured by Chisso Corporation) Using this resin composition, the tensile modulus in the fiber direction was determined according to the method described above. A prepreg having a matrix resin content of 24% by weight was prepared using carbon fibers of 294 GPa. (Comparative Example 2) Using the same resin composition as in Comparative Example 1, according to the method described above, the tensile modulus in the fiber direction was 343 GP.
A prepreg having a matrix resin content of 24% by weight was prepared using the carbon fiber of a. (Comparative Example 3) A prepreg having a matrix resin content of 24% by weight was prepared using the same resin composition as in Comparative Example 1 and using carbon fibers having a tensile modulus in the fiber direction of 392 GPa according to the method described above. . (Comparative Example 4) The following materials were mixed with a kneader to obtain a resin composition. Bisphenol A type epoxy resin 30% by weight (Epicoat 828, registered trademark, made by Yuka Shell Epoxy Co., Ltd.) Bisphenol A type epoxy resin 40% by weight (Epicoat 1001, registered trademark, made by Yuka Shell Epoxy Co., Ltd.) Phenol novolak Type epoxy resin 30% by weight (Epicoat 154, registered trademark, Yuka Shell Epoxy Co., Ltd.) Dicyandiamide 5% by weight (DICY7, model number, Yuka Shell Epoxy Co., Ltd.) 3- (3,4-dichlorophenyl)- 1,1-dimethylurea 3% by weight (DCMU99, model number, manufactured by Hodogaya Chemical Industry Co., Ltd.) Polyvinyl formal 7% by weight (vinylek K, registered trademark, manufactured by Chisso Corporation) Using this resin composition, According to the method, a carbon fiber having a tensile modulus in the fiber direction of 294 GPa Box resin content to prepare a 24% by weight of the prepreg. (Comparative Example 5) Using the same resin composition as in Comparative Example 4, the tensile modulus in the fiber direction was 343 GP according to the method described above.
A prepreg having a matrix resin content of 24% by weight was prepared using the carbon fiber of a. (Comparative Example 6) Using the same resin composition as in Comparative Example 4, according to the method described above, the tensile modulus in the fiber direction was 392 GP.
A prepreg having a matrix resin content of 24% by weight was prepared using the carbon fiber of a.

[0097]

[Table 1]

[0098]

[Table 2]

[0099]

According to the present invention, the amount of material cut by the cutting process is not excessive, the material is not easily dropped due to the separation of the reinforcing fiber and the matrix resin, and the dimensional stability is improved. It is possible to provide a carbon fiber reinforced plastic member which is excellent and has a small decrease in mechanical strength in the obtained finished product.

The carbon fiber reinforced plastic member of the present invention can be used for general industrial applications such as frames, pipes, and shafts of aircraft, ships, automobiles, bicycles, pumps and brush cutters, or fishing rods, golf club shafts, ski poles,
As a material for sports and leisure use such as badminton rackets, tent posts, skis, snowboards and golf club heads, and as a material for civil engineering construction, it exhibits good processing characteristics and mechanical strength, and can be suitably used.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08K 7/06 C08K 7/06 C08L 63/00 C08L 63/00 A D06M 15/55 D06M 15/55 // (C08L 63/00 75:06) D06M 101: 40 (72) Inventor Hirohide Wada 1515 Tsutsui, Matsumae-cho, Iyo-gun, Ehime Pref.

Claims (9)

[Claims] 1. A fiber reinforcement comprising a reinforcing fiber having a tensile modulus of 290 Gpa or more, a curing agent, and an epoxy resin composition containing the following component (A) and / or component (B): A fiber-reinforced plastic member, wherein the amount of the fiber-reinforced plastic member cut by wet cutting is 1% by weight or less. (A) a compound having one functional group and one or more amide bonds capable of reacting with an epoxy resin or a curing agent in the molecule (B) a polyester polyurethane having an aromatic ring in the molecule 2. The fiber reinforced plastic member according to claim 1, wherein the epoxy resin composition comprises the component (A). 3. The fiber reinforced plastic member according to claim 1, wherein the prepreg obtained by impregnating the reinforcing fiber with the epoxy resin composition is heated and cured. 4. The composition (A) is blended, and the blending amount of the composition (A) is 100% by weight of the total epoxy resin.
The fiber-reinforced plastic member according to any one of claims 1 to 3, which is 0.5 to 15% by weight based on the weight of the member. 5. Component (B) is blended, and the blending amount of component (B) is 100% by weight of the total epoxy resin.
The fiber reinforced plastic member according to any one of claims 1 to 4, wherein the content is 1 to 15% by weight based on the weight of the member. 6. The fiber-reinforced plastic member according to claim 1, wherein the reinforcing fibers are carbon fibers. 7. The surface carboxyl group concentration C of the carbon fiber measured by a chemically modified X-ray photoelectron spectroscopy.
The fiber reinforced plastic member according to claim 6, wherein OOH / C is 0.002 to 0.03. 8. The carbon fiber according to claim 1, wherein the surface specific oxygen concentration O / C measured by X-ray photoelectron spectroscopy is 0.02 to
The fiber reinforced plastic member according to claim 6 or 7, wherein the ratio is 0.3. 9. The method according to claim 1, wherein the epoxy resin composition contains 2
The fiber-reinforced plastic member according to any one of claims 1 to 8, comprising 70 to 100% by weight of an epoxy resin having two epoxy groups based on 100% by weight of the total epoxy resin.