JP2505994B2 - Fiber-reinforced composite epoxy resin composition and cured product thereof - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fiber reinforced composite material having an epoxy resin as a matrix material and having significantly improved toughness, and a cured product thereof.

[0002]

2. Description of the Related Art Conventionally, two or more kinds of materials have been compounded,
Research and development of composite materials that mutually complement the characteristics of constituent materials and produce new effective functions are being actively conducted. That is, composites are made by mixing polymer materials having mutually different properties, glass fibers useful as reinforcing fibers, carbon fibers, composites with high-strength fibers such as aramid fibers, etc. Performance modification such as deformation temperature and electrical characteristics is being carried out. As a matrix resin for this composite,
Epoxy resins are widely used. That is, since the epoxy resin is excellent in electrical characteristics, adhesiveness, thermal characteristics, cost, etc., its application range is very wide.
However, the epoxy resin is generally brittle, and there is a problem that cracks easily occur due to stress distortion during curing or use, heat or mechanical impact. To solve this problem, a curing agent having a long-chain aliphatic group or a rubber-like property is used, a compound having an elastomeric property is added, a plasticizer such as an asphalt substance or glycol is added, and an epoxy compound is further added. Its toughness is measured by introducing a molecular group showing rubber elasticity into itself (Koichi Ochi, Polymer 38
(3), 200 (1989).

[0003]

However, these substances are not sufficiently compatible with the epoxy resin, so that a sufficient compounding property cannot be obtained, and the epoxy resin has excellent properties such as heat resistance and adhesiveness. Problems such as impairing the image quality and increasing the cost are caused, and there are problems that a sufficient combined effect cannot be exhibited and that the device cannot be used in terms of cost. The present invention has been made in view of these problems, and an object of the present invention is to provide an epoxy resin composition that provides improved toughness without reducing the heat resistance, adhesiveness, and the like of the epoxy resin. Furthermore, it is intended to provide a cured product which is extremely useful in the fields of structural materials, electric and electronic materials, etc. by curing and molding these fiber reinforced composite materials under suitable conditions.

[0004]

DISCLOSURE OF THE INVENTION As a result of intensive studies for solving the above-mentioned problems, the present inventors have found that at least a phenolic hydroxyl group-containing aramid-polybutadiene-acrylonitrile block copolymer represented by the following general formula (I) is used. The inventors have found that the object of the present invention can be achieved by forming a fiber-reinforced composite material composed of a polymer, an epoxy resin, a curing agent, and inorganic / or organic fibers, and have completed the present invention. The present invention is a fiber containing a reaction product A of a phenolic hydroxyl group-containing aramid-polybutadiene-acrylonitrile block copolymer represented by the general formula (I) and an epoxy resin, an epoxy resin, an epoxy resin curing agent, and an inorganic or organic fiber. It is a reinforced composite epoxy resin composition.

Embedded image (In the formula, x = an integer of 3 to 7, y = 1 to an integer of 4, y /
(X + y) = 0.1 to 0.3, z = 5 to 15 integer, m = 1
~ 400 integer, n = 1-400 integer, n / (m +
n) = 0.01 to 0.50, 1 = an integer of 1 to 50, Ar ¹ , Ar
³ is a divalent aromatic group, Ar ² is a divalent aromatic group containing a phenolic hydroxyl group). In the present invention, the formula (I)
Aramids containing phenolic hydroxyl groups-Polybutadiene-
The content of the acrylonitrile block copolymer is preferably 0.1 to 15% by weight based on the epoxy resin.

That is, in the present invention, the phenolic hydroxyl group-containing aramid-polybutadiene-acrylonitrile copolymer represented by the above general formula (I) promotes the toughening of the epoxy resin. Since the epoxy resin is dispersed to make the epoxy resin tough, and the size of this molecular dispersion is very small compared to the distance between fibers,
The epoxy resin matrix having the interfiber spacing is a toughened continuous body, and it is presumed that the toughening of the fiber composite is performed with high efficiency. Further, it is considered that the phenolic compound promotes the toughening action of the aramid-polybutadiene-acrylonitrile copolymer component in a more hardening manner. Since the toughening modifying effect of the phenolic hydroxyl group-containing aramid-polybutadiene-acrylonitrile block copolymer is achieved with a small addition amount of these copolymers,
Not only does it not impair the excellent properties of epoxy resin, but it also has the major feature of improving its heat resistance.
A fiber-reinforced composite epoxy resin material having an epoxy resin as a matrix is significantly improved.

The block copolymer (I) used in the present invention can be synthesized by the following method. That have a phenolic hydroxyl group having the general formula divalent aromatic groups Ar ¹ in the aromatic dicarboxylic acid of the general formula (I) with divalent aromatic groups Ar ² having a phenolic hydroxyl group in (I) In excess of the aromatic dicarboxylic acid, an excess amount of the general formula (I)
Aromatic diamines having a divalent aromatic group Ar ³ therein are added, these are, for example, in the presence of a phosphite ester and a pyridine derivative, in an organic solvent represented by N-methyl-2-pyrrolidone, The mixture is heated and stirred under an inert atmosphere such as nitrogen. As a result, a polybutadiene-acrylonitrile copolymer having a carboxy group at both ends was added to the resulting polyaramid oligomer solution containing a phenolic hydroxyl group having aminoaryl groups at both ends, and polycondensation was performed to obtain block copolymerization. The combination (I) is obtained.

A polybutadiene-acrylonitrile copolymer having carboxyl groups at both ends is commercially available from Goodrich as Hycar CTBN, and these can be used.

As the aromatic dicarboxylic acid having a phenolic hydroxyl group, 4-hydroxyisophthalic acid,
5-Hydroxyisophthalic acid, 2-hydroxyphthalic acid and 2-hydroxyterephthalic acid are applicable, and examples of the aromatic dicarboxylic acid having no phenolic hydroxyl group include phthalic acid, isophthalic acid, terephthalic acid, 4,
4'-biphenyldicarboxylic acid, 3,3'-methylenedibenzoic acid, 4,4'-methylenedibenzoic acid, 4,4'-
Oxydibenzoic acid, 4,4'-thiodibenzoic acid, 3,
3'-carbonyldibenzoic acid, 4,4'-carbonyldibenzoic acid, 4,4'-carbonyldibenzoic acid, 4,4 '
-Sulfonyl dibenzoic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid and the like can be mentioned, but not limited thereto. These aromatic dicarboxylic acids may be used alone or in combination.

Further, examples of the aromatic diamine include m-phenylenediamine, p-phenylenediamine,
3,3'-oxydianiline, 3,4'-oxydianiline, 4,4'-oxydianiline, 3,3'-diaminobenzophenone, bis (4-aminophenyl) sulfone, bis (3-aminophenyl) ) Sulfone, bis (4-
Aminophenyl) sulfide, 1,4-naphthalenediamine, 2,6-naphthalenediamine, 4,4'-bis (4-phenoxy) diphenylsulfone, 4,4'-bis (3-phenoxy) diphenylsulfone, 2,2 ′-
Examples thereof include (4-aminophenyl) propane, bis (4-aminophenyl) methane, o-tolidine, and o-dianilidine, but are not limited thereto. These aromatic diamines can be mixed and used.

The epoxy resin used in the epoxy resin composition of the present invention is not limited, but those having two or more epoxy groups in one molecule are preferable. Examples of such compounds include glycidyl ethers, glycidyl esters, glycidyl amines, linear aliphatic epoxies, and alicyclic epoxides. Examples of the glycidyl ethers include glycidyl ether of bisphenol, polyglycidyl ether of phenol novarac,
Examples thereof include glycidyl ether of alkylene glycol or polyalkylene glycol. Examples of the glycidyl ether of bisphenol include bisphenol A, bisphenol F, bisphenol AD, bisphenol S, tetramethylbisphenol A, tetramethylbisphenol F, and tetramethylbisphenol A.
Diglycidyl ethers of dihydric phenols such as D, tetramethylbisphenol S, tetrachlorobisphenol A, and tetrabromobisphenol A are polyglycidyl ethers of phenol novolac, such as phenol novolac, cresol novolac, and brominated phenol novolac. Polyglycidyl ether of novolac resin, as the diglycidyl ether of alkylene glycol or polyalkylene glycol,
Examples thereof include diglycidyl ethers of glycols such as polyethylene glycol, polypropylene glycol and butanediol.

Examples of the glycidyl esters include hexahydrophthalic acid glycidyl ester and dimer acid glycidyl ester.
Examples of glycidyl amines include triglycidyl aminodiphenylmethane, triglycidyl aminophenol, triglycidyl isocyanurate, and the like. Further, linear aliphatic epoxides include, for example, epoxidized polybutadiene and epoxidized soybean oil, and alicyclic epoxides include, for example, 3,4-epoxy-6-methylcyclohexylmethylcarboxylate, 3,4. 4-epoxycyclohexyl methyl carboxylate and the like can be mentioned. In the epoxy resin composition of the present invention, these epoxy resins can be used alone or in combination.

Examples of the curing agent used in the present invention include bis (4-aminophenyl) sulfone, bis (4-aminophenyl) methane, 1,5-diaminonaphthalene, p
-Phenylenediamine, m-phenylenediamine, o-
Aromatic amine compounds such as phenylenediamine, 2,6-dichloro-1,4-benzenediamine, 1,3- (p-aminophenyl) bropane, m-xylenediamine,
Aliphatic amines such as ethylenediamine, diethylenetriamine, tetraethylenepentamine, diethylaminopropylamine, hexamethylenediamine, mensendiamine, isophoronediamine, bis (4-amino-3-methyldicyclohexyl) methane, polymethylenediamine, polyetherdiamine Compounds, polyaminoamide compounds, aliphatic acid anhydrides such as dodecyl succinic anhydride, polyadipic anhydride, polyazelaic anhydride, etc., alicyclic acid anhydrides such as hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, etc. , Phthalic anhydride, trimellitic anhydride, benzophenone tetracarboxylic acid anhydride, aromatic acid anhydrides such as ethylene glycol bis trimellitate, glycerol tris trimellitate, dicyandiamide, organic acid dihydrazide Basic active hydrogen compounds and the like,
Examples thereof include, but are not limited to, imidazole compounds, Lewis acids and brested acid salts, polymercaptan compounds, phenol resins, urea resins, melamine resins, isocyanates and blocked isocyanate compounds.

The reaction product used in the present invention is obtained by reacting the phenolic hydroxyl group-containing aramid-polybutadiene-acrylonitrile block copolymer represented by the general formula (I) with an epoxy resin in an amide solvent. Examples of amide solvents include N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-
2-pyrrolidone or the like is used. The amount of the epoxy resin used is 1 to 20 times equivalent, preferably 5 to 15 times equivalent to the block copolymer (I). Reaction temperature is 50
℃ or more, preferably 70 ℃ or more.

As the inorganic or organic fiber, carbon fiber,
Examples include glass fibers, boron fibers, silicon carbide fibers, alumina fibers, inorganic fibers such as silica-alumina fibers, and organic fibers such as aramid fibers and polyester fibers.
Advent fibers such as carbon fibers and aramid fibers are particularly preferred. The carbon fiber may be a PAN-based carbon fiber or a Pitch-based carbon fiber. 2 of these fibers
You may use it in mixture of 2 or more types. These fibers may be long fibers or short fibers. The fibers may be surface-treated. Further, the resin composition may be impregnated into fibers or fiber cloth arranged in one direction. The fiber content is usually 10 to 90% by weight, preferably 20 to 80%.

If a bisphenol compound is further added to the resin composition of the present invention, a tougher molded product can be obtained. The content of the bisphenol compound is 0.1 to 60% by weight based on the epoxy resin. Examples of the bisphenol compound used in the present invention include 2,2'-bis (4-hydroxyphenyl) propane, 2,2'-bis (2-methyl-4-hydroxyphenyl) propane, 2,2'-
Bis (4-hydroxyphenyl) methane, 1,1′-bis (4-hydroxyphenyl) ethane, 1,1′-bis (4-hydroxyphenyl) hexane, 1,1′-bis (4-hydroxyphenyl) docosyl 2,2'-bis (4-hydroxyphenyl) butane, 2,2'-bis (4-hydroxyphenyl) hexane, bis (4-hydroxyphenyl) sulfone, bis (3-chloro-4-)
Hydroxyphenyl) sulfone, bis (3,5-dimethyl-4-hydroxyphenyl) sulfone, bis (4
-Hydroxy-3,5-dibromophenyl) sulfone, bis (4-hydroxyphenyl) sulfide, bis (3-methyl-4-hydroxyphenyl) sulfide,
1,1-bis (4-hydroxyphenyl) cyclohexane, 4,4'-dihydroxybenzophenone, dihydroxynaphthalene, 1,4- (p-hydroxycumyl) benzene and the like can be mentioned, but not limited to these. .

The epoxy resin composition of the present invention may contain, if necessary, a curing accelerator, a reaction diluent for epoxy resin, a dye, an oxidation stabilizer, a coupling agent, other resin and the like. Examples of the curing accelerator include phosphorus-based compounds such as triphenylphosphine, tertiary amine-based compounds such as triethanolamine, tetraethylamine, 1,8-diaza-bicyclo [5,4,0] -7-undecene (DBU), and N, N. −
Dimethylbenzylamine, 1,1,3,3-tetramethylguanidine, 2-ethyl-4-methylimidazole,
Boron-based compounds such as N-methylpiperazine and the like, such as 1,8-diaza-bicyclo [5,4,0] -7-undecenium tetraphenylborate, are used.

The method for molding the epoxy resin composition of the present invention is not particularly limited, but is preferably an amide solvent which is a good solvent for both the block copolymer of the general formula (I) and the epoxy resin, for example, N, N-dimethylformamide,
Dissolve in N, N-dimethylacetamide, N-methyl-2-pyrrolidone, etc., uniformly, heat to react, and dry,
Furthermore, a cured molded article of the target epoxy resin composition can be obtained by molding an epoxy resin composition obtained by adding a predetermined amount of reinforcing fibers, a curing agent, a curing accelerator, etc. and heating and curing. I can. Further, a reinforcing fiber woven fabric is impregnated with an epoxy resin composition composed of a reaction product of a block copolymer of the general formula (I) and an epoxy resin, an epoxy resin, a curing agent and a curing accelerator, or a solution thereof. After that, it is possible to obtain a cured molded article of the target epoxy resin composition by molding and heating and curing. Further, the woven fabric impregnated with the epoxy resin composition can be heat-cured as it is or after being semi-cured and laminated. The epoxy resin composition of the present invention and the cured molded article thereof are not limited to the method for producing the composition and the molding method.

[0018]

The present invention will be described below with reference to examples, but the present invention is not limited to these examples. Synthesis Example 1 Synthesis of phenolic hydroxyl group-containing aramid-polybutadiene-acrylonitrile block copolymer (2 mol% of phenolic hydroxyl group contained in aramid part): isophthalic acid 19.60 g (118 mmo1), 3,4'-oxydiene Aniline 26.4 g (132 mmo1), 5-hydroxyisophthalic acid 0.41 g (2.3 mmo1), lithium chloride 3.9 g, calcium chloride 12.1 g, N-methyl-2-pyrrolidone 240 ml, and pyridine 54 ml were 11-4. Put in a round bottom flask and dissolve with stirring, then add 74 g of triphenyl phosphite, and add at 4 ° C at 90 ° C.
The reaction was carried out for a period of time to form an integral aramid oligomer containing phenolic hydroxyl group. In addition to this, polybutadiene-acrylonitrile copolymer (Hy
car CTBN, manufactured by BF Goodrich. A solution of 48 g of pyridine containing 48 g of acrylonitrile component contained in the polybutadiene acrylonitrile portion is 17 mol% and a molecular weight of about 3600) is added, and the mixture is further reacted for 4 hours.
After cooling to room temperature, the reaction solution is poured into methanol 201, and the aramid-polybutadiene-acrylonitrile block containing about 2 mol% of phenolic hydroxyl group whose content of the polybutadiene-acrylonitrile copolymer part used in the present invention is 50 wt% is used. The copolymer was precipitated. The precipitated polymer was further washed with methanol and refluxed with methanol for purification. Intrinsic viscosity of this polymer is 0.85dl
/ G (dimethylacetamide, 30 ° C). The infrared spectrum of the polymer powder was measured by the diffuse reflection method. As a result, it was found that the amide carbonyl group was 285 at 1674 cm ⁻¹ .
The absorption based on C-H bonds of the butadiene part in 6-2975cm ^-1, revealed absorption based on nitrile group in 2245 cm ^-1.

Synthesis Example 2 Synthesis of phenolic hydroxyl group-containing aramid-polybutadiene-acrylonitrile block copolymer (phenolic hydroxyl group contained in aramid portion is 14 mol%): Synthesis Example 1
Isophthalic acid 19.60g (118mmo1), 3,
26.4 g of 4'-oxydianine (132 mmo1),
5-Hydroxyisophthalic acid 0.41 g (2.3 mmo
1) and polybutadiene having carboxyl groups at both ends
Acrylonitrile copolymer (48 g) was charged in isophthalic acid (19.93 g (120 mmo1), 3,4'-oxydianiline (30.63 g (153 mmo1)), and 5-hydroxyisophthalic acid (3.64 g (20 mmo1)). Polybutadiene-acrylonitrile copolymer having a group (Hycar CTBN, manufactured by BF Goodrich. Polybutadiene acrylonitrile part contained 17 mol% of acrylonitrile and had a molecular weight of about 3600) except that the polymerization was changed to 55.5 g. The same post-treatment was carried out to deposit an aramid-polybutadiene-acrylonitrile block copolymer containing about 14 mol% of phenolic hydroxyl groups used in the present invention. The intrinsic viscosity of this polymer is 0.82 dl / g (dimethylacetamide, 3
It was 0 degreeC). It was measured infrared spectrum by diffusion reflection method polymer powder, based amide carbonyl group 1675 cm ^-1, the absorption based on C-H bonds of the butadiene part in 2854-2971Cm ^-1, the nitrile group to 2243cm ^-1 absorption Admitted.

Comparative Example 1 Epoxy resin (Epikote 828, average molecular weight: 380,
Epoxy equivalent: 190 ± 5, manufactured by Yuka Shell Co., Ltd.) 100
g, 1.0 g of tetraethylamine as a curing accelerator, 12.4 of bis (4-aminophenyl) methane as a curing agent
g was added, stirred and uniformly mixed to obtain a comparative epoxy resin sample.

Example 1 3 g of a phenolic hydroxyl group-containing aramid-polybutadiene-acrylonitrile block copolymer containing 2 mol% of the phenolic hydroxyl group obtained in Synthesis Example 1 was dissolved in 25 g of dimethylformaldehyde, and then the epoxy compound was prepared. (Epikote 828: average molecular weight: 380, epoxy equivalent: 1
90 ± 5, manufactured by Yuka Shell Co., Ltd.) 0.71 g, and 0.01 g of triphenylphosphine which is a reaction accelerator,
The reaction was performed at 0 ° C for 2 hours. This was added to water to precipitate a resin, washing with hot water was repeated, and tetrahydrofuran was further added to azeotrope these solvents under reduced pressure, followed by vacuum drying, and an epoxy compound reacted with the aramid part. A resin composition was obtained. The epoxy compound 96.
3 g and 1 g of tetraethylamine, which is a curing accelerator, were melted, added, stirred and uniformly mixed to obtain an epoxy resin composition used in the present invention.

Example 2 3.0 g to 5.0 g of the aramid-polybutadiene-acrylonitrile block copolymer containing 2 mol% of the phenolic hydroxyl group of Example 1 and 0.7% of the epoxy resin were used.
From 1 g to 1.3 g, triphenylphosphine was added to 0.
The same operation was performed instead of 01 g to 0.02 g to obtain a resin composition of an aramid-polybutadiene-acrylonitrile block copolymer and an epoxy resin. 93.7 g of the epoxy resin and 12.4 g of bis (4-aminophenyl) methane were added to this resin composition and the same operation was performed to obtain an epoxy resin composition used in the present invention.

Example 3 Aramid-polybutadiene-acrylonitrile containing the aramid-polybutadiene acrylonitrile block copolymer containing 2 mol% of the phenolic hydroxyl group of Example 1 and containing about 14 mol% of the phenolic hydroxyl group obtained in Synthesis Example 2 Replace the block copolymer with 0.71 epoxy resin
g to 1.8 g, triphenylphosphine to 0.0
The same operation was performed instead of 1 g to 0.02 g to obtain a composition of an aramid-polybutadiene-acrylonitrile block copolymer and an epoxy resin. This resin composition was subjected to exactly the same operation except that the epoxy resin was changed from 96.3 g to 95.2 g to obtain an epoxy resin composition used in the present invention.

Example 4 5.0 g of an aramid-polybutadiene-acrylonitrile block copolymer containing about 14 mol% of 3.0 g of the aramid-polybutadiene-acrylonitrile block copolymer containing 2 mol% of the phenolic hydroxyl group of Example 2.
In the same manner, except that the epoxy resin was changed from 1.8 g to 3.0 g and triphenylphosphine 0.02 g was changed to 0.03 g, the same operation was carried out to obtain a composition of the aramid-polybutadiene-acrylonitrile block copolymer and the epoxy resin. I got a thing. 95.2 g of epoxy compound to 92.0
Except for replacing g, the same operation was performed to obtain an epoxy resin composition used in the present invention.

Comparative Example 2 Comparison was made in the same manner as in Comparative Example 1, except that 2,2'-bis (4-hydroxyphenyl) propane bisphenol A was added in an amount of 14.3 g to 13 wt% with respect to the epoxy resin. An epoxy resin composition for use was obtained.

Comparative Example 3 In Comparative Example 2, 24.3 g of bisphenol A was added.
A comparative epoxy resin composition was obtained in exactly the same manner except that the amount was changed to 8.1 g (about 33 mol% based on the total epoxy resin).

Example 5 In a resin composition of an aramid-polybutadiene-acrylonitrile block copolymer obtained by reacting an aramid part obtained in Example 1 with an epoxy resin and an epoxy resin, 96.3 g of the epoxy resin and bisphenol A as a total epoxy resin were prepared. 28.1 g of 26 wt% with respect to the resin was added, and 12.4 g of bis (4-aminophenyl) propane, which is a curing agent, was melted and added, and then the mixture was stirred and uniformly mixed, and then at 80 ° C. for 2 hours.
It was heated at 180 ° C. for 6 hours to obtain an epoxy resin composition used in the present invention.

Example 6 A resin composition of an aramid-polybutadiene-acrylonitrile block copolymer obtained by reacting an aramid part obtained in Example 2 with an epoxy resin and epoxy was added to the above-mentioned epoxy resin in an amount of 93.7 g of bisphenol A. The amount of 14.3 g, which is 13% by weight, is further added, and 12.4 g of bis (4-aminophenyl) propane, which is a curing agent, is melted and added, and then the mixture is stirred and uniformly mixed, and at 80 ° C. for 2 hours and The epoxy resin composition used in the present invention was obtained by heating at 180 ° C. for 6 hours.

Example 7 From 14.3 g of bisphenol A of Example 6 to 28.1
An epoxy resin composition used in the present invention was obtained by the same method except that g (about 33 mol% based on the total epoxy resin) was used.

Example 8 From 28.1 g to 46.6 of the bisphenol A of Example 7
An epoxy resin composition used in the present invention was obtained in exactly the same manner except that g (about 45 mol% relative to the total epoxy resin) was used.

Example 9 An epoxy resin composition used in the present invention was obtained in exactly the same manner as in Example 3 except that when 95.2 g of the epoxy resin was added, 28.1 g of bisphenol A was newly added. It was

Example 10 An epoxy resin composition used in the present invention was obtained in the same manner as in Example 4, except that when 95.2 g of the epoxy resin was added, 28.1 g of bisphenol A was newly added. It was

Carbon fibers (T400, 36 manufactured by Toray Industries, Inc.) were added to the epoxy resin compositions of Comparative Examples 1 to 3 and Examples 1 to 10.
(00 denier, 6000 filaments) was dipped by the Durham winding method, and acetone was evaporated at 40 to 80 ° C. in an oven to obtain a prepreg. The fiber-reinforced composite epoxy resin composition of the present invention composed of this prepreg was arranged in one direction to obtain a unidirectional carbon fiber-reinforced resin molded sample having a thickness of 2 × 12 × 120 (mm) and a fiber content of 65% by volume. This molded sample was cured by heating at 200 ° C for 4 hours, and the 0 ° bending strength was measured at 25 ° C (span 64 mm was 3 mm).
Point bending test method). The results are summarized in Table 1.

[0034]

[Table 1] a) In the block copolymer, the mol% of the hydroxyl group contained in the aramid part is shown.

The fiber-reinforced composite epoxy resin composition of the present invention can produce an epoxy resin molded product having improved toughness. This molded product can be used for golf shafts, tennis rackets, fishing rods, printed wiring boards and the like.

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Claims (4)

(57) [Claims] 1. A fiber reinforced composite containing a reaction product of an aramid-polybutadiene-acrylonitrile block copolymer having a phenolic hydroxyl group represented by the general formula (I) and an epoxy resin, an epoxy resin, a curing agent and an inorganic or organic fiber. Epoxy resin composition. Embedded image (In the formula, x = an integer of 3 to 7, y = 1 to an integer of 4, y /
(X + y) = 0.1 to 0.3, z = 5 to 15 integer, m = 1
~ 400 integer, n = 1-400 integer, n / (m +
n) = 0.01 to 0.50, 1 = an integer of 1 to 50, Ar ¹ , Ar
³ is a divalent aromatic group, Ar ² is a divalent aromatic group containing a phenolic hydroxyl group). 2. A cured molded article obtained by thermosetting after curing the composition of claim 1. 3. The phenolic hydroxyl group-containing aramid-polybutadiene-acrylonitrile block copolymer represented by the general formula (I) is contained in an amount of 0.1 to 15% by weight based on the epoxy resin. The resin composition according to claim 2. 4. The resin composition according to claim 1, wherein the bisphenol compound is contained in an amount of 0.1 to 60% by weight based on the epoxy resin.