JPH08325394A - Prepreg and fiber-reinforced composite material - Google Patents

Abstract

PURPOSE: To obtain a prepreg, comprising reinforcing fibers, an epoxy resin composition having a specific value or above of flexural elastic modulus and an epoxy resin composition, having a specific value or above of tensile breaking elongation and present on the surface side thereof, excellent in mechanical characteristics of a compression system and impact resistance and suitable as a structural material. CONSTITUTION: This prepreg contains (A) reinforcing fibers, (B) an epoxy resin composition, capable of providing a cured product having >=380kgf/mm flexural elastic modulus at ambient temperature and >=280kgf/mm<2> flexural elastic modulus at 82 deg.C after absorbing boiling water for 20hr and containing diaminodiphenyl sulfone as a curing agent component and (C) an epoxy resin composition, capable of affording a cured product having >=5%, preferably >=7% tensile breaking elongation and containing a compound of the formula (X1 to X8 are each H, a halogen or a 1-5C alkyl; Y1 is a 1-10C alkylene), etc., as a curing agent component and present on the surface side thereof.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a prepreg for producing a fiber-reinforced composite material. More specifically, the present invention relates to a prepreg that is excellent in compression system mechanical properties and impact resistance and provides a fiber-reinforced composite material suitable as a structural material, and a fiber-reinforced composite material using the prepreg.

[0002]

2. Description of the Related Art Polymer-based composite materials composed of reinforcing fibers and a matrix resin are lightweight and have excellent mechanical properties, and are therefore widely used in sports equipment, aerospace applications, and general industrial applications. Various methods are used for producing the fiber-reinforced composite material, and a method using a prepreg which is a sheet-shaped intermediate base material in which reinforcing fibers are impregnated with a matrix resin is widely used. In this method, a molded article of a composite material is obtained by laminating a plurality of prepregs and then heating them.

As the matrix resin used in the prepreg, both thermosetting resins and thermoplastic resins are used, but in most cases, thermosetting resins having excellent handleability are used, and among them, epoxy resins are the most common. in use. Further, a maleimide resin, a cyanate resin and a combination thereof are also often used. Compressive strength is one of the important physical properties when a composite material is used as a structural material. Since bolt holes are often provided when used as a structural member, the compressive strength of a perforated plate is particularly important.

In general, polymer materials have low strength and elastic modulus under high temperature or high humidity conditions. Therefore, the physical properties such as strength of the fiber-reinforced composite material using the polymer as a matrix are likely to be deteriorated under high temperature or high humidity conditions. However, when the composite material is applied as a structural material for aircraft, vehicles, ships, etc., it is required to sufficiently maintain the physical properties even under high temperature or high humidity conditions.

Compressive strength is a particularly important physical property when a composite material is used as a structural material. To measure the compressive strength,
Although it is performed using a test piece such as a non-perforated plate, a perforated plate, or a cylinder, in actual use, it is often the shape of a plate material provided with bolt holes, so the compressive strength of the perforated plate, especially Strength under high temperature and high humidity conditions becomes important.

Impact resistance is also important when using composite materials as structural materials. A particularly important physical property with respect to impact resistance is post-impact compression strength. This is because there is a phenomenon that the compression strength is reduced due to peeling between the layers of the composite material due to the impact on the member due to the drop of the tool or the collision of pebbles, and if this is remarkable, it becomes impossible to use it as a structural material. is there.

In order to improve the compressive strength of the composite material, it is generally effective to increase the elastic modulus of the matrix resin. It is possible to increase the elastic modulus of the epoxy resin cured product by selecting the raw materials to be mixed. However, in general, epoxy resin cured products with high elastic modulus have small tensile fracture elongation and are brittle, so impact resistance, especially compressive strength after impact, and fatigue and other properties become poor, so use a product with a large elastic modulus in practice. I couldn't.

On the other hand, when epoxy resin cured products having a large fracture elongation which can increase the compressive strength after impact are used as the matrix resin, generally, these cured products cannot have a very high elastic modulus and therefore have a high compressive strength. It was not possible to obtain a fiber-reinforced composite material.

As described above, at present, no material has been obtained which can achieve both high compressive strength, especially perforated plate compressive strength, and high impact resistance, especially post-impact compressive strength.

[0010]

SUMMARY OF THE INVENTION An object of the present invention is to provide a fiber-reinforced composite material which is excellent in mechanical properties of a compression system, particularly in compressive strength of a perforated plate at high temperature and high humidity and excellent in impact resistance, and which is suitable as a structural material. Is to provide a prepreg.

[0011]

The prepreg of the present invention which meets the above object comprises the following components (A), (B) and (C), wherein (C) is present on the surface side of (B). It is a prepreg characterized by that.

(A) Reinforcing fiber (B) Cured product having a flexural modulus at room temperature of 380 kgf / m
Epoxy resin composition having a m ² or more (C) Epoxy resin composition having a tensile fracture elongation of 5% or more of a cured product The fiber-reinforced composite material according to the present invention is formed by curing such a prepreg. It consists of things.

The present invention will be specifically described below.

At least two kinds of epoxy resin compositions are used in the prepreg of the present invention. That is, for the surface layer of the prepreg, which is involved in impact resistance and fatigue, an epoxy resin composition having a high elongation of the cured product, specifically, a tensile elongation at break of 5% or more, is used. Indicates that the cured product has a high elastic modulus, specifically, a bending elastic modulus at room temperature of 38.
By using an epoxy resin composition of 0 kgf / mm ² or more, an epoxy resin composition in which a cured product has a high elastic modulus or an epoxy resin composition in which a cured product has a high elongation is used alone as a matrix resin of a prepreg. It eliminates the drawbacks of using it.

As the reinforcing fiber (A) used in the present invention,
Glass fiber, carbon fiber, aramid fiber, boron fiber, alumina fiber, silicon carbide fiber and the like are used. Of these, carbon fibers are preferable because they are particularly excellent in mechanical properties and have good adhesiveness to the matrix resin.
As the form of the reinforcing fiber, long fibers aligned in one direction,
Tows, fabrics, mats, knits, braids, etc. are used.

The epoxy resin composition (B) used in the prepreg has a cured product having a high elastic modulus, specifically, a flexural elastic modulus at room temperature of 380 kgf / mm ² or more. The flexural modulus was obtained by curing and cutting the epoxy resin composition using the same curing temperature and curing time as the prepreg curing conditions, and the thickness was 2 mm, the width was 10 mm, and the length was 60 mm.
mm test piece was prepared, and the distance between fulcrums was set to 32 mm and 3
It is obtained by measurement by a point bending test.

Further, the higher the flexural modulus of the cured product, the higher the compressive strength of the composite, but since the resin may become brittle, which may adversely affect the tensile strength and the impact strength, the elastic modulus of the cured product at room temperature. Is more preferably 380 kgf / mm ² or more and 550 kgf / mm ² or less.

When the fiber reinforced composite material is used as a structural material, it is necessary that the deterioration of physical properties at high temperature and high humidity is small. It is important in this respect that the decrease in the elastic modulus of the matrix resin at high temperature and high humidity is small. Resin composition (B)
Is a test piece of the above-mentioned size using the cured product.
After soaking for 0 hours, the flexural modulus measured at 82 ° C is 28.
0 kgf / mm ² or more, more preferably 320 kgf /
It is desirable that it is at least mm ² .

Further, the higher the flexural modulus of the cured product measured at 82 ° C., the higher the compressive strength of the composite when it is hot and humid, but the resin becomes brittle, which may adversely affect the tensile strength and the impact strength. Therefore, the elastic modulus of the cured product measured at 82 ° C is 280 kgf / mm ² or more and 440 k.
It is more preferable to set it to gf / mm ² or less.

The epoxy resin composition (B) is mainly composed of
It consists of epoxy resin and curing agent.

The epoxy resin is bisphenol A.
Type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol B type epoxy resin, naphthalene type epoxy resin, novolac type epoxy resin, epoxy resin having fluorene skeleton,
Epoxy resin made from a copolymer of phenol compound and dicyclopentadiene, diglycidyl resorcinol, tetrakis (glycidyloxyphenyl) ethane,
Glycidyl ether type epoxy resins such as tris (glycidyloxyphenyl) methane, tetraglycidyl diaminodiphenylmethane, triglycidyl aminophenol, triglycidyl aminocresol, glycidyl amine type epoxy resins such as tetraglycidyl xylene diamine and mixtures thereof are used. .

In order to realize a high elastic modulus of the resin cured product, it is preferable that 70% or more of the epoxy resin component is a trifunctional or more functional epoxy resin. As a trifunctional or higher functional epoxy resin, it is effective to blend a glycidyl ether type epoxy resin such as tetrakis (glycidyloxyphenyl) ethane or tris (glycidyloxyphenyl) methane or a glycidylamine type epoxy resin as a main component. . In particular, it is preferable to add tetraglycidyldiaminodiphenylmethane, which is a tetrafunctional glycidylamine type epoxy resin, as a main component because the elastic modulus is less likely to decrease under high temperature and high humidity conditions.

Further, an epoxy resin having a rigid skeleton,
For example, blending of an epoxy resin having a naphthalene skeleton or a fluorene skeleton is also preferable because a high elastic modulus and a small elastic modulus reduction under high temperature and high humidity conditions can be realized.

As the curing agent, aromatic amines such as diaminodiphenylmethane and diaminodiphenylsulfone, aliphatic amines, imidazole derivatives, dicyandiamide, tetramethylguanidine, thiourea-added amine,
Examples thereof include carboxylic acid anhydrides such as methylhexahydrophthalic anhydride, carboxylic acid hydrazides, carboxylic acid amides, polyphenol compounds, novolac resins, polymercaptans, and Lewis acid complexes such as boron trifluoride ethylamine complex.

These hardening agents may be combined with a suitable hardening aid to enhance the hardening activity. As a preferable example, dicyandiamide is added to 3- (3,4-dichlorophenyl) -1,1-dimethylurea (DCMU).
Examples of the combination of as a curing auxiliary agent, examples of combining boron trifluoride ethylamine complex with an aromatic amine as a curing auxiliary agent, and examples of combining a tertiary amine as a curing auxiliary agent with a carboxylic acid anhydride or novolac resin. To be

In order to obtain a cured product having a high elastic modulus and a small elastic modulus decrease under high temperature and high humidity conditions, it is preferable to use diaminodiphenyl sulfone as a curing agent, and among its isomers, 3,3. It is particularly preferred to use'-diaminodiphenyl sulfone.

The epoxy resin composition (B) may further contain a thermoplastic resin soluble in the epoxy resin. As the thermoplastic resin, those having a high elastic modulus and a high glass transition temperature are preferable, and specific examples thereof include polysulfone, polyether sulfone, polyimide, and polyetherimide.

The epoxy resin composition (C) used on the surface side of the prepreg has a high breaking elongation of the cured product, specifically, the tensile breaking elongation of the cured product is 5% or more, preferably 7% or more. Some are used. Further, the higher the fracture elongation of the cured product, the higher the impact resistance of the composite, but if the fracture elongation is increased, the elastic modulus decreases, which may adversely affect the compressive strength of the composite.
The breaking elongation is more preferably 7% or more and 30% or less. The tensile fracture elongation of the cured product referred to here is JIS-K-
It is a value obtained by conducting a tensile test on a cured resin plate according to the method described in 7113.

The epoxy resin composition (C) is mainly composed of
It consists of epoxy resin and curing agent.

The epoxy resin is bisphenol A.
Type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol B type epoxy resin, naphthalene type epoxy resin, novolac type epoxy resin, epoxy resin having fluorene skeleton,
Epoxy resin made from a copolymer of phenol compound and dicyclopentadiene, diglycidyl resorcinol, tetrakis (glycidyloxyphenyl) ethane,
Glycidyl ether type epoxy resins such as tris (glycidyloxyphenyl) methane, tetraglycidyl diaminodiphenylmethane, triglycidyl aminophenol, triglycidyl aminocresol, glycidyl amine type epoxy resins such as tetraglycidyl xylene diamine and mixtures thereof are used. .

As the curing agent, aromatic amines such as diaminodiphenylmethane and diaminodiphenylsulfone, aliphatic amines, imidazole derivatives, dicyandiamide, tetramethylguanidine, thiourea-added amines,
Examples thereof include carboxylic acid anhydrides such as methylhexahydrophthalic anhydride, carboxylic acid hydrazides, carboxylic acid amides, polyphenol compounds, novolac resins, polymercaptans, and Lewis acid complexes such as boron trifluoride ethylamine complex.

These hardening agents may be combined with a suitable hardening aid to enhance the hardening activity. As a preferable example, dicyandiamide is added to 3- (3,4-dichlorophenyl) -1,1-dimethylurea (DCMU).
Examples of the combination of as a curing auxiliary agent, examples of combining boron trifluoride ethylamine complex with an aromatic amine as a curing auxiliary agent, and examples of combining a tertiary amine as a curing auxiliary agent with a carboxylic acid anhydride or novolac resin. To be

Various methods are known for obtaining an epoxy resin composition having a high fracture elongation of a cured product.

The method of blending the epoxy resin is as follows:
A method of reducing the crosslink density is effective, and it is preferable to blend 50% or more of the monofunctional or bifunctional epoxy resin in the epoxy resin component. As the bifunctional epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin,
Examples thereof include bisphenol B type epoxy resin, naphthalene type epoxy resin, epoxy resin having a fluorene skeleton, epoxy resin using a copolymer of phenol compound and dicyclopentadiene as a raw material, diglycidyl resorcinol, and various reactive diluents. . For the bifunctional epoxy resin, it is effective to use a product having a large epoxy equivalent capable of increasing the distance between the crosslinking points. However, since this alone lowers the elastic modulus and heat resistance, it is necessary to take a method such as blending a glycidyl amine type epoxy resin or a novolac type epoxy resin. Among the bifunctional epoxy resins, those having a naphthalene skeleton, a fluorene skeleton and a biphenyl skeleton, and those made of a copolymer of a phenol compound and dicyclopentadiene as a raw material are excellent in elastic modulus and heat resistance, and therefore are preferably used. it can.

The tensile elongation at break of the cured epoxy resin can also be increased by selecting a curing agent. Preferred curing agents include compounds having the structures of the following general formulas (I) to (III).

[0036]

[Chemical 4] In the formula, X _{1 to} X ₈ are hydrogen atom, halogen atom, and carbon number 1
To Y 5 represent a group selected from alkyl groups, and Y ₁ represents an alkylene group having 1 to 10 carbon atoms.

Preferred examples of X _{1 to} X ₈ are hydrogen atom, chlorine atom, bromine atom, methyl group, ethyl group and isopropyl group, and preferred specific examples of Y ₁ are methylene group, ethylene group and trimethylene. Group, isopropylidene group, neopentylene group, hexamethylene group, octamethylene group.

[0038]

Embedded image In the formula, X _{9 to} X ₂₀ are hydrogen atom, halogen atom, and carbon number 1
To Y ₅ and Y ₃ each represent an alkylene group having 1 to 5 carbon atoms.

Preferred examples of X _{9 to} X ₂₀ are hydrogen atom, chlorine atom, bromine atom, methyl group, ethyl group and isopropyl group, and preferred examples of Y ₂ and Y ₃ are methylene group and ethylene. Group, trimethylene group, isopropylidene group, neopentylene group, hexamethylene group,
An octamethylene group may be mentioned.

[0040]

[Chemical 6] In the formula, X _{21 to} X ₂₈ are a hydrogen atom, a halogen atom, and a carbon number 1
Represents a group selected from alkyl groups of to 5, Y ₄ represents an alkylene group having 1 to 10 carbon atoms.

Preferred examples of X _{21 to} X ₂₈ are hydrogen atom, chlorine atom, bromine atom, methyl group, ethyl group and isopropyl group, and preferred specific examples of Y ₄ are methylene group, ethylene group and trimethylene. Group, isopropylidene group, neopentylene group, hexamethylene group, octamethylene group.

Preferred specific examples of the compound having the structure of formula (I) are 4,4'-diaminodiphenylmethane, 4,4'-methylenebis (2,5-diethylaniline) and 4,4'-methylenebis (2). , 6-diisopropylaniline), 4,4'-methylenebis (2-ethyl-)
6-methylaniline), 4,4-methylenebis (3-chloro-2,6-diethylaniline) and the like.

Preferred specific examples of the compound having the structure of formula (II) include 4,4'-phenylenediisopropylidene bis (2,6-dimethylaniline). Preferred specific examples of the compound having the structure of formula (III) include trimethylenebis (4-aminobenzoate), hexamethylenebis (4-aminobenzoate), neopentylenebis (4-aminobenzoate).
And the like.

When these compounds are used as a curing agent, the epoxy resin component is a trifunctional or higher functional epoxy resin,
For example, even when tetraglycidyldiaminodiphenylmethane is used as a main component, a high tensile elongation at break can be realized, and the heat resistance is less deteriorated, which is preferable.

As a method of increasing the breaking elongation, a method of blending at least one thermoplastic resin or elastomer soluble in an epoxy resin is also effective. Where the thermoplastic resin,
The fact that the elastomer is soluble in the epoxy resin means that there is a temperature range in which the epoxy resin composition containing the thermoplastic resin and the elastomer is in a uniform phase. Phase separation of the resin composition at room temperature or phase separation in the curing process of the resin composition may occur. As the thermoplastic resin, polysulfone, polyether sulfone, polyether ketone, polyimide, polyetherimide, aromatic polyester or the like can be used. As the elastomer, butadiene-acrylonitrile copolymer, chloroprene rubber, silicone rubber, thermoplastic elastomer, etc. can be used. Here, the thermoplastic elastomer is an elastomer having properties of a thermoplastic resin, and a urethane-based thermoplastic elastomer, a polyester-based thermoplastic elastomer, a polyamide-based thermoplastic elastomer, or the like can be used.

When the phases rich in the thermoplastic resin and the elastomer are separated during the curing process, the tensile elongation at break may not be improved if the adhesion between the phases is insufficient. in this case,
When a thermoplastic resin or an elastomer has a functional group such as an epoxy group, a carboxyl group, a hydroxyl group or an amino group capable of reacting with an epoxy resin or a curing agent, the adhesion between phases is improved and the breaking elongation of a cured product is improved. Therefore, it is preferable. It is also preferable to add a compatibilizing agent having an affinity for both the epoxy resin, the thermoplastic resin and the elastomer to be mixed with the epoxy resin for improving the adhesiveness.

In general, comparing the addition of the elastomer and the thermoplastic resin, the addition of the thermoplastic resin is preferable because the fiber-reinforced composite material has excellent heat resistance. The thermoplastic elastomer is also preferable because it is possible to obtain a fiber-reinforced composite material having excellent heat resistance unlike a normal elastomer.

The above methods can be applied to the epoxy resin composition (C) in an appropriate combination.

The preferred weight ratio of the epoxy resin composition (B) to the epoxy resin composition (C) in the prepreg of the present invention is 50:50 to 90:10.

In order to increase the compressive strength after impact, a high toughness material is present in the vicinity of one or both surfaces of the prepreg, and the high toughness material is distributed between the layers of the composite material obtained by laminating and curing. It is known that the above method is effective. As the high toughness material, for example, JP-A-63-1 is used.
A thermoplastic resin as disclosed in JP 62732, for example, an elastomer as disclosed in JP-A-4-268361, or an elastomer-modified thermosetting resin as disclosed in US Pat. No. 3,472,730 is used. The method is known.

Although the above-mentioned interlaminar strengthening technique can be applied to the present invention, when the interlaminar strengthening technique is applied to the present invention, an elastomer or an elastomer-modified thermosetting resin is used as a material for interlaminar strengthening. Therefore, it is preferable to use a thermoplastic resin because the physical properties at high temperature deteriorate. The interlayer strengthening referred to in the present invention is a technique for localizing a component that does not dissolve in the epoxy resin in the interlayer portion in the temperature range from room temperature to the curing temperature to strengthen the laminated layers. Therefore, the material used for the interlayer reinforcement and the epoxy resin-soluble thermoplastic resin and elastomer which are added to the epoxy resin composition (C) for the purpose of improving the breaking elongation of the resin are strictly distinguished.

When the interlaminar strengthening technique is applied, if the breaking elongation of the matrix resin around the interlaminar reinforcing material is small, the interlaminar strengthening effect is difficult to appear, and conversely, if the breaking elongation of the matrix resin is high, the interlaminar strengthening effect is large. Become. Therefore, when only a matrix resin having a high elastic modulus is used, it is difficult to sufficiently bring out the effect even by using the interlayer strengthening technique, but in the prepreg of the present invention, a resin having a large breaking elongation in the interlayer portion is used. Since it is present, the effect of interlayer reinforcement can be better exhibited, and a fiber-reinforced composite material having high compressive strength and compressive strength after impact can be obtained.

As the thermoplastic resin to be present near the surface of one or both surfaces of the prepreg, polyamide, polyimide, polyetherimide, polyamideimide, polysulfone, polyethersulfone and the like are preferable. Among these, polyamide is particularly preferable because it has excellent toughness and adhesiveness to the matrix resin. It is also possible to use a polyamide modified with an epoxy resin as disclosed in JP-A-1-104624.

The form of the thermoplastic resin is a film,
Particles and fibers can be taken.

In film form, US Pat. No. 4,60
When the surface of the prepreg is completely covered as in Japanese Patent No. 4,319, the tackiness, that is, the tackiness of the surface is lost. However, as shown in Japanese Patent Laid-Open No. 63-97635, a through hole is provided. The tackiness of the surface can be maintained by adopting a method such as making it porous as shown in JP-A-138785 or arranging a tape-like film as shown in JP-A-5-287091. .

In the case of the particle form, the shape of the particles is as described in JP-A-1.
Even with spherical particles as disclosed in Japanese Patent Laid-Open No. 110537.
Non-spherical particles as disclosed in JP-A-1-110536 or porous particles as disclosed in JP-A-5-1159 may be used.

As the fiber form, there is disclosed in JP-A-2-69566.
Short fibers as disclosed in Japanese Patent Application Laid-Open No. 4-29263
Long-fiber parallel arrangement as shown in Japanese Patent Laid-Open No.
A woven fabric as shown in 32843, a nonwoven fabric as shown in International Publication No. 94016003, a knit or the like can be used.

The prepreg of the present invention is prepared by first impregnating a sheet of reinforced fiber with resin from a film obtained by coating an epoxy resin composition (B) on a release paper or the like to form a primary prepreg. Is made,
Then, the epoxy resin composition (C) is coated on a release paper or the like, a film is attached to both sides of the release paper, and impregnation is performed to produce the film.

In order to manufacture a prepreg when the interlayer strengthening technique is applied to the present invention, the following methods can be used. The first method is a method in which the thermoplastic resin for interlayer reinforcement is attached or sprinkled on one or both surfaces of the prepreg produced by the above method. The second method is a method that can be applied when the thermoplastic resin for interlayer strengthening takes a sheet form such as a porous film, a woven fabric, a knit, or a nonwoven fabric, and for the interlayer strengthening that takes a sheet form on one side or both sides of the primary prepreg. This is a method of adhering a thermoplastic resin impregnated with the epoxy resin composition (C) and producing the same. The third method is a method applicable when the interlayer reinforcing thermoplastic resin has a discrete form such as particles and short fibers, and an epoxy resin in which the interlayer reinforcing thermoplastic resin is dispersed on both surfaces of the primary prepreg. In this method, a film obtained by applying the composition (C) to release paper or the like is attached. Hereinafter, the present invention will be described in more detail with reference to Examples. The number of parts described in the examples represents parts by weight.

[0060]

【Example】

 Example 1 (a) Preparation of resin composition The following raw materials were kneaded to obtain a primary resin composition.

(1) Tetraglycidyldiaminodiphenylmethane (ELM434, manufactured by Sumitomo Chemical Co., Ltd.) 90.0 parts (2) Bisphenol A type epoxy resin (Epicoat 825, manufactured by Yuka Shell Epoxy Co., Ltd.) 10.0 parts (3) Polyether sulfone (PES5003P, manufactured by Mitsui Toatsu Chemicals, Inc.) 12.3 parts (4) 3,3′-diaminodiphenyl sulfone (manufactured by Wakayama Seika Co., Ltd.) 36.0 parts The following raw materials are kneaded. Then, a secondary resin composition was obtained.

(1) Tetraglycidyldiaminodiphenylmethane (ELM434, manufactured by Sumitomo Chemical Co., Ltd.) 35.0 parts (2) Bisphenol A type epoxy resin (Epicoat 825, manufactured by Yuka Shell Epoxy Co., Ltd.) 15.0 parts (3) Bisphenol F type epoxy resin (Epiclon 830, manufactured by Dainippon Ink and Chemicals, Inc.) 50.0 parts (4) Polyether sulfone (PES5003P, manufactured by Mitsui Toatsu Chemicals, Inc.) 18.0 parts (5 ) 4,4'-Diaminodiphenyl sulfone (Sumicure S, manufactured by Sumitomo Chemical Co., Ltd.) 41.1 parts (b) Measurement of physical properties of cured resin The resin prepared in (a) was cured at 180 ° C for 2 hours. A plate of a resin cured product having a thickness of 2 mm was produced.

The flexural modulus was measured by cutting the plate into a width of 10 mm and a length of 60 mm and performing a three-point bending test at a fulcrum distance of 32 mm and a test speed of 2.5 mm / min. The tensile breaking elongation is measured by cutting a plate into a width of 10 mm and a length of 120 mm and processing it with a dumbbell-type test piece processing machine JIS-
The test was carried out at a test speed of 1 mm / min using a 1 (1/2) type small test piece described in K-7113.

The room temperature flexural modulus of the cured product of the primary resin composition was 420 kgf / mm ² , and the flexural modulus at 82 ° C. after absorbing boiling water for 20 hours was 330 kgf / mm ² . The tensile elongation at break of the secondary resin composition was 7.6%.

(C) Preparation of prepreg The primary resin prepared in (a) was coated on a release paper with a reverse roll coater so that the coating amount was 31.2 g / m ² to prepare a resin film. Next, a secondary resin was applied so that the applied amount was 20.5 g / m ² , to produce a resin film.

Carbon fibers aligned in one direction (T800
H and Toray Co., Ltd. are sandwiched from both sides with the primary resin film, heated and pressed to impregnate the resin, and a secondary resin film is attached to both sides of the primary resin film.
A prepreg having a carbon fiber content of 90 g / m ² and a carbon fiber content of 64.8% was obtained.

(D) Preparation of cured plate The prepreg prepared in (c) was (+ 45/0 / -45 /
90 degree) _2S , and (+ 45/0 / -45 / 90 degree) _3S
It laminated in the composition. This is placed in an autoclave at a temperature of 1
Curing was performed for 2 hours under the conditions of 80 ° C. and a pressure of 6 kgf / cm ² .

[0068] The (e) Measurement of compressive strength (+ 45/0 / -45 / 90 °) _2S cured plate of the configuration of,
30 ° in the 0 ° direction and 38.1 mm in the 90 ° direction
To a rectangular shape, and a circular hole with a diameter of 6.35 mm is punched in the center to form a perforated plate.
C.) and high-temperature high-humidity compressive strength (measured at 82 ° C. after immersion in warm water at 71 ° C. for 2 weeks) were measured using an Instron 1128 type tester. The results were as follows.

Room temperature compressive strength: 31.6 kgf / mm ² Compressive strength at high temperature and high humidity: 27.4 kgf / mm ² Furthermore, (+ 45/0 / −45 / 90 degrees) A cured plate having a _3S configuration is oriented at 0 °. 152.4 mm, 10 in 90 ° direction
Cut out into a 1.6 mm rectangle and 3111 k in the center
A falling weight impact of gf · mm was applied and the compressive strength after impact was measured. The results were as follows.

Compressive strength after impact: 17.2 kgf / mm ² Comparative Example 1 (a) Preparation of resin composition The following raw materials were kneaded to obtain a resin composition.

(1) Tetraglycidyldiaminodiphenylmethane (ELM434, manufactured by Sumitomo Chemical Co., Ltd.) 90.0 parts (2) Bisphenol A type epoxy resin (Epicoat 825, manufactured by Yuka Shell Epoxy Co., Ltd.) 10.0 parts (3) Polyether sulfone (PES5003P, manufactured by Mitsui Toatsu Chemicals, Inc.) 12.3 parts (4) 4,4′-diaminodiphenyl sulfone (Sumicure S, manufactured by Sumitomo Chemical Co., Ltd.) 41.1 parts ( b) Measurement of Physical Properties of Cured Resin Product The resin prepared in (a) was cured at 180 ° C. for 2 hours to prepare a plate of a cured resin product, and physical properties were evaluated in the same manner as in Example 1.

The tensile elongation at break of the resin composition was 2.9%.

(C) Preparation of prepreg The resin prepared in (a) was coated on release paper using a reverse roll coater so that the coating amount was 51.7 g / m ² , to prepare a resin film.

Carbon fibers aligned in one direction (T800
H, Toray Co., Ltd. is sandwiched from both sides with the above resin film, heated and pressed to impregnate the resin, and a secondary resin film is attached to both sides thereof to form a carbon fiber basis weight 190
A prepreg having a g / m ² and carbon fiber content of 64.8% was obtained.

(D) Preparation of Hardened Plate The prepreg prepared in (c) was (+ 45/0 / −45 /
90 degree) _2S , and (+ 45/0 / -45 / 90 degree) _3S
It laminated in the composition. These were cured under the same conditions as in Example 1.

[0076] The (e) Measurement of compressive strength (+ 45/0 / -45 / 90 °) _2S cured plate of the configuration of,
It processed into a perforated board like Example 1, and measured room temperature compressive strength and compressive strength at the time of high temperature and high humidity. The results were as follows.

Room temperature compressive strength: 31.8 kgf / mm ² Compressive strength at high temperature and high humidity: 27.4 kgf / mm ² Further, a cured plate having a (+ 45/0 / −45 / 90 degree) _3S configuration was used as in Example 1. After processing in the same way, 3111k in the center
A drop impact of gf · mm was applied and the compressive strength after impact was measured. The results were as follows.

Compressive strength after impact: 12.8 kgf / mm ² Example 2 (a) Preparation of resin composition The following raw materials were kneaded to obtain a primary resin composition.

(1) Tetraglycidyldiaminodiphenylmethane (ELM434, manufactured by Sumitomo Chemical Co., Ltd.) 90.0 parts (2) Bisphenol A type epoxy resin (Epicoat 825, manufactured by Yuka Shell Epoxy Co., Ltd.) 10.0 parts (3) Polyether sulfone (PES5003P, manufactured by Mitsui Toatsu Chemicals, Inc.) 12.3 parts (4) 3,3′-diaminodiphenyl sulfone (manufactured by Wakayama Seika Co., Ltd.) 36.0 parts The following raw materials are kneaded. Then, a secondary resin composition was obtained.

(1) Tetraglycidyldiaminodiphenylmethane (ELM434, manufactured by Sumitomo Chemical Co., Ltd.) 35.0 parts (2) Bisphenol F type epoxy resin (Epiclon 830, manufactured by Dainippon Ink and Chemicals, Inc.) 35.0 Parts (3) Brominated bisphenol A type epoxy resin (Epiclon 152, manufactured by Dainippon Ink and Chemicals, Inc.) 30.0 parts (4) Polyether sulfone (PES5003P, manufactured by Mitsui Toatsu Chemicals, Inc.) 13.0 Parts (5) 4,4′-diaminodiphenyl sulfone (Sumicure S, manufactured by Sumitomo Chemical Co., Ltd.) 35.0 parts (b) Physical Properties of Cured Resin: 180% of the secondary resin composition prepared in (a) The plate was cured at 2 ° C. for 2 hours to prepare a cured resin plate, and the physical properties were evaluated in the same manner as in Example 1.

The tensile breaking elongation of the secondary resin composition is 6.0.
%Met.

(C) Preparation of prepreg The primary resin prepared in (a) was coated on a release paper with a reverse roll coater to a coating amount of 31.2 g / m ² to prepare a resin film. Next, a secondary resin was applied so that the applied amount was 20.5 g / m ² , to produce a resin film.

Carbon fibers aligned in one direction (T800
H and Toray Co., Ltd. are sandwiched from both sides with the primary resin film, heated and pressed to impregnate the resin, and a secondary resin film is attached to both sides of the primary resin film.
A prepreg having a carbon fiber content of 90 g / m ² and a carbon fiber content of 64.8% was obtained.

(D) Preparation of cured plate The prepreg prepared in (c) was (+ 45/0 / -45 /
90 degree) _2S , and (+ 45/0 / -45 / 90 degree) _3S
It laminated in the composition. These were cured under the same conditions as in Example 1.

(E) Measurement of compressive strength (+ 45/0 / -45 / 90 degrees) A hardened plate having a 2S configuration was processed into a perforated plate in the same manner as in Example 1 to obtain room temperature compressive strength,
The compressive strength at high temperature and high humidity was measured. The results were as follows.

[0086] room temperature compressive strength: 31.6kgf / mm ² high temperature and high humidity when compression strength: 27.5kgf / mm ² Further, similar to the embodiment of the curing plate configuration of (+ 45/0 / -45 / 90 °) _3S After processing, 3111kgf ・ m
A falling weight impact of m was applied and the compressive strength after impact was measured. The results were as follows.

Compressive strength after impact: 15.4 kg
f / mm ² Example 3 (a) Preparation of resin composition The following raw materials were kneaded to obtain a primary resin composition.

(1) Tetraglycidyldiaminodiphenylmethane (ELM434, manufactured by Sumitomo Chemical Co., Ltd.) 90.0 parts (2) Bisphenol A type epoxy resin (Epicoat 825, manufactured by Yuka Shell Epoxy Co., Ltd.) 10.0 parts (3) Polyether sulfone (PES5003P, manufactured by Mitsui Toatsu Chemicals, Inc.) 12.3 parts (4) 3,3′-diaminodiphenyl sulfone (manufactured by Wakayama Seika Co., Ltd.) 36.0 parts The following raw materials are kneaded. Then, a secondary resin composition was obtained.

(1) Tetraglycidyldiaminodiphenylmethane (ELM434, manufactured by Sumitomo Chemical Co., Ltd.) 60.0 parts (2) Bisphenol F type epoxy resin (Epiclone 830, manufactured by Dainippon Ink and Chemicals, Inc.) 40.0 Parts (3) polyether sulfone (PES5003P, manufactured by Mitsui Toatsu Chemicals, Inc.) 14.0 parts (4) 4,4'-methylenebis (2,6-diethylaniline) (Kayabond C-300, Nippon Kayaku ( Manufactured by K.K.) 49.1 parts (b) Measurement of physical properties of resin cured product The resin prepared in (a) is cured at 180 ° C. for 2 hours to prepare a resin cured product plate, and the physical properties are the same as in Example 1. Was evaluated.

The breaking elongation of the secondary resin composition was 7.9%.

(C) Preparation of prepreg The primary resin prepared in (a) was coated on a release paper using a reverse roll coater so that the coating amount was 31.2 g / m ² to prepare a resin film. Next, a secondary resin was applied so that the applied amount was 20.5 g / m ² , to produce a resin film.

Carbon fibers aligned in one direction (T800
H and Toray Co., Ltd. are sandwiched from both sides with the primary resin film, heated and pressed to impregnate the resin, and a secondary resin film is attached to both sides of the primary resin film.
A prepreg having a carbon fiber content of 90 g / m ² and a carbon fiber content of 64.8% was obtained.

(D) Preparation of hardened plate The prepreg prepared in (c) was (+ 45/0 / -45 /
90 degree) _2S , and (+ 45/0 / -45 / 90 degree) _3S
It laminated in the composition. This was cured under the same conditions as in Example 1.

[0094] The (e) Measurement of compressive strength (+ 45/0 / -45 / 90 °) _2S cured plate of the configuration of,
It processed into a perforated board like Example 1, and measured room temperature compressive strength and compressive strength at the time of high temperature and high humidity. The results were as follows.

Compressive strength at room temperature: 30.2 kgf / mm ² Compressive strength at high temperature and high humidity: 26.9 kgf / mm ² Furthermore, a cured plate having a (+ 45/0 / −45 / 90 degree) _3S configuration was used as in Example 1. After processing in the same way, 311 in the center
A falling weight impact of 1 kgf · mm was applied and the compressive strength after impact was measured. The results are as follows.

Compressive strength after impact: 18.2 kgf / mm ² Example 4 (a) Preparation of resin composition The following raw materials were kneaded to obtain a primary resin composition.

(1) Tetraglycidyldiaminodiphenylmethane (ELM434, manufactured by Sumitomo Chemical Co., Ltd.) 90.0 parts (2) Bisphenol A type epoxy resin (Epicoat 825, manufactured by Yuka Shell Epoxy Co., Ltd.) 10.0 parts (3) Polyether sulfone (PES5003P, manufactured by Mitsui Toatsu Chemicals, Inc.) 12.3 parts (4) 3,3′-diaminodiphenyl sulfone (manufactured by Wakayama Seika Co., Ltd.) 36.0 parts The following raw materials are kneaded. Then, a secondary resin composition was obtained.

(1) Tetraglycidyldiaminodiphenylmethane (ELM434, manufactured by Sumitomo Chemical Co., Ltd.) 60.0 parts (2) Bisphenol F type epoxy resin (Epiclone 830, manufactured by Dainippon Ink and Chemicals, Inc.) 20.0 Part (3) Brominated bisphenol A type epoxy resin (Epiclon 152, manufactured by Dainippon Ink and Chemicals, Inc.) 20.0 parts (4) Polyether sulfone (PES5003P, manufactured by Mitsui Toatsu Chemicals, Inc.) 13.2 Parts (5) trimethylene bis (4-aminobenzoate) (CUA-4, manufactured by Ihara Chemical Industry Co., Ltd.) 52.0 parts (b) Physical properties of cured resin The resin prepared in (a) was heated at 180 ° C. A cured resin plate was prepared by curing for 2 hours, and physical properties were evaluated in the same manner as in Example 1.

The breaking elongation of the secondary resin composition was 6.2%.

(C) Preparation of prepreg A resin film was prepared by applying the primary resin prepared in (a) onto release paper using a reverse roll coater so that the coating amount was 31.2 g / m ² . Next, a secondary resin was applied so that the applied amount was 20.5 g / m ² , to produce a resin film.

Carbon fibers aligned in one direction (T800
H and Toray Co., Ltd. are sandwiched from both sides with the primary resin film, heated and pressed to impregnate the resin, and a secondary resin film is attached to both sides of the primary resin film.
A prepreg having a carbon fiber content of 90 g / m ² and a carbon fiber content of 64.8% was obtained.

(D) Preparation of cured plate The prepreg prepared in (c) was (+ 45/0 / -45 /
90 degree) _2S , and (+ 45/0 / -45 / 90 degree) _3S
It laminated in the composition. This was cured under the same conditions as in Example 1.

[0103] The (e) Measurement of compressive strength (+ 45/0 / -45 / 90 °) _2S cured plate of the configuration of,
It processed into a perforated board like Example 1, and measured room temperature compressive strength and compressive strength at the time of high temperature and high humidity. The results were as follows.

Compressive strength at room temperature: 30.2 kgf / mm ² Compressive strength at high temperature and high humidity: 27.1 kgf / mm ² Further, a cured plate having a (+ 45/0 / −45 / 90 degree) _3S configuration was used as in Example 1. After processing in the same way, 311 in the center
A falling weight impact of 1 kgf · mm was applied and the compressive strength after impact was measured. The results are as follows.

Compressive strength after impact: 15.5 kgf / mm ² Example 5 (a) Preparation of resin composition The following raw materials were kneaded to obtain a primary resin composition.

(1) Tetraglycidyldiaminodiphenylmethane (ELM434, manufactured by Sumitomo Chemical Co., Ltd.) 90.0 parts (2) Bisphenol A type epoxy resin (Epicoat 825, manufactured by Yuka Shell Epoxy Co., Ltd.) 10.0 parts (3) Polyether sulfone (PES5003P, manufactured by Mitsui Toatsu Chemicals, Inc.) 12.3 parts (4) 3,3′-diaminodiphenyl sulfone (manufactured by Wakayama Seika Co., Ltd.) 36.0 parts The following raw materials are kneaded. Then, a secondary resin composition was obtained.

(1) Tetraglycidyldiaminodiphenylmethane (ELM434, manufactured by Sumitomo Chemical Co., Ltd.) 50.0 parts (2) Bisphenol F type epoxy resin (Epiclone 830, manufactured by Dainippon Ink and Chemicals, Inc.) 40.0 Part (3) Bisphenol A type epoxy resin (Epicoat 825, manufactured by Yuka Shell Epoxy Co., Ltd.) 10.0 parts (4) polyether sulfone (PES5003P, manufactured by Mitsui Toatsu Chemicals, Inc.) 10.0 parts (5) ) 4,4'-Phenylene diisopropylidene (2,6-dimethylaniline) (HPT1062, manufactured by Shell Chemical Company) 73.0 parts (b) Physical properties of cured resin The resin prepared in (a) was used. The plate was cured at 180 ° C. for 2 hours to prepare a plate of a cured resin, and the physical properties were evaluated in the same manner as in Example 1.

The breaking elongation of the secondary resin composition was 7.3%.

(C) Preparation of prepreg A resin film was prepared by applying the primary resin prepared in (a) onto release paper using a reverse roll coater so that the coating amount was 31.2 g / m ² . Next, a secondary resin was applied so that the applied amount was 20.5 g / m ² , to produce a resin film.

Carbon fibers aligned in one direction (T800
H and Toray Co., Ltd. are sandwiched from both sides with the primary resin film, heated and pressed to impregnate the resin, and a secondary resin film is attached to both sides of the primary resin film.
A prepreg having a carbon fiber content of 90 g / m ² and a carbon fiber content of 64.8% was obtained.

(D) Preparation of Hardened Plate The prepreg prepared in (c) was (+ 45/0 / −45 /
90 degree) _2S , and (+ 45/0 / -45 / 90 degree) _3S
It laminated in the composition. This was cured under the same conditions as in Example 1.

[0112] The (e) Measurement of compressive strength (+ 45/0 / -45 / 90 °) _2S cured plate of the configuration of,
It processed into a perforated board like Example 1, and measured room temperature compressive strength and compressive strength at the time of high temperature and high humidity. The results were as follows.

Compressive strength at room temperature: 30.9 kgf / mm ² Compressive strength at high temperature and high humidity: 27.4 kgf / mm ² Further, a cured plate having a (+ 45/0 / −45 / 90 degree) _3S configuration was used as in Example 1. After processing in the same way, 311 in the center
A falling weight impact of 1 kgf · mm was applied and the compressive strength after impact was measured. The results are as follows.

Compressive Strength after Impact: 17.1 kgf / mm ² Comparative Example 2 The following raw materials were kneaded to obtain a resin composition.

(1) Tetraglycidyldiaminodiphenylmethane (ELM434, manufactured by Sumitomo Chemical Co., Ltd.) 35.0 parts (2) Bisphenol A type epoxy resin (Epicoat 825, manufactured by Yuka Shell Epoxy Co., Ltd.) 15.0 parts (3) Bisphenol F type epoxy resin (Epiclon 830, manufactured by Dainippon Ink and Chemicals, Inc.) 50.0 parts (4) Polyether sulfone (PES5003P, manufactured by Mitsui Toatsu Chemicals, Inc.) 18.0 parts (5 ) 4,4'-Diaminodiphenyl sulfone (Sumicure S, manufactured by Sumitomo Chemical Co., Ltd.) 41.1 parts (b) Measurement of physical properties of cured resin The resin prepared in (a) was cured at 180 ° C for 2 hours. A plate of a cured resin product was prepared and the physical properties were evaluated in the same manner as in Example 1.

The room temperature flexural modulus of the cured product of the resin composition is
350 kgf / mm ² and 8 after absorbing water for 20 hours with boiling water
The flexural modulus at 2 ° C. was 250 kgf / mm ² .

(C) Preparation of prepreg The resin prepared in (a) was coated on a release paper with a reverse roll coater so that the coating amount was 51.7 g / m ² to prepare a resin film.

Carbon fibers aligned in one direction (T800
H, Toray Co., Ltd. is sandwiched from both sides with the above resin film, heated and pressed to impregnate the resin, and a secondary resin film is attached to both sides thereof to form a carbon fiber basis weight 190
A prepreg having a g / m ² and carbon fiber content of 64.8% was obtained.

(D) Preparation of cured plate The prepreg prepared in (c) was (+ 45/0 / -45 /
90 degree) _2S , and (+ 45/0 / -45 / 90 degree) _3S
It laminated in the composition. These were cured under the same conditions as in Example 1.

[0120] The (e) Measurement of compressive strength (+ 45/0 / -45 / 90 °) _2S cured plate of the configuration of,
It processed into a perforated board like Example 1, and measured room temperature compressive strength and compressive strength at the time of high temperature and high humidity. The results were as follows.

Compressive strength at room temperature: 25.3 kgf / mm ² Compressive strength at high temperature and high humidity: 21.9 kgf / mm ² Furthermore, a cured plate having a (+ 45/0 / −45 / 90 degree) _3S configuration was used as in Example 1. After processing in the same manner, 3111 kgf
A falling weight impact of mm was given and the compressive strength after the impact was measured.
The results were as follows.

Compressive strength after impact: 17.5 kgf / mm ² Comparative Example 3 (a) Preparation of resin composition The following raw materials were kneaded to obtain a resin composition.

(1) Tetraglycidyldiaminodiphenylmethane (ELM434, manufactured by Sumitomo Chemical Co., Ltd.) 35.0 parts (2) Bisphenol F type epoxy resin (Epiclone 830, manufactured by Dainippon Ink and Chemicals, Inc.) 35.0 Parts (3) Brominated bisphenol A type epoxy resin (Epiclon 152, manufactured by Dainippon Ink and Chemicals, Inc.) 30.0 parts (4) Polyether sulfone (PES5003P, manufactured by Mitsui Toatsu Chemicals, Inc.) 13.0 Parts (5) 4,4′-diaminodiphenyl sulfone (Sumicure S, manufactured by Sumitomo Chemical Co., Ltd.) 35.0 parts (b) Physical properties measurement of resin cured product Resin prepared in (a) is 180 ° C. for 2 hours A resin cured product plate was prepared by curing, and physical properties were evaluated in the same manner as in Example 1.

The room temperature flexural modulus of the cured product of the resin composition is
365 kgf / mm ^2, which is 8 after absorbing boiling water for 20 hours.
The flexural modulus at 2 ° C. was 270 kgf / mm ² .

(C) Preparation of prepreg The resin prepared in (a) was coated on a release paper with a reverse roll coater so that the coating amount was 51.7 g / m ² to prepare a resin film.

Carbon fibers aligned in one direction (T800
H and Toray Co., Ltd. are sandwiched from both sides with the primary resin film, heated and pressed to impregnate the resin, and a secondary resin film is attached to both sides of the primary resin film.
A prepreg having a carbon fiber content of 90 g / m ² and a carbon fiber content of 64.8% was obtained.

(D) Preparation of Hardened Plate The prepreg prepared in (c) was (+ 45/0 / −45 /
90 degree) _2S , and (+ 45/0 / -45 / 90 degree) _3S
It laminated in the composition. These were cured under the same conditions as in Example 1.

[0128] The (e) Measurement of compressive strength (+ 45/0 / -45 / 90 °) _2S cured plate of the configuration of,
It processed into a perforated board like Example 1, and measured room temperature compressive strength and compressive strength at the time of high temperature and high humidity. The results were as follows.

Compressive strength at room temperature: 26.0 kgf / mm ² Compressive strength at high temperature and high humidity: 22.6 kgf / mm ² Further, a cured plate having a (+ 45/0 / −45 / 90 degree) _3S configuration was used as in Example 1. Similarly, after processing, 3111 kgf · mm
The falling weight impact was applied, and the compressive strength after the impact was measured. The results were as follows.

Compressive strength after impact: 15.5 kgf / mm ² Comparative Example 4 (a) Preparation of resin composition The following raw materials were kneaded to obtain a resin composition.

(1) Tetraglycidyldiaminodiphenylmethane (ELM434, manufactured by Sumitomo Chemical Co., Ltd.) 60.0 parts (2) Bisphenol F type epoxy resin (Epiclon 830, manufactured by Dainippon Ink and Chemicals, Inc.) 20.0 Part (3) brominated bisphenol A type epoxy resin (Epiclon 152, manufactured by Dainippon Ink and Chemicals, Inc.) 20.0 parts (4) polyether sulfone (PES5003P, manufactured by Mitsui Toatsu Chemicals, Inc.) 13.2 Parts (5) trimethylene bis (4-aminobenzoate) (CUA-4, manufactured by Ihara Chemical Industry Co., Ltd.) 52.0 parts (b) Physical properties of cured resin The resin prepared in (a) was heated at 180 ° C. A resin cured product plate was prepared by curing for 2 hours, and physical properties were evaluated in the same manner as in Example 1.

The room temperature flexural modulus of the cured product of the resin composition is
370 kgf / mm ² and 8 after absorbing 20 hours of boiling water
The flexural modulus at 2 ° C. was 260 kgf / mm ² .

(C) Preparation of prepreg The resin prepared in (a) was coated on release paper using a reverse roll coater so that the coating amount was 51.7 g / m ² to prepare a resin film.

Carbon fibers aligned in one direction (T800
H and Toray Co., Ltd. are sandwiched from both sides with the primary resin film, heated and pressed to impregnate the resin, and a secondary resin film is attached to both sides of the primary resin film.
A prepreg having a carbon fiber content of 90 g / m ² and a carbon fiber content of 64.8% was obtained.

(D) Preparation of Hardened Plate The prepreg prepared in (c) was (+ 45/0 / −45 /
90 degree) _2S , and (+ 45/0 / -45 / 90 degree) _3S
It laminated in the composition. These were cured under the same conditions as in Example 1.

[0136] The (e) Measurement of compressive strength (+ 45/0 / -45 / 90 °) _2S cured plate of the configuration of,
It processed into a perforated board like Example 1, and measured room temperature compressive strength and compressive strength at the time of high temperature and high humidity. The results were as follows.

Compressive strength at room temperature: 25.9 kgf / mm ² Compressive strength at high temperature and high humidity: 22.5 kgf / mm ² Further, a cured plate having a (+ 45/0 / −45 / 90 degree) _3S configuration was used as in Example 1. Similarly, after processing, 3111 kgf · mm
The falling weight impact was applied, and the compressive strength after the impact was measured. The results were as follows.

Compressive strength after impact: 15.9 kgf / mm ² Example 6 (a) Preparation of resin composition The following raw materials were kneaded to obtain a primary resin composition.

(1) Tetraglycidyldiaminodiphenylmethane (ELM434, manufactured by Sumitomo Chemical Co., Ltd.) 90.0 parts (2) Bisphenol A type epoxy resin (Epicoat 825, manufactured by Yuka Shell Epoxy Co., Ltd.) 10.0 parts (3) Polyether sulfone (PES5003P, manufactured by Mitsui Toatsu Chemicals, Inc.) 12.3 parts (4) 3,3′-diaminodiphenyl sulfone (manufactured by Wakayama Seika Co., Ltd.) 36.0 parts The following raw materials are kneaded. Then, a secondary resin composition was obtained.

(1) Tetraglycidyldiaminodiphenylmethane (ELM434, manufactured by Sumitomo Chemical Co., Ltd.) 35.0 parts (2) Bisphenol A type epoxy resin (Epicoat 825, manufactured by Yuka Shell Epoxy Co., Ltd.) 15.0 parts (3) Bisphenol F type epoxy resin (Epiclon 830, manufactured by Dainippon Ink and Chemicals, Inc.) 50.0 parts (4) Polyether sulfone (PES5003P, manufactured by Mitsui Toatsu Chemicals, Inc.) 7.5 parts (5) ) 4,4'-Diaminodiphenyl sulfone (Sumicure S, manufactured by Sumitomo Chemical Co., Ltd.) 41.1 parts (6) Epoxy-modified nylon particles 77.0 parts Epoxy of (6) among the raw materials of the secondary resin composition The modified nylon particles used were those shown in Example 1 of JP-A-1-104624.

(B) Measurement of physical properties of cured resin product The resin prepared in (a) was cured at 180 ° C. for 2 hours to prepare a cured resin plate, and the physical properties were evaluated in the same manner as in Example 1.

The room temperature flexural modulus of the cured product of the primary resin composition was 420 kgf / mm ² , and the flexural modulus at 82 ° C. after absorbing boiling water for 20 hours was 330 kgf / mm ² .

The tensile fracture elongation of the cured product of the secondary resin composition ((1) to (5)) excluding the epoxy-modified nylon particles is
It was 7.3%.

(C) Preparation of prepreg A resin film was prepared by coating the primary resin prepared in (a) on release paper using a reverse roll coater so that the coating amount was 31.2 g / m ² . Next, a secondary resin was applied so that the applied amount was 20.5 g / m ² , to produce a resin film.

Carbon fibers aligned in one direction (T800
H and Toray Co., Ltd. are sandwiched from both sides with the primary resin film, heated and pressed to impregnate the resin, and a secondary resin film is attached to both sides of the primary resin film.
A prepreg having a carbon fiber content of 90 g / m ² and a carbon fiber content of 64.8% was obtained.

(D) Preparation of Hardened Plate The prepreg prepared in (c) was (+ 45/0 / −45 /
90 degree) _2S , and (+ 45/0 / -45 / 90 degree) _3S
It laminated in the composition. These were cured under the same conditions as in Example 1.

[0147] The (e) Measurement of compressive strength (+ 45/0 / -45 / 90 °) _2S cured plate of the configuration of,
It processed into a perforated board like Example 1, and measured room temperature compressive strength and compressive strength at the time of high temperature and high humidity. The results were as follows.

Compressive strength at room temperature: 31.5 kgf / mm ² Compressive strength at high temperature and high humidity: 27.5 kgf / mm ² Furthermore, a cured plate having a (+ 45/0 / −45 / 90 degree) _3S configuration was used as in Example 1. After processing in the same manner, 3111 kgf
A falling weight impact of mm was given and the compressive strength after the impact was measured.
The results were as follows.

Compressive strength after impact: 32.9 kgf / mm ² Example 7 (a) Preparation of resin composition The following raw materials were kneaded to obtain a primary resin composition.

(1) Tetraglycidyldiaminodiphenylmethane (ELM434, manufactured by Sumitomo Chemical Co., Ltd.) 90.0 parts (2) Bisphenol A type epoxy resin (Epicoat 825, manufactured by Yuka Shell Epoxy Co., Ltd.) 10.0 parts (3) Polyether sulfone (PES5003P, manufactured by Mitsui Toatsu Chemicals, Inc.) 12.3 parts (4) 3,3′-diaminodiphenyl sulfone (manufactured by Wakayama Seika Co., Ltd.) 36.0 parts The following raw materials are kneaded. Then, a secondary resin composition was obtained.

(1) Tetraglycidyldiaminodiphenylmethane (ELM434, manufactured by Sumitomo Chemical Co., Ltd.) 60.0 parts (2) Bisphenol F type epoxy resin (Epiclon 830, manufactured by Dainippon Ink and Chemicals, Inc.) 40.0 Part (3) Polyethersulfone (PES5003P, manufactured by Mitsui Toatsu Chemicals, Inc.) 6.2 parts (4) 4,4′-methylenebis (2,6-diethylaniline) (Kayabond C-300, Nippon Kayaku ( Manufactured by Co., Ltd.) 49.1 parts (5) Epoxy-modified nylon particles 74.0 parts Epoxy-modified nylon particles (5) among the raw materials of the secondary resin composition are shown in Example 1 of JP-A-1-104624. The one used was used.

(B) Measurement of Physical Properties of Cured Resin The resin prepared in (a) was cured at 180 ° C. for 2 hours to prepare a cured resin plate, and the physical properties were evaluated in the same manner as in Example 1.

The room temperature flexural modulus of the cured product of the primary resin composition was 420 kgf / mm ² , and the flexural modulus at 82 ° C. after absorbing boiling water for 20 hours was 330 kgf / mm ² .

The tensile breaking elongation of the cured product of the secondary resin composition ((1) to (5)) excluding the epoxy-modified nylon particles is
It was 7.5%.

(C) Preparation of prepreg A resin film was prepared by applying the primary resin prepared in (a) onto release paper using a reverse roll coater so that the coating amount was 31.2 g / m ² . Next, a secondary resin was applied so that the applied amount was 20.5 g / m ² , to produce a resin film. Carbon fibers aligned in one direction (T8
00H, manufactured by Toray Industries, Inc., sandwiched from both sides with the primary resin film, heated and pressed to impregnate the resin, and a secondary resin film attached to both sides thereof, and a carbon fiber basis weight of 190 g / m ² , A prepreg having a carbon fiber content of 64.8% was obtained.

(D) Preparation of Hardened Plate The prepreg prepared in (c) was (+ 45/0 / −45 /
90 degree) _2S , and (+ 45/0 / -45 / 90 degree) _3S
It laminated in the composition. These were cured under the same conditions as in Example 1.

[0157] The (e) Measurement of compressive strength (+ 45/0 / -45 / 90 °) _2S cured plate of the configuration of,
It processed into a perforated board like Example 1, and measured room temperature compressive strength and compressive strength at the time of high temperature and high humidity. The results were as follows.

Compressive strength at room temperature: 30.3 kgf / mm ² Compressive strength at high temperature and high humidity: 26.7 kgf / mm ² Further, a cured plate having a (+ 45/0 / −45 / 90 degree) _3S configuration was used as in Example 1. After processing in the same manner, 3111 kgf
A falling weight impact of mm was given and the compressive strength after the impact was measured.
The results were as follows.

Compressive strength after impact: 34.3 kgf / mm ²

[0160]

The prepreg of the present invention uses a combination of specific matrix resins. As a result, as is clear from the above examples, the fiber-reinforced composite material obtained by curing the prepreg has mechanical properties of the compression system, which have been considered to be difficult in the past, and particularly high perforated plate under high temperature and high humidity conditions. Both compression strength and high impact resistance (compression strength after impact) can be achieved at the same time. Therefore, the fiber-reinforced composite material obtained by using the prepreg of the present invention is suitable as a perforated structural material having a bolt hole or the like, and the applicable applications can be greatly expanded.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI technical display location B29K 105: 08

Claims (12)

[Claims] 1. A prepreg comprising the following components (A), (B) and (C), wherein (C) is present on the surface side of (B). (A) Reinforcing fiber (B) Cured product has a flexural modulus at room temperature of 380 kgf / m
Epoxy resin composition having m ² or more (C) Epoxy resin composition having a tensile elongation at break of 5% or more 2. A flexural modulus at 82 ° C. after absorption of boiling water for 20 hours in a cured product of the epoxy resin composition (B) is 280 kgf.
/ Mm ² or more, the prepreg according to claim 1. 3. The prepreg according to claim 1, wherein the cured product of the epoxy resin composition (C) has a tensile breaking elongation of 7% or more. 4. A flexural modulus at 82 ° C. of a cured product of an epoxy resin composition (B) after absorbing water with boiling water for 20 hours at 320 kgf.
/ Mm ² or more, the prepreg according to any one of claims 1 to 3. 5. The prepreg according to claim 1, wherein 70% or more of the epoxy resin component in the epoxy resin composition (B) is a trifunctional or more functional epoxy resin. 6. The prepreg according to claim 1, which contains diaminodiphenyl sulfone as a curing agent component in the epoxy resin composition (B). 7. The prepreg according to claim 1, wherein 50% or more of the epoxy resin component in the epoxy resin composition (C) is a monofunctional or bifunctional epoxy resin. 8. The epoxy resin composition (C) according to claim 1, which contains at least one compound having a structure of the following general formulas (I) to (III) as a curing agent component. Prepreg described in. Embedded image (In the formula, X _{1 to} X ₈ represent a group selected from a hydrogen atom, a halogen atom and an alkyl group having 1 to 5 carbon atoms, and Y ₁ represents an alkylene group having 1 to 10 carbon atoms.) (In the formula, X _{9 to} X ₂₀ represent a group selected from a hydrogen atom, a halogen atom, and an alkyl group having 1 to 5 carbon atoms, and Y ₂ , Y ₃
Represents an alkylene group having 1 to 10 carbon atoms. ) [Chemical 3] (In the formula, X _{21 to} X ₂₈ represent a group selected from a hydrogen atom, a halogen atom and an alkyl group having 1 to 5 carbon atoms, and Y ₄ represents an alkylene group having 1 to 10 carbon atoms.) 9. The prepreg according to claim 1, wherein the epoxy resin composition (C) contains at least one kind of a thermoplastic resin and an elastomer which is soluble in the epoxy resin. 10. A thermoplastic resin soluble in an epoxy resin,
The prepreg according to claim 9, wherein the elastomer has a functional group capable of reacting with an epoxy resin or a curing agent. 11. The prepreg according to claim 1, wherein the reinforcing fibers (A) are carbon fibers. 12. A fiber-reinforced composite material obtained by curing the prepreg according to any one of claims 1 to 11.