JP3508346B2 - Prepreg and fiber reinforced composite materials - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a prepreg for molding a fiber-reinforced composite material, and a fiber-reinforced composite material molded from the prepreg. More specifically, the present invention relates to a prepreg which has excellent mechanical properties of a compression system and provides a fiber-reinforced composite material suitable as a structural material, and a composite material obtained from the prepreg.

[0002]

2. Description of the Related Art Polymer-based composite materials composed of reinforcing fibers and matrix resins are widely used in sports equipment, aerospace applications, and general industrial applications because of their light weight and excellent mechanical properties. In the manufacture of fiber reinforced composite materials,
Although various methods are used, a method using a prepreg which is a sheet-shaped intermediate base material in which reinforced fibers are impregnated with an uncured matrix resin is widely used. In this method, a molded article of a composite material is usually obtained by heating a plurality of prepregs after laminating them.

As the matrix resin used for the prepreg, both thermosetting resin and thermoplastic resin are used, but in most cases, thermosetting resin having excellent handling property is used, and among them, epoxy resin is the most preferable. Many are used. Further, a maleimide resin, a cyanate resin and a combination thereof are often used, and one of the important physical properties when the fiber reinforced composite material is used as a structural material is the compressive strength. When used as a structural member, bolt holes are often provided, so that the compressive strength of a perforated plate is particularly required.

[0004] In general, polymer materials have low strength and elastic modulus under high temperature and / 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 an aircraft, a vehicle, a ship, etc., it is required to sufficiently retain the physical properties even under high temperature and / or high humidity conditions.

Compressive strength is a particularly important physical property when fiber-reinforced composite materials are used as structural materials. The compressive strength is measured using a test piece such as a non-perforated plate, a perforated plate, or a cylinder.In actual use, it is often a plate material with bolt holes, The compressive strength of the perforated plate, especially the strength under high temperature and high humidity conditions, becomes important.

However, in the conventional polymer matrix composite material,
Although it has the advantage of being lightweight, the compressive strength under high-temperature or high-humidity conditions may not be sufficient, which may limit the applicable applications.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to provide a prepreg 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 which provides a fiber reinforced composite material suitable as a structural material. It is in.

[0008]

Means for Solving the Problems A prepreg of the present invention which meets the above-mentioned object contains reinforcing fibers and a matrix resin, and the thermosetting resin in the matrix resin is (A) cyanate ester resin, or maleimide resin and cyan resin. A mixture of acid ester resins or a pre-reactant (B) consisting of a trifunctional or higher functional glycidylamine type epoxy resin , and the weight ratio of (A) and (B) is 70: 3.
0 to 90: 10 in a by and at least including prepreg thermoplastic resin is in the matrix resin (C) a glass transition temperature of 180 ° C. or higher.

[0009] In addition, the fiber-reinforced composite material according to the present invention,
It is formed by curing and molding such a prepreg.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be specifically described below.
A thermosetting resin is used as the matrix resin used in the prepreg of the present invention.

[0011] In the present invention, the matrix resin is composed of a (A) cyanate ester resin or a mixture or pre-reaction product of the maleimide resin and cyanate ester resin (B) 3 or more functional glycidyl amine type epoxy resin, And the weight ratio of (A) and (B) is 70: 3.
0 to 90: 10 in a by and at least including prepreg thermoplastic resin is in the matrix resin (C) a glass transition temperature of 180 ° C. or higher.

By using the specific matrix resin as described above, it is possible to improve the perforated plate compressive strength when the prepreg according to the present invention is formed into a fiber reinforced composite material, especially at high temperature and high humidity.

One of the constituents of the matrix resin is a cyanate ester resin, or a mixture of a maleide resin and a cyanate ester resin or a pre-reactant.

The maleimide resin is a compound having a plurality of maleimide groups in the molecule, and examples thereof include methylenebis-p-phenylene dimaleimide.

The cyanate ester resin is a compound having a plurality of cyanato groups in the molecule, and examples thereof include bisphenol A dicyanate, bisphenol F dicyanate, and cyanate ester of novolac oligomer.

In the mixture of the maleimide resin and the cyanate ester resin or the preliminary reaction product as described above, the maleimide resin is methylenebis-p-phenylene dimaleimide and the cyanate ester resin is bisphenol A.
Those that are dicyanates are preferred. At this time, the weight ratio of methylene bis-p-phenylene dimaleimide and bisphenol A dicyanate is preferably 30:70 to 0: 100. 0: 100 is a case where the maleimide resin is 0 and the composition (A) is composed only of the esfual cyanate resin.

The mixture of the maleimide resin and the cyanate ester resin or the pre-reacted product, as it is, has a high temperature required for curing, and is practically limited. 18 in practical use
A curing temperature of 0 ° C. or lower is desirable. A radical initiator and an epoxy resin are blended in order to optimize the curing temperature. If only cyanate ester resin is used, no radical initiator is needed.

As the radical initiator to be blended, an organic peroxide such as dicumyl peroxide is preferably used.

Bisphenol A type epoxy resin and bisphenol F type epoxy resin are generally used as the epoxy resin to be blended. When these are used, the compressive strength of the fiber reinforced composite material at high temperature and high humidity is high. Becomes insufficient. Excellent compressive strength can be obtained by using (B ) a trifunctional or higher functional glycidylamine type epoxy resin as the epoxy resin .

Here, the glycidylamine type epoxy resin is a compound having one or more glycidylamino groups in the molecule and may further have a glycidyloxy group.

The trifunctional or higher functional glycidylamine type epoxy resin is not particularly limited, but tetraglycidyldiaminodiphenylmethane is preferable because it provides particularly high compressive strength at high temperature and high humidity.

[0022]

[0023]

These may be used alone or in combination of two or more.

The matrix resin of the prepreg of the present invention contains a thermoplastic resin having a glass transition temperature of 180 ° C. or higher as the component (C). The thermoplastic resin used in the present invention has a glass transition temperature of 1 from the viewpoint of heat resistance.
It is not particularly limited as long as it is 80 ° C. or higher, but from the viewpoint of improving toughness, polysulfone or polyimide is preferable. Further, those having an ether bond in the skeleton are more preferable from the viewpoint of compatibility with the thermoplastic resin which is the main component of the matrix resin. As such a thermoplastic resin, polyether sulfone or polyether imide is preferably used.

The polyether sulfone is preferably a polymer having an aromatic divalent group, an ether bond and a sulfonyl group. As a preferable polyether sulfone, one having the following structural formula (II) can be given as an example.

[0027]

[Chemical 4] The polyetherimide is an aromatic divalent group and an ether bond,
Polymers consisting of imide groups are preferred. Examples of preferable polyether imides include those having the following structural formula (III).

[0028]

[Chemical 5] In the prepreg according to the present invention, (A),
The mixing ratio is not particularly limited as long as the components (B) and (C) are included, but in order to efficiently increase the compressive strength at high temperature and high humidity, the mixture of (A) or the preliminary reaction product and (B) The weight ratio with the epoxy resin is preferably 70:30 to 90:10. Further, the weight ratio of the mixture or the preliminary reaction product of (A) and the epoxy resin of (B) to the polyether sulfone of (C) is 100: 2 to 100: 2.
It is preferably 0.

As the reinforcing fiber of the prepreg according to the present invention, glass fiber, carbon fiber, aramid fiber, boron fiber, alumina fiber, silicon carbide fiber and the like are used.
Of these, carbon fiber is particularly preferable. The form of the reinforcing fiber is not particularly limited, and for example, long fibers aligned in one direction, tows, woven fabrics, mats, knits,
Braid is used.

The production of the prepreg is not particularly limited, and a usual prepreg manufacturing process can be applied.

When a composite material produced by laminating prepregs is used as a structural material, an important physical property is compressive strength after impact. This is because there is a phenomenon in which the composite material is delaminated between layers due to an impact on a member due to a drop of a tool or a collision such as a small stone, and the compressive strength is lowered. If this is remarkable, it cannot be used as a structural material.

Generally, in order to increase the compressive strength after impact,
It is known that it is effective to allow a high toughness material to exist near the surface of one or both surfaces of the prepreg and to distribute the high toughness material between the layers of the composite material obtained by laminating and curing. Examples of the high toughness material include, for example, JP-A-63-162.
No. 732, a thermoplastic resin, for example, an elastomer as shown in JP-A-4-268361, an elastomer-modified thermosetting resin as shown in U.S. Pat. No. 3,472,730. Although a method of using the same is known, a thermoplastic resin is preferable in the present invention because the physical properties at high temperature are deteriorated when an elastomer or an elastomer-modified thermosetting resin is used.

The thermoplastic resin to be present on one side or the surface of the prepreg includes polyamide, polyimide, polyetherimide, polyamideimide, polysulfone,
Polyether sulfone and the like are preferable. Among these,
Polyamides, which have excellent toughness and adhesion to the matrix resin, are particularly preferable. Polyamide is disclosed in JP-A-1-10
It is also possible to use those modified with an epoxy resin as disclosed in Japanese Patent No. 4624.

The thermoplastic resin may be in the form of a film, particles or fibers. In the case of the film form, when the surface of the prepreg is completely covered as in U.S. Pat. No. 4,604,319, the surface tack is lost, but as shown in JP-A-63-97635, a through hole is provided. To retain the surface tack by adopting a method such as making it porous as shown in JP-A-5-138785, or arranging tape-like films as shown in JP-A-5-287091. You can

In the case of a 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.

Regarding 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.
Woven fabric as shown in 32843, International Publication No. 9
Nonwoven fabrics, knits, and the like as disclosed in Japanese Patent No. 4016003 can be used.

As a method for allowing the above-mentioned thermoplastic resin to exist near the surface of the prepreg, a method in which the thermoplastic resin is simply pasted or sprinkled on one or both sides of the prepreg prepared by a conventional method, or a conventional method is used. A method in which a film obtained by impregnating a thermoplastic resin with a matrix resin or a film obtained by dispersing a thermoplastic resin in a matrix resin is attached to one or both surfaces of the prepared prepreg can be used.

[0038]

EXAMPLES The present invention will now be described in more detail with reference to examples.

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

(1) Preliminary reaction product of methylenebis-p-phenylene dimaleimide and bisphenol A dicyanate (1: 9) (BT2160, manufactured by Mitsubishi Gas Chemical Co., Inc.) 80.0 parts (2) tetraglycidyldiaminodiphenylmethane (ELM434) , Sumitomo Chemical Co., Ltd.) 20.0 parts (3) Polyethersulfone (PES5003P, manufactured by Mitsui Toatsu Chemicals, Inc.) 7.0 parts (4) Dicumyl peroxide 0.1 part (5) p- Toluenesulfonic acid 0.04 parts (B) Preparation of prepreg The resin prepared in (A) was coated on release paper using a reverse roll coater to a coating amount of 51.7 g / m ² to prepare a resin film. did. Carbon fibers (T800H, manufactured by Toray Industries, Inc.) aligned in one direction are sandwiched with the above resin film from both sides, impregnated with heat and pressure to impregnate the resin, and the carbon fiber areal weight is 190 g / m ² , the carbon fiber content rate is 64. .8
% Prepreg was obtained.

(C) Preparation of Hardened Plate The prepreg prepared in (B) was laminated at an angle of (+ 45/0 / −45 / 90 degrees) _{2 s} with respect to the longitudinal direction.
This is placed in an autoclave at a temperature of 180 ° C and a pressure of 0.5.
Curing was performed for 2 hours under the condition of 88 MPa.

(D) Measurement of compressive strength The cured plate was set to 12 inches in the 0 ° direction and 1.5 in the 90 ° direction.
Cut out into a rectangular of 1 inch, punch a circular hole with a diameter of 0.25 inch in the center and process it into a perforated plate, compressive strength at room temperature (24 ° C) and high temperature and high humidity (in hot water at 71 ° C Instron 1128 (measured at 82 ° C after immersion for 2 weeks)
It measured using the type | mold tester. The results are as follows.

Room temperature compressive strength: 316 MPa Compressive strength at high temperature and high humidity: 287 MPa Example 2 (A) Preparation of resin composition The following raw materials were kneaded to obtain a primary resin composition.

[0044] (1) Methylenebis-p-phenylenedimaleimide and bisphenol A dicyanene (1: 9) pre-reactant     (BT2160, manufactured by Mitsubishi Gas Chemical Co., Inc.) 80.0 parts (2) Tetraglycidyl diaminodiphenylmethane     (ELM434, manufactured by Sumitomo Chemical Co., Ltd.) 20.0 parts (3) Polyether sulfone     (PES5003P, manufactured by Mitsui Toatsu Chemicals, Inc.) 7.0 parts (4) Dicumyl peroxide 0.1 part (5) p-toluenesulfonic acid 0.04 part Further, the following raw materials were kneaded to obtain a secondary resin composition.

(1) Preliminary reaction product of methylenebis-p-phenylene dimaleimide and bisphenol A dicyanate (1: 9) (BT2160, manufactured by Mitsubishi Gas Chemical Co., Inc.) 80.0 parts (2) tetraglycidyldiaminodiphenylmethane (ELM434) , Sumitomo Chemical Co., Ltd.) 20.0 parts (3) Polyethersulfone (PES5003P, Mitsui Toatsu Chemical Co., Ltd.) 5.0 parts (4) Dicumyl peroxide 0.1 part (5) p- Toluenesulfonic acid 0.04 parts (6) Epoxy-modified nylon particles 35.5 parts Of the raw materials of the secondary resin, the epoxy-modified nylon resin (6) is shown in Example 1 of JP-A-1-104624. I used the one.

(B) 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 (T80
OH, manufactured by Toray Co., Ltd., is sandwiched with the above-mentioned primary resin film from both sides, impregnated with heat and pressure to impregnate the resin, and a secondary resin film is 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.

(C) Preparation of Hardened Plate The prepreg prepared in (B) was (+ 45/0 / −45 /
90 degrees) _2s , and (+ 45/0 / -45 / 90 degrees) _3s
It laminated in the composition. These were cured under the same conditions as in Example 1.

[0048] The (D) 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 are as follows.

Compressive strength at room temperature: 314 MPa Compressive strength at high temperature and high humidity: 287 MPa Further, a hardened plate having a constitution of (+ 45/0 / −45 / 90 degrees) _3s is 12 inches in 0 ° direction and 1.5 in 90 ° direction. A rectangular piece of inch was cut out, and a falling weight impact of 30.5 Nm was applied to the center thereof, and the compressive strength after the impact was measured. The results are as follows.

[0050] Compressive strength after impact: 272 MPa Example 3 (A) Preparation of resin composition The following raw materials were kneaded to obtain a resin composition.

(1) Preliminary reaction product of methylenebis-p-phenylene dimaleimide and bisphenol A dicyanate (1: 9) (BT2160, manufactured by Mitsubishi Gas Chemical Co., Inc.) 80.0 parts (2) N, N′-diglycidyl -M-glycidyloxyaniline (ELM120, manufactured by Sumitomo Chemical Co., Ltd.) 20.0 parts (3) polyether sulfone (PES5003P, manufactured by Mitsui Toatsu Chemicals, Inc.) 7.0 parts (4) dicumyl peroxide 0 .1 part (5) p-toluenesulfonic acid 0.04 part (B) Preparation of prepreg The resin prepared in (A) was applied to release paper using a reverse roll coater to give a coating amount of 51.7 g / m ² . Thus, a resin film was prepared. Carbon fibers (T800H, manufactured by Toray Industries, Inc.) aligned in one direction are sandwiched with the above resin film from both sides, impregnated with heat and pressure to impregnate the resin, and the carbon fiber areal weight is 190 g / m ² , the carbon fiber content rate is 64. .8
% Prepreg was obtained.

(C) Preparation of Hardened Plate The prepreg prepared in (B) was (+ 45/0 / −45 /
90 degrees) _2s was laminated. This was cured in an autoclave at a temperature of 180 ° C. and a pressure of 0.588 MPa for 2 hours.

(D) Measurement of compressive strength The hardened plate was processed into a perforated plate in the same manner as in Example 1, and the room temperature compressive strength and the high temperature and high humidity compressive strength were measured. The results are as follows.

[0054] Room temperature compressive strength: 311 MPa Compressive strength at high temperature and high humidity: 283 MPa Example 4 (A) Preparation of resin composition The following raw materials were kneaded to obtain a resin composition.

(1) Preliminary reaction product of methylenebis-p-phenylene dimaleimide and bisphenol A dicyanate (1: 9) (BT2160, manufactured by Mitsubishi Gas Chemical Co., Inc.) 80.0 parts (2) N, N′-diglycidyl -4-Glycidyloxy-2-methylaniline (ELM100, manufactured by Sumitomo Chemical Co., Ltd.) 20.0 parts (3) Polyethersulfone (PES5003P, manufactured by Mitsui Toatsu Chemicals, Inc.) 7.0 parts (4) Dicumyl peroxide 0.1 part (5) p-toluenesulfonic acid 0.04 part (B) Preparation of prepreg The resin prepared in (A) was coated on release paper with a reverse roll coater at an amount of 51.7 g / A resin film was prepared by coating so as to have a thickness of m ² . Carbon fibers (T800H, manufactured by Toray Industries, Inc.) aligned in one direction are sandwiched with the above resin film from both sides, impregnated with heat and pressure to impregnate the resin, and the carbon fiber areal weight is 190 g / m ² , the carbon fiber content rate is 64. .8
% Prepreg was obtained.

(C) Preparation of Hardened Plate The prepreg prepared in (B) was (+ 45/0 / −45 /
90 degrees) _2s was laminated. This was cured in an autoclave at a temperature of 180 ° C. and a pressure of 0.588 MPa for 2 hours.

(D) Measurement of compressive strength The cured plate was processed into a perforated plate in the same manner as in Example 1, and the room temperature compressive strength and the high temperature and high humidity compressive strength were measured. The results are as follows.

[0058] Room temperature compressive strength: 312 MPa Compressive strength at high temperature and high humidity: 285 MPa Example 5 (A) Preparation of resin composition The following raw materials were kneaded to obtain a resin composition.

(1) Preliminary reaction product of methylenebis-p-phenylene dimaleimide and bisphenol A dicyanate (1: 9) (BT2160, manufactured by Mitsubishi Gas Chemical Co., Inc.) 80.0 parts (2) 1,6-diglycidyl Oxynaphthalene (HP4032, manufactured by Dainippon Ink Co., Ltd.) 20.0 parts (3) Polyethersulfone (PES5003P, manufactured by Mitsui Toatsu Chemicals, Inc.) 7.0 parts (4) Dicumyl peroxide 0.1 part ( 5) p-Toluenesulfonic acid 0.04 parts (B) 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. A resin film was produced. Carbon fibers (T800H, manufactured by Toray Industries, Inc.) aligned in one direction are sandwiched with the above resin film from both sides, impregnated with heat and pressure to impregnate the resin, and the carbon fiber areal weight is 190 g / m ² , the carbon fiber content rate is 64. .8
% Prepreg was obtained.

(C) Preparation of Hardened Plate The prepreg prepared in (B) was (+ 45/0 / −45 /
90 degrees) _2s was laminated. This was cured in an autoclave at a temperature of 180 ° C. and a pressure of 0.588 MPa for 2 hours.

(D) Measurement of compressive strength The cured plate was processed into a perforated plate in the same manner as in Example 1, and the room temperature compressive strength and the high temperature and high humidity compressive strength were measured. The results are as follows.

[0062] Room temperature compressive strength: 313 MPa Compressive strength at high temperature and high humidity: 285 MPa Example 6 (A) Preparation of resin composition The following raw materials were kneaded to obtain a resin composition.

(1) Preliminary reaction product of methylenebis-p-phenylene dimaleimide and bisphenol A dicyanate (1: 9) (BT2160, manufactured by Mitsubishi Gas Chemical Co., Inc.) 80.0 parts (2) tris (4-glycidyloxy) Phenyl) methane (TACTIX 742, manufactured by Dow Chemical Co., Ltd.) 20.0 parts (3) polyether sulfone (PES5003P, manufactured by Mitsui Toatsu Chemical Co., Ltd.) 7.0 parts (4) dicumyl peroxide 0.1 part ( 5) p-Toluenesulfonic acid 0.04 parts (B) 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. A resin film was produced. Carbon fibers (T800H, manufactured by Toray Industries, Inc.) aligned in one direction are sandwiched with the above resin film from both sides, impregnated with heat and pressure to impregnate the resin, and the carbon fiber areal weight is 190 g / m ² , the carbon fiber content rate is 64. .8
% Prepreg was obtained.

(C) Preparation of Hardened Plate The prepreg prepared in (B) was (+ 45/0 / −45 /
90 degrees) _2s was laminated. This was cured in an autoclave at a temperature of 180 ° C. and a pressure of 0.588 MPa for 2 hours.

(D) Measurement of compressive strength The hardened plate was processed into a perforated plate in the same manner as in Example 1, and the room temperature compressive strength and the high temperature and high humidity compressive strength were measured. The results are as follows.

[0066] Room temperature compressive strength: 314 MPa Compressive strength at high temperature and high humidity: 286 MPa Comparative Example 1 (A) Preparation of resin composition The following raw materials were kneaded to obtain a resin composition.

(1) Preliminary reaction product of methylene bis-p-phenylene dimaleimide and bisphenol A dicyanate (1: 9) (BT2160, manufactured by Mitsubishi Gas Chemical Co., Inc.) 80.0 parts (2) Bisphenol F type epoxy resin ( Epicron 830, manufactured by Dainippon Ink and Chemicals, Inc. 20.0 parts (3) Polyethersulfone (PES5003P, manufactured by Mitsui Toatsu Chemicals, Inc.) 7.0 parts (4) Dicumyl peroxide 0.1 part (5) p-Toluenesulfonic acid 0.04 part (B) Preparation of prepreg The resin prepared in (A) was coated on release paper with a reverse roll coater at an amount of 51.7.
A resin film was prepared by coating so as to have g / m ² .
Coal cord fibers aligned in one direction (T800H, Toray Industries, Inc.
Made from both sides, sandwiched with the resin film, heated,
190 g / m ^{2 of} carbon fiber areal weight by pressurizing and impregnating with resin,
A prepreg having a carbon fiber content of 64.8% was obtained.

(C) Preparation of Hardened Plate The prepreg prepared in (B) was (+ 45/0 / −45 /
90 degrees) _2s was laminated. This was cured in an autoclave at a temperature of 180 ° C. and a pressure of 0.588 MPa for 2 hours.

(D) Measurement of compressive strength The hardened plate was processed into a perforated plate in the same manner as in Example 1, and the room temperature compressive strength and the high temperature and high humidity compressive strength were measured. The results are as follows.

[0070] Room temperature compressive strength: 296 MPa Compressive strength at high temperature and high humidity: 236MPa Example 7 (A) Preparation of resin composition The following raw materials were kneaded to obtain a resin composition.

(1) Bisphenol A dicyanate (Skylex CA260, manufactured by Mitsubishi Gas Chemical Co., Inc.) 80.0 parts (2) Tetraglycidyldiaminodiphenylmethane (ELM434, manufactured by Sumitomo Chemical Co., Ltd.) 20.0 parts (3) ) Polyethersulfone (PES5003P, manufactured by Mitsui Toatsu Chemicals, Inc.) 7.0 parts (4) p-toluenesulfonic acid 0.04 part (B) Preparation of prepreg The resin prepared in (A) was placed on a reverse roll coater. A resin film was prepared by coating the release paper with a coating amount of 51.7 g / m ² . Carbon fibers (T800H, manufactured by Toray Industries, Inc.) aligned in one direction are sandwiched with the above resin film from both sides, impregnated with heat and pressure to impregnate the resin, and the carbon fiber areal weight is 190 g / m ² , the carbon fiber content rate is 64. .8
% Prepreg was obtained.

(C) Preparation of Hardened Plate The prepreg prepared in (B) was (+ 45/0 / −45 /
90 degrees) _2s was laminated. This was cured in an autoclave for 2 hours at a temperature of 180 ° C. and a pressure of 0.588 MPa.

(D) Measurement of compressive strength The hardened plate was processed into a perforated plate in the same manner as in Example 1, and the room temperature compressive strength and the high temperature and high humidity compressive strength were measured. The results are as follows.

[0074] Room temperature compressive strength: 309 MPa Compressive strength at high temperature and high humidity: 283 MPa

[0075]

As described above, when the prepreg of the present invention is used, as is clear from the above examples, since a specific matrix resin is used, the fiber-reinforced composite material obtained from the prepreg is It showed high compressive strength of perforated plate under high temperature and high humidity conditions. Therefore, the fiber-reinforced composite material obtained by using the prepreg according to the present invention is suitable as a perforated structural material having bolt holes and the like, and the applicable applications can be greatly expanded.

Continuation of front page (51) Int.Cl. ⁷ identification code FI C08L 81:06 C08L 81:06 (56) References JP 62-185720 (JP, A) JP 62-275123 (JP, A) JP-A-4-239536 (JP, A) JP-A-5-9261 (JP, A) JP-A-2-311522 (JP, A) JP-A-3-166223 (JP, A) JP-A-63-162732 (JP, A) JP 5-287091 (JP, A) JP 5-329837 (JP, A) JP 6-207035 (JP, A) JP 62-252417 (JP, A) International Publication 96/071006 (WO, A1) (58) Fields investigated (Int.Cl. ⁷ , DB name) C08J 5/24 C08L 63/00 C08G 59/32 CA (STN) REGISTRY (STN)

Claims (13)

(57) [Claims] 1. A thermosetting resin containing a reinforcing fiber and a matrix resin, wherein the thermosetting resin in the matrix resin is (A) a cyanate ester resin, or a mixture of a maleimide resin and a cyanate ester resin or a pre-reactant (B) trifunctional or more. Of the glycidyl amine type epoxy resin , and the weight ratio of (A) and (B) is 70: 3.
0 to 90: 10 in a by and at least including prepreg thermoplastic resin is in the matrix resin (C) a glass transition temperature of 180 ° C. or higher. 2. The total amount of (A) and (B) is the total matrix.
X resin of 80.7% by weight or more.
The listed prepreg. 3. The total amount of (A) and (B) is the total matrix.
X-resin of 93% by weight or more, according to claim 1.
Prepreg. 4. The maleimide resin of (A) is methylene.
Bis-p-phenylenedimaleimide, cyanate
The prepreg according to any one of claims 1 to 3, wherein the steal resin is bisphenol A dicyanate . 5. The methylenebis-p- phenyl of (A) above.
Of range maleimide and bisphenol A dicyanate
The prepreg according to claim 4, wherein the weight ratio is 30:70 to 0: 100 . 6. The trifunctional or higher functional glycidylamine type ether
Poxy resin is tetraglycidyl diaminodiphenyl meta
Down a prepreg according to any one of claims 1 to 5 is. 7. The glass transition temperature of (C) is 180 ° C.
The above-mentioned thermoplastic resin is polysulfone or polyimid.
The prepreg according to claim 1, which is a cord. 8. The thermoplastic resin (C) has an acetic acid in the skeleton.
The prepreg according to any one of claims 1 to 7, which is a polysulfone or a polyimide having a tel bond . 9. The thermoplastic resin (C) is a polyether.
A sulfone, the cyanate ester resin of (A) above
Mixture of oil or maleimide resin and cyanate ester resin
Of compound or pre-reactant and epoxy resin of (B)
And the weight ratio of the polyether sulfone is 100: 2-1
The prepreg according to any one of claims 1 to 8, which is 00:20 . 10. The prepreg according to claim 1 , wherein the reinforcing fibers are carbon fibers . 11. A thermoplastic resin film, particles or
The prepreg according to any one of claims 1 to 10, wherein the fibers are present on one side or both sides . 12. The thermoplastic film, particles or
The prepreg according to claim 11, wherein the fiber is made of polyamide . 13. The method according to any one of claims 1 to 12.
A fiber-reinforced composite material obtained by curing the prepreg of.