JP2014043507A - Glass fiber fabric prepreg and glass fiber reinforced composite material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a glass fiber reinforced composite material that has both excellent antistatic performance and mechanical characteristics such as compression strength, and a glass fiber fabric prepreg that is suitably used for the same.SOLUTION: A glass fiber fabric prepreg includes at least following components: (A) glass fiber fabric, (B) epoxy resin, (C) epoxy resin curing agent, and (D) conductive filler. In an epoxy resin composition including (B), (C) and (D), 0.001-10 mass% of (D) is included, and an average grain diameter of (D) is 1 μm or less.

Description

  The present invention relates to a glass fiber woven prepreg suitably used as an antistatic material excellent in mechanical properties such as compressive strength, and a glass fiber reinforced composite material obtained by molding it.

  Various applications such as automobiles, aircraft, space equipment, railway vehicles, semiconductors, computer applications such as IC trays and notebook PC housings, sports applications such as golf shafts, bats, badminton and tennis rackets, and general industrial applications Glass fiber reinforced composite materials are used in the manufacture of simple products. In general, thermoplastic resins and short glass fibers on the order of several millimeters to several centimeters are used for glass fiber reinforced composite materials due to the features of fast molding cycles and low molding costs. Since such a glass fiber reinforced composite material is essentially electrically insulating, it is not useful for applications that require electrostatic discharge (antistatic) or electromagnetic shielding, and is used as it is for applications that require electrical conductivity. I can't do that. Therefore, as a thermoplastic resin for antistatic and electromagnetic shielding, in order to give excellent conductivity, a method of incorporating an organic antistatic material, metal particles, metal fibers, carbon fibers, carbon nanotubes, fullerenes, carbon A method of mixing a conductive filler such as black has been used. However, when an organic antistatic agent is used, the antistatic agent bleeds out to the surface, so that a change with time occurs, it is influenced by the use environment, and if it is severe, the effect is lost. In addition, when conductive filler is used, adding a sufficient amount of filler to impart electrical conductivity makes the viscosity of the thermoplastic resin extremely high, and the short glass fiber is not sufficiently impregnated with the thermoplastic resin, or the glass fiber is reinforced. There was a drawback that the mechanical properties of the composite material were greatly deteriorated (see Patent Documents 1, 2, and 3). In particular, in structural materials such as automobile outer plates, aircraft primary and secondary structural materials, windmills, space equipment, railway vehicles, and ships, high voltage is locally applied due to lightning strikes and defects in electrical wiring. In some cases, there is an extremely high demand for a material having sufficient mechanical properties while maintaining antistatic performance so that no spark is generated under the high voltage.

  In a glass fiber reinforced composite material using short glass fibers, sufficient mechanical properties that can withstand structural materials cannot be obtained (see Patent Document 3). Therefore, it is necessary to use a glass fiber fabric that can exhibit high mechanical properties at low cost. Although required, thermoplastic resins with antistatic properties using conductive fillers have high viscosity and cannot be sufficiently impregnated when impregnating glass fiber fabrics. There was a decrease in mechanical properties due to the partial aggregation. In addition, since the void becomes a local low-conductivity part, when a high voltage is applied, a spark may be generated in the low-conductivity part. Therefore, a glass fiber reinforced composite material composed of a thermoplastic resin having an antistatic property and a glass fiber fabric is not suitable for such an electric shock, such as an automobile outer plate, an aircraft primary structural material and an secondary structural material, a windmill, It was unsuitable as a housing for semiconductors, IC trays, and notebook personal computers that are required to exhibit materials for structural materials such as space equipment, railway vehicles, and ships, as well as antistatic performance (see Patent Document 1).

JP-A-7-228707 Special table 2011-513546 gazette JP 2004-182866 A

  Accordingly, an object of the present invention is to solve the above-mentioned problems and to obtain a glass fiber reinforced composite material having excellent antistatic performance and mechanical properties such as compressive strength, and a glass fiber fabric prepreg suitably used therefor. .

In order to achieve the above object, the present invention has one of the following configurations. Namely, a glass fiber woven prepreg comprising at least the following components (A), (B), (C), (D), and an epoxy comprising (B), (C) and (D) The prepreg which contains 0.001-10 mass% of (D) in a resin composition, and the average particle diameter of (D) is 1 micrometer or less.
(A) Glass fiber woven fabric (B) Epoxy resin (C) Epoxy resin curing agent (D) Conductive filler Or a glass fiber reinforced composite material formed by molding the above prepreg.

  According to the present invention, it becomes possible to provide a glass fiber reinforced composite material excellent in mechanical properties such as antistatic performance and compressive strength, and it is possible to provide an automobile outer plate, an aircraft primary structure material and secondary structure material, a windmill, and a space equipment. In addition, it can be suitably used for sports applications such as structural materials such as railway vehicles and ships, as well as golf shafts, bats, badminton and tennis rackets. In addition, it can be suitably used for semiconductors, IC trays, notebook computer cases, and the like that are required to exhibit antistatic performance.

  As a result of pursuing a mechanism for achieving a high degree of compatibility between mechanical properties such as antistatic performance and compressive strength, the present inventors have found that a conductive filler having a specific particle size is more than a specific blending amount and a thermoplastic resin. An epoxy resin composition blended with an epoxy resin having high mechanical properties and low viscosity is obtained, and a glass fiber fabric is impregnated with the epoxy resin composition to obtain a prepreg that maintains excellent resin impregnation properties. The glass fiber reinforced composite material obtained by using such a prepreg is found to have a conductive path formed by a well-dispersed conductive filler, and to achieve both excellent antistatic performance and mechanical properties such as compressive strength. Has been reached.

  The glass fiber fabric (A) used in the present invention can use any kind of glass fiber depending on the application. Useful glass fibers are fiberable, commonly known as E glass, A glass, C glass, D glass, R glass, S glass, ECR glass, NE glass, quartz and fluorine-free and / or boron-free E glass derivatives. Including those prepared from various glass compositions. In addition to glass fiber, inorganic fiber such as carbon fiber, metal fiber, ceramic fiber, polyamide fiber, polyester fiber, polyolefin fiber, organic synthetic fiber such as novoloid fiber, gold, etc. A metal wire made of silver, copper, bronze, brass, phosphor bronze, aluminum, nickel, steel, stainless steel, a metal mesh, a metal nonwoven fabric, or the like can be used in combination. Carbon fiber, metal fiber, gold, silver, copper, bronze, brass, phosphor bronze, aluminum, nickel, steel, stainless steel, etc., metal wire, metal mesh, metal non-woven fabric, etc. give conductivity to glass fiber woven prepreg However, it is possible to improve the antistatic performance, and it is preferably used.

  Moreover, a conventionally well-known two-dimensional fabric can be used for the glass fiber fabric (A) of this invention. The woven structure of the glass fiber woven fabric (A) is preferably any one selected from plain weave, twill weave, tangle weave, imitation weave, oblique woven, double weave and satin weave. They can be used in combination.

In the present invention, the glass fiber weight per unit area of the glass fiber fabric (A) is preferably 20 to 300 g / m ^2, more preferably from 40~200g / ^{m 2.} When the basis weight of the glass fiber is 20 g / m ² or more, the weaving property of the glass fiber fabric is good. When the basis weight of the glass fiber is 300 g / m ² or less, the resin is in the thickness direction when impregnated with the epoxy resin composition. It becomes a glass fiber reinforced composite material that can easily reach the center part and the non-impregnated part (void) hardly remains, and as a result, exhibits excellent mechanical properties such as compressive strength.

  The yarn density of the glass fiber woven fabric (A) is from the viewpoint of improving the uniformity of single fiber dispersion in the weaving yarn in the ease of weaving operation, opening, widening, and flattening treatment. It is preferable to use a glass fiber fabric having a plain weave structure of 80/25 mm. Considering the effect of reducing the weight of the molded product, a glass fiber fabric having a plain weave structure of warp and weft yarn density of 30 to 70/25 mm is used. It is preferred to use. Furthermore, it is preferable to use the same number of single fibers and the same fineness for the warp and the weft, and to equalize the yarn density in the warp direction and the weft direction.

  The epoxy resin (B) used in the present invention is not particularly limited, and is not limited to bisphenol type epoxy resin, amine type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, resorcinol type epoxy resin, phenol aralkyl. At least one of epoxy type epoxy resin, naphthol aralkyl type epoxy resin, dicyclopentadiene type epoxy resin, epoxy resin having biphenyl skeleton, isocyanate modified epoxy resin, tetraphenylethane type epoxy resin, triphenylmethane type epoxy resin, etc. It can be selected and used.

  Here, the bisphenol type epoxy resin is obtained by glycidylation of two phenolic hydroxyl groups of a bisphenol compound. The bisphenol A type, bisphenol F type, bisphenol AD type, bisphenol S type, or halogens and alkyls of these bisphenols. Examples include substituted products and hydrogenated products. Moreover, not only a monomer but the high molecular weight body which has several repeating units can also be used conveniently.

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

  Commercially available products of bisphenol F type epoxy resin include “jER (registered trademark)” 806, 807, 4002P, 4004P, 4007P, 4009P, 4010P (above, manufactured by Mitsubishi Chemical Corporation), “Epiclon (registered trademark)” 830. 835 (above, manufactured by DIC Corporation), “Epototo (registered trademark)” YDF2001, YDF2004 (above, manufactured by Nippon Steel Chemical Co., Ltd.), and the like. Examples of the tetramethylbisphenol F type epoxy compound include YSLV-80XY (manufactured by Nippon Steel Chemical Co., Ltd.).

  Examples of the bisphenol S-type epoxy resin include “Epiclon (registered trademark)” EXA-154 (manufactured by DIC Corporation).

  Examples of amine-type epoxy resins include tetraglycidyl diaminodiphenylmethane, tetraglycidyl diaminodiphenyl sulfone, tetraglycidyl diaminodiphenyl ether, triglycidylaminophenol, triglycidylaminocresol, tetraglycidylxylylenediamine, and their halogen and alkynol substitutions. Body and hydrogenated products.

  Commercially available products of tetraglycidyldiaminodiphenylmethane include “Sumiepoxy (registered trademark)” ELM434 (manufactured by Sumitomo Chemical Co., Ltd.), YH434L (manufactured by Nippon Steel Chemical Co., Ltd.), and “jER (registered trademark)” 604 (Mitsubishi Chemical). (Manufactured by Co., Ltd.), “Araldide (registered trademark)” MY720, MY721, MY725 (manufactured by Huntsman Advanced Materials Co., Ltd.).

  Commercially available products of triglycidylaminophenol or triglycidylaminocresol include “SUMI Epoxy (registered trademark)” ELM100, ELM120 (manufactured by Sumitomo Chemical Co., Ltd.), “Araldide (registered trademark)” MY0500, MY0510, MY0600, MY0610. (The above is manufactured by Huntsman Advanced Materials Co., Ltd.), “jER (registered trademark)” 630 (manufactured by Mitsubishi Chemical Corporation), and the like.

  Examples of commercially available tetraglycidylxylylenediamine and hydrogenated products thereof include “TETRAD (registered trademark)”-X, “TETRAD (registered trademark)”-C (manufactured by Mitsubishi Gas Chemical Co., Ltd.), and the like. .

  Examples of commercially available tetraglycidyl diaminodiphenyl sulfone include TG4DAS and TG3DAS (manufactured by Mitsui Chemicals Fine Co., Ltd.).

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

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

  Examples of the resin of the resorcinol type epoxy compound include “Denacol (registered trademark)” EX-201 (manufactured by Nagase ChemteX Corporation).

  Examples of commercially available glycidyl aniline type epoxy resins include GAN and GOT (manufactured by Nippon Kayaku Co., Ltd.).

  Examples of commercially available epoxy resins having a biphenyl skeleton include “jER (registered trademark)” YX4000H, YX4000, YL6616 (manufactured by Mitsubishi Chemical Corporation), NC-3000 (manufactured by Nippon Kayaku Co., Ltd.), and the like. It is done.

  Commercially available dicyclopentadiene type epoxy resins include “Epicron (registered trademark)” HP7200L, “Epicron (registered trademark)” HP7200, “Epicron (registered trademark)” HP7200H, “Epicron (registered trademark)” HP7200HH (above, Dainippon Ink Chemical Co., Ltd.), XD-1000-L, XD-1000-2L (above, manufactured by Nippon Kayaku Co., Ltd.), “Tactix (registered trademark)” 556 (manufactured by Vantico Inc.) Etc.

  Examples of commercially available isocyanate-modified epoxy resins include XAC4151, AER4152 (Asahi Kasei Epoxy Co., Ltd.) and ACR1348 (ADEKA Co., Ltd.) having an oxazolidone ring.

  Examples of commercially available tetraphenylethane type epoxy resins include “jER (registered trademark)” 1031 (manufactured by Mitsubishi Chemical Corporation), which is a tetrakis (glycidyloxyphenyl) ethane type epoxy compound.

  As a commercial item of a triphenylmethane type epoxy resin, “Tactics (registered trademark)” 742 (manufactured by Huntsman Advanced Materials Co., Ltd.) and the like can be mentioned.

  Among these epoxy resins (B), an aromatic epoxy resin (B1) having at least one glycidylamine skeleton and having a trifunctional or higher functional epoxy group is preferable. This is because the aromatic epoxy resin (B1) has a high crosslinking density and can improve the heat resistance and compressive strength of the glass fiber reinforced composite material.

  Examples of the polyfunctional glycidylamine type epoxy resin that is the aromatic epoxy resin (B1) include the above-mentioned tetraglycidyldiaminodiphenylmethane, tetraglycidyldiaminodiphenylsulfone, tetraglycidyldiaminodiphenylether, triglycidylaminophenol, and triglycidylaminocresol. Is mentioned.

  Further, as the epoxy resin (B), the following general formula (1)

(In formula (1), R ¹ and R ² are each an aliphatic hydrocarbon group having 1 to 4 carbon atoms, an alicyclic hydrocarbon group having 3 to 6 carbon atoms, and an aromatic hydrocarbon having 6 to 10 carbon atoms. Represents at least one selected from the group consisting of a group, a halogen atom, an acyl group, a trifluoromethyl group, and a nitro group, n is an integer of 0 to 4, and m is an integer of 0 to 5. R ¹ and R ^{When two} or more are present, they may be the same or different, and X is selected from —O—, —S—, —CO—, —C (═O) O—, —SO ₂ —. An amine type epoxy resin having a structure represented by 1) can also be preferably used.

Examples of the amine-type epoxy resin having the structure represented by the general formula (1) include N, N-diglycidyl-4-phenoxyaniline, N, N-diglycidyl-4- (4-methylphenoxy) aniline, N, N- And diglycidyl-4- (4-tert-butylphenoxy) aniline and N, N-diglycidyl-4- (4-phenoxyphenoxy) aniline. In many cases, these resins are obtained by adding epichlorohydrin to a phenoxyaniline derivative and cyclizing with an alkali compound. Since the viscosity increases as the molecular weight increases, N, N-diglycidyl-4-phenoxyaniline in which R ¹ and R ^{2 in} the above general formula (1) are both hydrogen is particularly preferably used from the viewpoint of handleability. It is done.

  Specific examples of the phenoxyaniline derivative include 4-phenoxyaniline, 4- (4-methylphenoxy) aniline, 4- (3-methylphenoxy) aniline, 4- (2-methylphenoxy) aniline, 4- (4 -Ethylphenoxy) aniline, 4- (3-ethylphenoxy) aniline, 4- (2-ethylphenoxy) aniline, 4- (4-propylphenoxy) aniline, 4- (4-tert-butylphenoxy) aniline, 4- (4-cyclohexylphenoxy) aniline, 4- (3-cyclohexylphenoxy) aniline, 4- (2-cyclohexylphenoxy) aniline, 4- (4-methoxyphenoxy) aniline, 4- (3-methoxyphenoxy) aniline, 4- (2-methoxyphenoxy) aniline, 4- (3-phenoxyf) Noxy) aniline, 4- (4-phenoxyphenoxy) aniline, 4- [4- (trifluoromethyl) phenoxy] aniline, 4- [3- (trifluoromethyl) phenoxy] aniline, 4- [2- (trifluoro) Methyl) phenoxy] aniline, 4- (2-naphthyloxyphenoxy) aniline, 4- (1-naphthyloxyphenoxy) aniline, 4-[(1,1′-biphenyl-4-yl) oxy] aniline, 4- ( 4-nitrophenoxy) aniline, 4- (3-nitrophenoxy) aniline, 4- (2-nitrophenoxy) aniline, 3-nitro-4-aminophenyl phenyl ether, 2-nitro-4- (4-nitrophenoxy) Aniline, 4- (2,4-dinitrophenoxy) aniline, 3-nitro-4-phenoxyaniline, -(2-chlorophenoxy) aniline, 4- (3-chlorophenoxy) aniline, 4- (4-chlorophenoxy) aniline, 4- (2,4-dichlorophenoxy) aniline, 3-chloro-4- (4- Chlorophenoxy) aniline, 4- (4-chloro-3-tolyloxy) aniline, and the like.

  Next, a method for producing an amine type epoxy resin having the structure represented by the general formula (1) will be described as an example.

  The amine type epoxy resin having the structure represented by the general formula (1) is represented by the following general formula (2).

(In the formula (2), R ¹ and R ² are each an aliphatic hydrocarbon group having 1 to 4 carbon atoms, an alicyclic hydrocarbon group having 3 to 6 carbon atoms, and an aromatic hydrocarbon having 6 to 10 carbon atoms. Represents at least one selected from the group consisting of a group, a halogen atom, an acyl group, a trifluoromethyl group, and a nitro group, n is an integer of 0 to 4, and m is an integer of 0 to 5. R ¹ and R ^{When two} or more are present, they may be the same or different, and X is selected from —O—, —S—, —CO—, —C (═O) O—, —SO ₂ —. Can be produced by reacting a phenoxyaniline derivative represented by 1) with epichlorohydrin.

  That is, similar to the general epoxy resin production method, the amine type epoxy resin production method is such that two molecules of epichlorohydrin are added to one molecule of the phenoxyaniline derivative, and the following general formula (3)

(In formula (3), R ¹ and R ² are each an aliphatic hydrocarbon group having 1 to 4 carbon atoms, an alicyclic hydrocarbon group having 3 to 6 carbon atoms, and an aromatic hydrocarbon having 6 to 10 carbon atoms. Represents at least one selected from the group consisting of a group, a halogen atom, an acyl group, a trifluoromethyl group, and a nitro group, n is an integer of 0 to 4, and m is an integer of 0 to 5. R ¹ and R ^{When two} or more are present, they may be the same or different, and X is selected from —O—, —S—, —CO—, —C (═O) O—, —SO ₂ —. And the following dichlorohydrin compound is dehydrochlorinated with an alkali compound to form a dichlorohydrin compound represented by the following general formula (1) having two epoxy groups:

(In formula (1), R ¹ and R ² are each an aliphatic hydrocarbon group having 1 to 4 carbon atoms, an alicyclic hydrocarbon group having 3 to 6 carbon atoms, and an aromatic hydrocarbon having 6 to 10 carbon atoms. Represents at least one selected from the group consisting of a group, a halogen atom, an acyl group, a trifluoromethyl group, and a nitro group, n is an integer of 0 to 4, and m is an integer of 0 to 5. R ¹ and R ^{When two} or more are present, they may be the same or different, and X is selected from —O—, —S—, —CO—, —C (═O) O—, —SO ₂ —. A cyclization step in which an amine-type epoxy resin represented by

  PxGAN (diglycidyl-p-phenoxyaniline, Toray Fine Chemical Co., Ltd.) etc. are mentioned as a commercial item of the amine type epoxy resin which has a structure shown by the said General formula (1).

  The aromatic epoxy resin (B1) having at least one glycidylamine skeleton and having a trifunctional or higher functional epoxy group has an effect of increasing heat resistance and elastic modulus in the epoxy resin composition, and the ratio is as follows: It is preferable that 50 mass% or more is contained in an epoxy resin (B), More preferably, it is 60 mass% or more. By setting the ratio of the aromatic epoxy resin (B1) to 50% by mass or more, the glass fiber reinforced composite material can exhibit good heat resistance and compressive strength.

  In addition to the epoxy resin (B) used in the present invention, a resin that undergoes a crosslinking reaction by heat or light and at least partially forms a three-dimensional crosslinked structure may be included. Examples of such resins include unsaturated polyester resins, vinyl ester resins, benzoxazine resins, phenol resins, urea resins, melamine resins, thermosetting polyimide resins, and the like. Etc. can also be used. In addition, these resins may be those that are self-cured by heating, or may be those that contain a curing agent or a curing accelerator.

  As unsaturated polyester resin, what melt | dissolved the unsaturated polyester obtained by making the acid component and alcohol which contain (alpha), (beta) -unsaturated dicarboxylic acid react in a polymerizable unsaturated monomer is mentioned. Examples of the α, β-unsaturated dicarboxylic acid include maleic acid, fumaric acid, itaconic acid and the like, derivatives of these acid anhydrides and the like, and these may be used in combination of two or more. In addition, as necessary, as an acid component other than α, β-unsaturated dicarboxylic acid, saturated dicarboxylic acid such as phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, adipic acid, sebacic acid, and acid anhydrides thereof, etc. The derivative may be used in combination with an α, β-unsaturated dicarboxylic acid.

  Examples of the alcohol include aliphatic glycols such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,2-propanediol, 1,2-butanediol, 1,3-butanediol, and 1,4-butanediol, cyclohexane Alicyclic diols such as pentanediol and cyclohexanediol, hydrogenated bisphenol A, bisphenol A propylene oxide (1 to 100 mol) adducts, aromatic diols such as xylene glycol, polyhydric alcohols such as trimethylolpropane and pentaerythritol Two or more of these may be used in combination.

  Specific examples of the unsaturated polyester resin include, for example, a condensation product of fumaric acid or maleic acid and an adduct of bisphenol A with ethylene oxide (hereinafter abbreviated as EO), propylene oxide of fumaric acid or maleic acid and bisphenol A (hereinafter referred to as EO). And abbreviated as PO.) Condensates with adducts and fumaric acid or maleic acid with EO and PO adducts of bisphenol A (addition of EO and PO may be random or block), etc. These condensates may be dissolved in a monomer such as styrene as necessary. Commercially available unsaturated polyester resins include “Yupica (registered trademark)” (manufactured by Nippon Yupica Co., Ltd.), “Rigolac (registered trademark)” (manufactured by Showa Denko KK), and “Polyset (registered trademark)”. (Manufactured by Hitachi Chemical Co., Ltd.).

  Examples of the vinyl ester resin include epoxy (meth) acrylate obtained by esterifying the epoxy compound and an α, β-unsaturated monocarboxylic acid. Examples of the α, β-unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, crotonic acid, tiglic acid and cinnamic acid, and two or more of these may be used in combination. Specific examples of the vinyl ester resin include, for example, a modified bisphenol type epoxy compound (meth) acrylate (terminal (meth) obtained by reacting an epoxy group of a bisphenol A type epoxy compound and a carboxyl group of (meth) acrylic acid). Acrylate-modified resins and the like), and these modified products may be dissolved in a monomer such as styrene as necessary. Commercially available vinyl ester resins include “Dicklight (registered trademark)” (manufactured by DIC Corporation), “Neopol (registered trademark)” (manufactured by Nippon Yupica Corporation), “Lipoxy (registered trademark)” (Showa) Polymer Co., Ltd.).

  Examples of the benzoxazine resin include o-cresol aniline type benzoxazine resin, m-cresol aniline type benzoxazine resin, p-cresol aniline type benzoxazine resin, phenol-aniline type benzoxazine resin, phenol-methylamine type benzoxazine resin, Phenol-cyclohexylamine type benzoxazine resin, phenol-m-toluidine type benzoxazine resin, phenol-3,5-dimethylaniline type benzoxazine resin, bisphenol A-aniline type benzoxazine resin, bisphenol A-amine type benzoxazine resin, Bisphenol F-aniline type benzoxazine resin, bisphenol S-aniline type benzoxazine resin, dihydroxydiphenylsulfone-aniline type Nzooxazine resin, dihydroxydiphenyl ether-aniline type benzoxazine resin, benzophenone type benzoxazine resin, biphenyl type benzoxazine resin, bisphenol AF-aniline type benzoxazine resin, bisphenol A-methylaniline type benzoxazine resin, phenol-diaminodiphenylmethane type benzoxazine Examples thereof include resins, triphenylmethane type benzoxazine resins, and phenolphthalein type benzoxazine resins. Examples of commercially available benzoxazine resins include BF-BXZ, BS-BXZ, BA-BXZ (manufactured by Konishi Chemical Industry Co., Ltd.).

  Examples of the phenolic resin include resins obtained by condensation of phenols such as phenol, cresol, xylenol, t-butylphenol, nonylphenol, cashew oil, lignin, resorcin, and catechol with aldehydes such as formaldehyde, acetaldehyde, and furfural. , Novolak resins and resol resins. The novolak resin can be obtained by reacting phenol and formaldehyde in the same amount or in excess of phenol in the presence of an acid catalyst such as oxalic acid. The resole resin can be obtained by reacting phenol and formaldehyde in the same amount or in an excess of formaldehyde in the presence of a base catalyst such as sodium hydroxide, ammonia or organic amine. Commercially available phenolic resins include “Sumilite Resin (registered trademark)” (manufactured by Sumitomo Bakelite Co., Ltd.), Resitop (manufactured by Gunei Chemical Industry Co., Ltd.), and “AV Light (registered trademark)” (Asahi Organic Materials). Kogyo Co., Ltd.).

  Examples of the urea resin include a resin obtained by condensation of urea and formaldehyde. Examples of commercially available urea resins include UA-144 (manufactured by Sunbake Co., Ltd.).

  Examples of the melamine resin include a resin obtained by polycondensation of melamine and formaldehyde. Examples of commercially available melamine resins include “Nicalac (registered trademark)” (manufactured by Sanwa Chemical Co., Ltd.).

  Examples of the thermosetting polyimide resin include resins containing at least an imide ring in the main structure and at least one selected from a phenylethynyl group, a nadiimide group, a maleimide group, an acetylene group and the like in the terminal or main chain. It is done. Examples of commercially available polyimide resin include PETI-330 (manufactured by Ube Industries).

  In the present invention, an epoxy resin curing agent (C) is blended and used. As the epoxy resin curing agent (C), any compound having an active group capable of reacting with an epoxy group can be used. As the curing agent, a compound having an amino group, an acid anhydride group and an azide group is suitable. Specifically, an aromatic amine curing agent, dicyandiamide or a derivative thereof is preferable.

  The aromatic amine curing agent is not particularly limited as long as it is an aromatic amine. Specifically, 3,3′-diaminodiphenylsulfone (3,3′-DDS), 4,4 ′ -Diaminodiphenylsulfone (4,4'-DDS), diaminodiphenylmethane (DDM), 3,3'-diisopropyl-4,4'-diaminodiphenylmethane, 3,3'-di-t-butyl-4,4'- Diaminodiphenylmethane, 3,3′-diethyl-5,5′-dimethyl-4,4′-diaminodiphenylmethane, 3,3′-diisopropyl-5,5′-dimethyl-4,4′-diaminodiphenylmethane, 3,3 '-Di-t-butyl-5,5'-dimethyl-4,4'-diaminodiphenylmethane, 3,3', 5,5'-tetraethyl-4,4'-diaminodiphenyl Rumethane, 3,3′-diisopropyl-5,5′-diethyl-4,4′-diaminodiphenylmethane, 3,3′-di-t-butyl-5,5′-diethyl-4,4′-diaminodiphenylmethane, 3,3 ′, 5,5′-tetraisopropyl-4,4′-diaminodiphenylmethane, 3,3′-di-t-butyl-5,5′-diisopropyl-4,4′-diaminodiphenylmethane, 3,3 ', 5,5'-tetra-t-butyl-4,4'-diaminodiphenylmethane, diaminodiphenyl ether (DADPE), bisaniline, benzyldimethylaniline, 2- (dimethylaminomethyl) phenol (DMP-10), 2,4 , 6-Tris (dimethylaminomethyl) phenol (DMP-30), 2,4,6-tris (dimethylaminomethyl) phenol It can be used 2-ethylhexanoic acid esters of Nord. These may be used alone or in admixture of two or more. Among them, 3,3′-diaminodiphenylsulfone (3,3′-DDS), 4,4′-diaminodiphenylsulfone (4,4′-) capable of imparting excellent elastic modulus, toughness and heat resistance to the epoxy resin composition An aromatic amine curing agent containing a diphenylsulfone skeleton such as DDS) is preferably used.

  Commercially available aromatic amine curing agents include Seika Cure S (manufactured by Wakayama Seika Kogyo Co., Ltd.), MDA-220 (manufactured by Mitsui Chemicals), “jER Cure (registered trademark)” W (Japan Epoxy Resin ( ), And 3,3′-DAS (Mitsui Chemicals), Lonacure (registered trademark) M-DEA (manufactured by Lonza), “Lonzacure (registered trademark)” M-DIPA (Lonza ( Co., Ltd.), “Lonacure (registered trademark)” M-MIPA (manufactured by Lonza), “Lonzacure (registered trademark)” DETDA80 (manufactured by Lonza), and the like.

  Examples of commercially available dicyandiamide include DICY-7 and DICY-15 (manufactured by Japan Epoxy Resin Co., Ltd.).

  When an aromatic amine curing agent containing a diphenylsulfone skeleton is used as the epoxy resin curing agent (C), 20 to 70 parts by mass is mixed with 100 parts by mass of the epoxy resin (B) from the viewpoint of heat resistance and mechanical properties. Preferably, it is 30 to 50 parts by mass. When the aromatic amine curing agent containing the diphenylsulfone skeleton is less than 20 parts by mass, the cured product may be poorly cured, and mechanical properties such as compression strength of the glass fiber reinforced composite material may be deteriorated. When the aromatic amine curing agent containing the diphenylsulfone skeleton exceeds 70 parts by mass, the crosslink density of the epoxy resin cured product becomes too high, and mechanical properties such as impact resistance of the glass fiber reinforced composite material may be deteriorated. is there.

  When dicyandiamide or a derivative thereof is used as the epoxy resin curing agent (C), it is preferable to blend 1 to 10 parts by mass with respect to 100 parts by mass of the epoxy resin (B), more preferably from the viewpoint of heat resistance and mechanical properties. Is 2-8 parts by mass. When dicyandiamide or a derivative thereof is less than 1 part by mass, the cured product may be poorly cured and the compression strength of the glass fiber reinforced composite material may be reduced. When dicyandiamide or a derivative thereof exceeds 10 parts by mass, the crosslink density of the cured epoxy resin becomes too high, and mechanical properties such as impact resistance of the glass fiber reinforced composite material may be deteriorated. It is preferable to blend dicyandiamide or a derivative thereof as a powder into the resin from the viewpoint of storage stability at room temperature and viscosity stability during prepreg formation. When dicyandiamide or a derivative thereof is used as a powder, the average particle size is preferably 10 μm or less, more preferably 7 μm or less. When it exceeds 10 μm, for example, when used for glass fiber fabric prepreg, when impregnating the glass fiber bundle with the epoxy resin composition by heating and pressurizing, the powder of dicyandiamide or its derivative does not enter the glass fiber bundle. It may be left behind on the surface of the fiber bundle.

  Moreover, it is preferable that the total amount of an epoxy resin hardening | curing agent (C) contains the quantity from which an active hydrogen group becomes the range of 0.6-1.2 equivalent with respect to 1 equivalent of epoxy groups of an epoxy resin (B) component, More preferably, the amount is in the range of 0.7 to 0.9 equivalent. Here, the active hydrogen group means a functional group that can react with the epoxy group of the curing agent component, and when the active hydrogen group is less than 0.6 equivalent, the reaction rate, heat resistance, and elastic modulus of the cured product. May be insufficient, and the heat resistance and compressive strength of the glass fiber reinforced composite material may be insufficient. When the active hydrogen group exceeds 1.2 equivalents, the reaction rate, heat resistance, and elastic modulus of the cured product are sufficient, but the plastic deformation ability is insufficient, so the impact resistance of the glass fiber reinforced composite material, etc. The mechanical properties of

  Moreover, a hardening accelerator can also be mix | blended for the purpose of accelerating hardening. Examples of the curing accelerator include urea compounds, tertiary amines and salts thereof, imidazoles and salts thereof, triphenylphosphine or derivatives thereof, carboxylic acid metal salts, Lewis acids, Bronsted acids and salts thereof, and the like. Among these, a urea compound is preferably used from the balance between storage stability and catalytic ability. In particular, a combination of a urea compound and dicyandiamide is preferably used.

  Examples of the urea compound include N, N-dimethyl-N ′-(3,4-dichlorophenyl) urea, toluenebis (dimethylurea), 4,4′-methylenebis (phenyldimethylurea), 3-phenyl-1, 1-dimethylurea or the like can be used. Examples of commercially available urea compounds include DCMU99 (manufactured by Hodogaya Chemical Co., Ltd.), “Omicure (registered trademark)” 24, 52, 94 (manufactured by Emerald Performance Materials, LLC).

  It is preferable that the compounding quantity of a urea compound shall be 1-4 mass parts with respect to 100 mass parts of epoxy resins (B). When the compounding quantity of this urea compound is less than 1 mass part, reaction may not fully advance and the elasticity modulus and heat resistance of hardened | cured material may be insufficient. Moreover, when the compounding quantity of this urea compound exceeds 4 mass parts, since the self-polymerization reaction of an epoxy resin (B) inhibits reaction with an epoxy resin (B) and an epoxy resin hardening | curing agent (C), it is hardened | cured The toughness of the object may be insufficient, and the elastic modulus may decrease.

  Further, these epoxy resin (B) and epoxy resin curing agent (C), or a product obtained by pre-reacting a part of them can be blended in the composition. This method may be effective for viscosity adjustment and storage stability improvement.

  Epoxy resin curing agents (C) other than those described above include amines such as alicyclic amines, phenolic compounds, acid anhydrides, polyaminoamides, organic acid hydrazides, and isocyanates as aromatic amine curing agents, dicyandiamide, or derivatives thereof. You may use together.

  The epoxy resin composition used in the present invention is soluble in the epoxy resin (B) in addition to the epoxy resin (B), the epoxy resin curing agent (C), and the conductive filler (D) described below. It is preferable that the thermoplastic resin (E) is included. This thermoplastic resin (E) controls the viscoelasticity of the epoxy resin composition to improve the tack and drape characteristics of the glass fiber woven prepreg, and to improve the mechanical properties such as impact resistance of the glass fiber reinforced composite material. Preferably used.

  The thermoplastic resin (E) exhibiting solubility in the epoxy resin (B) has a carbon-carbon bond, amide bond, imide bond, ester bond, ether bond, carbonate bond, urethane bond, thioether bond, sulfone bond and main chain. A thermoplastic resin having a bond selected from the group consisting of carbonyl bonds is preferred. Further, this thermoplastic resin may have a partially crosslinked structure, and may be crystalline or amorphous. In particular, polyamide, polycarbonate, polyvinyl formal, polyvinyl butyral, polyvinyl alcohol, polyacetal, polyphenylene oxide, polyphenylene sulfide, polyarylate, polyester, phenoxy resin, polyamideimide, polyimide, polyetherimide, polyimide having phenyltrimethylindane structure, polysulfone Preferably, at least one resin selected from the group consisting of polyethersulfone, polyetherketone, polyetheretherketone, polyaramid, polyethernitrile and polybenzimidazole is dissolved in the epoxy resin (B). It is.

  Furthermore, as the terminal functional group of this thermoplastic resin, those such as a hydroxyl group, a carboxyl group, a thiol group, and an acid anhydride can react with the cationic polymerizable compound and are preferably used. Examples of the thermoplastic resin having a hydroxyl group include polyvinyl acetal resins such as polyvinyl formal and polyvinyl butyral, polyvinyl alcohol, polyether sulfone, and phenoxy resin.

  Among them, the average molecular weight is preferably 5000 to 2000000 g / mol. If it is less than 5,000, the effect of improving the mechanical properties such as impact resistance of the glass fiber reinforced composite material may be small. If it exceeds 2,000,000, the viscosity will increase too much, so the viscosity of the epoxy resin composition will increase. Pre-preg may not be possible.

  Among them, polyvinyl acetal resins such as polypinyl formal, poly vinyl butyral, polyether sulfone, polyether imide, or polyphenylene ether are easily dissolved in epoxy resin by heating, and without impairing the heat resistance of the cured product. It is preferably used because it improves the adhesion between the fiber and the epoxy resin composition and can easily adjust the viscosity by selecting the molecular weight or adjusting the blending amount. Of these, polyethersulfone, which is excellent in terms of the balance between elastic modulus and toughness, is particularly preferably used.

  Specific examples of commercially available thermoplastic resins include polyvinyl acetal resins such as “VINYREC” (registered trademark) K, “VINYREC” (registered trademark) L, “VINYREC” (registered trademark) H, “VINYREC”. "(Registered trademark) E (above, manufactured by Chisso Corporation) and other polypinyl formals," ESREC "(registered trademark) K (manufactured by Sekisui Chemical Co., Ltd.) and other polypinyl acetals," ESREC "( Examples thereof include polypinyl butyral such as registered trademark B (manufactured by Sekisui Chemical Co., Ltd.) and Denkabutyral (manufactured by Denki Kagaku Kogyo Co., Ltd.). Commercially available polyethersulfone products include “Sumika Excel (registered trademark)” PES3600P, “Sumika Excel (registered trademark)” PES5003P, “Sumika Excel (registered trademark)” PES5200P, “Sumika Excel (registered trademark)” PES7600P, “ SUMIKAEXCEL (registered trademark) “PES7200P (above, manufactured by Sumitomo Chemical Co., Ltd.),“ Ultrason (registered trademark) ”E2020P SR,“ Ultrason (registered trademark) ”E2021SR (above, manufactured by BASF Corp.),“ GAFONE ” (Registered trademark) “3600RP”, “GAFONE (registered trademark)” 3000RP (above, manufactured by Solvay Advanced Polymers), “Virantage (registered trademark)” PESU VW-10200, “Virantage ( Registered trademark) "PESU VW-10700 (above, manufactured by Solvay Advance Polymers Co., Ltd.) and the like, and polyether sulfone and polyether ether sulfone as described in JP-T-2004-506789 Copolymer oligomers, and polyetherimide commercially available products "Ultem (registered trademark)" 1000, "Ultem (registered trademark)" 1010, "Ultem (registered trademark)" 1040 (above, SABIC Innovative Plastics Co., Ltd.) Manufactured).

  When the thermoplastic resin (E) is dissolved and used in the epoxy resin (B), the blending ratio of the thermoplastic resin (E) is preferably 1 to 40% by mass in the epoxy resin composition in terms of balance, More preferably, it is 5-30 mass%, More preferably, it is the range of 8-20 mass%. When there are too many compounding quantities of a thermoplastic resin, the viscosity of an epoxy resin composition will raise and the manufacturing process property and handleability of an epoxy resin composition and a glass fiber fabric prepreg may be impaired. If the blended amount of the thermoplastic resin is too small, the toughness of the cured epoxy resin may be insufficient, and the resulting glass fiber reinforced composite material may have insufficient mechanical properties such as impact resistance.

  In addition, the acrylic resin has high compatibility with the epoxy resin (B) and is suitably used for controlling viscoelasticity, and among them, polymethacrylic acid ester is preferably used. Examples of commercially available products of polymethacrylic acid esters include “Dianal (registered trademark)” BR-83, “Dianal (registered trademark)” BR-85, “Dianal (registered trademark)” BR-87, “Dianal” (Registered trademark) “BR-88”, “Dianar (registered trademark)” BR-108 (manufactured by Mitsubishi Rayon Co., Ltd.), “Matsumoto Microsphere (registered trademark)” M, “Matsumoto Microsphere (registered) Trademarks ”“ M100 ”,“ Matsumoto Microsphere (registered trademark) ”M500 (manufactured by Matsumoto Yushi Seiyaku Co., Ltd.), and the like.

  Furthermore, in the epoxy resin composition of the present invention, for the purpose of improving the toughness of the resin and the mechanical properties such as impact resistance and compressive strength of the glass fiber reinforced composite material, organic particles such as rubber particles and thermoplastic resin particles, Inorganic particles and the like can be blended.

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

  Commercially available crosslinked rubber particles include FX501P (manufactured by Nippon Synthetic Rubber Industry Co., Ltd.) made of a crosslinked product of carboxyl-modified butadiene-acrylonitrile copolymer, and CX-MN series (Nippon Catalyst Co., Ltd.) made of acrylic rubber fine particles. Product), YR-500 series (manufactured by Toto Kasei Co., Ltd.) and the like can be used.

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

  For example, a block copolymer which can be produced by anionic polymerization and can be produced by the method described in European Patent No. EP524,054 or European Patent No. EP749,987 can be used. Commercially available block copolymers include “Nanostrength (registered trademark)” M22 and “Nanostrength (registered trademark)” M22N having polar functional groups (above, manufactured by Arkema Co., Ltd.). Specific examples of the triblock copolymer S-B-M include “Nanostrength (registered trademark)” 123, “Nanostrength (registered trademark)” 250, “Nanostrength” as copolymers comprising styrene-butadiene-methyl methacrylate. (Registered trademark) “012,” “Nanostrength (registered trademark)” E20, “Nanostrength (registered trademark)” E20F, “Nanostrength (registered trademark)” E40, “Nanostrength (registered trademark)” E40F (above, manufactured by Arkema Corporation) ).

  As the thermoplastic resin particles, thermoplastic resins which are the same as the various thermoplastic resins exemplified above and can be used by mixing with the epoxy resin composition can be used. Among them, polyamide is most preferable, and among polyamides, nylon 12, nylon 6, nylon 11, nylon 6/12 copolymer and nylon modified with an epoxy compound (epoxy modified nylon) are particularly good epoxy resins (B). And give the adhesive strength. The shape of the thermoplastic resin particles may be spherical particles, non-spherical particles, or porous particles, but the spherical shape is superior in viscoelasticity because it does not deteriorate the flow characteristics of the resin, and there is no origin of stress concentration. This is a preferred embodiment in terms of giving high impact resistance. Commercially available polyamide particles include SP-500, SP-10, TR-1, TR-2, 842P-48, 842P-80 (above, manufactured by Toray Industries, Inc.), “Trepearl (registered trademark)” TN ( Toray Industries, Inc.), “Orgasol (registered trademark)” 1002D, 2001UD, 2001EXD, 2002D, 3202D, 3501D, 3502D (above, manufactured by Arkema Co., Ltd.) and the like can be used.

  In the present invention, the organic particles such as rubber particles and thermoplastic resin particles are used in an amount of 0.1 to 30 with respect to 100 parts by mass of the epoxy resin (B) from the viewpoint of achieving both the elastic modulus and toughness of the obtained cured resin. A mass part is preferable and it is more preferable to mix | blend 1-25 mass parts.

  The epoxy resin composition used in the present invention has a glass transition temperature Tg of a cured epoxy resin obtained by curing at 180 ° C. for 2 hours, preferably 180 ° C. or higher, more preferably 190 ° C. or higher. And good. When the glass transition temperature is lower than the above temperature, the heat resistance of the cured product is insufficient, and warping or distortion may occur during molding or use of the glass fiber reinforced composite material. Moreover, since there exists a tendency for a plastic deformation capability and toughness to fall when the heat resistance of hardened | cured material is raised, it is preferable that the upper limit of heat resistance is generally 220 degrees C or less. Here, the glass transition temperature is determined by heating the epoxy resin composition to 180 ° C. at a heating rate of 1.5 ° C./min and curing it for 2 hours to produce a 2 mm thick resin cured plate. In addition, this cured resin plate was cut into a length of 60 mm and a width of 10 mm, and this cured resin plate was compliant with SACMA SRM 18R-94 using a dynamic viscoelasticity measuring device (ARES, manufactured by TA Instruments Inc.). Can be measured.

  Furthermore, the epoxy resin composition used in the present invention preferably has a flexural modulus of 3 GPa or more, more preferably 3 GPa or more, of an epoxy resin cured product obtained by curing at 180 ° C. for 2 hours. 3 GPa or more. If the flexural modulus is too low, mechanical properties such as compressive strength of the glass fiber reinforced composite material obtained using such an epoxy resin composition may deteriorate. If the flexural modulus is too high, the glass fiber obtained The toughness of the reinforced composite material may be reduced. The bending elastic modulus here can be measured by a three-point bending test in accordance with JIS K7171-1994.

In addition, the epoxy resin composition used in the present invention has a volume resistivity of a cured epoxy resin obtained by curing at 180 ° C. for 2 hours, preferably 10 ³ to 10 ¹¹ Ωcm, more preferably 10 ^5. 10 to 10 ¹⁰ Ωcm, and more preferably 10 ⁸ to 10 ¹⁰ Ωcm. If the volume specific resistance of the cured epoxy resin is too high, the volume specific resistance of the resulting glass fiber reinforced composite material may be too high to obtain sufficient antistatic performance. If the volume resistivity of the cured epoxy resin is too low, the volume resistivity of the resulting glass fiber reinforced composite material may be too low to obtain sufficient antistatic performance. The volume specific resistance of the cured epoxy resin here is that the epoxy resin composition is heated to 180 ° C. at a rate of temperature increase of 1.5 ° C./min and cured over 2 hours, and is a resin cured plate having a thickness of 2 mm. A 50 mm long x 50 mm wide sample was cut out from this cured resin plate, and a sample in which conductive paste “Dotite” (registered trademark) D-550 (manufactured by Fujikura Kasei Co., Ltd.) was applied on both sides was prepared. These samples are obtained by measuring resistance in the thickness direction under a voltage of 200 V using a resistance meter of SM-8220 manufactured by HIOKI Corporation.

  The epoxy resin composition used in the present invention preferably has a viscosity at 80 ° C. of 0.1 to 500 Pa · s, more preferably 1 to 300 Pa · s, and still more preferably 3 to 100 Pa · s. Range. If the viscosity at 80 ° C. is too low, the resin film necessary for producing the glass fiber woven prepreg cannot be produced, or the handleability of the glass fiber woven prepreg is deteriorated. It may be too strong and cause problems in workability. When the viscosity at 80 ° C. is too high, the tack is lowered, the glass fiber woven prepreg cannot be laminated on the mold, and there is a problem in workability, and the resin film necessary for producing the glass fiber woven prepreg is produced. Further, since the viscosity is too high, an excessive film forming temperature is required, and a resin film cannot be produced, or the storage stability of the obtained glass fiber woven prepreg may be impaired.

  Here, the viscosity at 80 ° C. means using a dynamic viscoelasticity measuring device (ARES, manufactured by TA Instruments Inc.), using a parallel plate, and simply raising the temperature at a rate of temperature rise of 2 ° C./min. Viscosity at 80 ° C. when measured from 40 ° C. to 130 ° C. at a strain of 100%, a frequency of 0.5 Hz, and a plate interval of 1 mm.

  Examples of the conductive filler (D) used in the present invention include carbon black, carbon nanotube, vapor grown carbon fiber (VGCF), fullerene, metal nanoparticles, and the like. . Among these, carbon black that is inexpensive and highly effective in improving conductivity is preferably used. As such carbon black, for example, furnace black, acetylene black, thermal black, channel black, ketjen black and the like can be used, and carbon black obtained by blending two or more of these is also preferably used.

  The average particle diameter of the conductive filler (D) used in the present invention is required to be 1 μm or less, and more preferably 0.5 μm or less. When the average particle diameter of the conductive filler is small, it is possible to efficiently disperse the glass fibers and in the epoxy resin composition, thereby improving the conductivity of the glass fiber reinforced composite material. The particle size of the conductive filler (D) is preferably 0.01 μm or more. When the average particle diameter of the conductive filler exceeds 1 μm, the conductive filler is not efficiently dispersed between the glass fibers, the conductive path by the conductive filler cannot be obtained, and the antistatic performance of the glass fiber reinforced composite material cannot be sufficiently obtained.

  Regarding the average particle diameter of the conductive filler (D), the particles are magnified 1000 times or more with a microscope such as a scanning electron microscope, photographed, the particles are randomly selected, and the diameter of the circle circumscribing the particles is determined. The particle diameter is obtained as an average value (n = 50) of the particle diameters.

  The compounding quantity of the electroconductive filler (D) used for this invention needs to be 0.001-10 mass% in an epoxy resin composition, Preferably it is 0.05-5 mass%, More preferably, it is 0.00. It is 1-3 mass%. When there are too many compounding quantities of an electroconductive filler (D), the viscosity of an epoxy resin composition will rise and it will be difficult to manufacture a glass fiber fabric prepreg. When there are too few compounding quantities of an electroconductive filler (D), the antistatic performance of the glass fiber reinforced composite material obtained will not be obtained.

  The glass fiber fabric prepreg of the present invention is a glass fiber fabric impregnated with an epoxy resin composition which is a matrix resin. The glass fiber fabric prepreg can be produced, for example, by a method such as a wet method in which a matrix resin is dissolved in a solvent such as methyl ethyl ketone or methanol to lower the viscosity and impregnated, or a hot melt method in which the viscosity is lowered by heating and impregnated. .

  In the wet method, a glass fiber fabric prepreg can be obtained by immersing the glass fiber fabric in a liquid containing a matrix resin, then pulling it up and evaporating the solvent using an oven or the like.

  In the hot melt method, a glass fiber fabric is directly impregnated with a matrix resin whose viscosity has been reduced by heating, or a film in which a matrix resin composition is once coated on release paper is first prepared, and then a glass fiber fabric is prepared. A glass fiber fabric prepreg can be produced by a method in which the glass fiber fabric is impregnated with a matrix resin by overlapping the film from both sides or one side of the substrate and applying heat and pressure. The hot melt method is a preferable means because there is no solvent remaining in the glass fiber fabric prepreg.

  The cover factor of the glass fiber fabric prepreg of the present invention means that the area occupied by the woven yarn (glass fiber bundle) when the glass fiber fabric prepreg is occupied is the ratio of the total area of the glass fiber fabric prepreg. When the cover factor is small, the resin is not impregnated into the textured portion of the glass fiber fabric when laminated and cured, and voids are generated in the resulting glass fiber reinforced composite material, and the compressive strength of the glass fiber reinforced composite material, etc. When the mechanical properties of the glass fiber bundle are reduced, the texture portion where the glass fiber bundle does not exist becomes a resin rich portion, and stress concentration occurs in the glass fiber reinforced composite material, it becomes a starting point of fracture. Moreover, when the cover factor is sufficient, it becomes easy to keep the resin on the surface of the glass fiber woven prepreg, and the change with time of the tack of the glass fiber woven prepreg can be reduced. Furthermore, it is possible to improve mechanical properties such as compressive strength of the obtained glass fiber reinforced composite material. Here, the range of the cover factor of the glass fiber fabric prepreg is preferably 80% or more, more preferably 90% or more, and further preferably 95% or more. When the cover factor is less than 80%, when the glass fiber fabric prepreg is laminated and cured, the weave portion of the glass fiber fabric is not impregnated with the resin, and voids are generated in the obtained glass fiber reinforced composite material. The mechanical properties such as compressive strength of the glass fiber reinforced composite material may be deteriorated, or the texture portion where the glass fiber bundle does not exist may become a starting point of fracture when stress concentration occurs in the glass fiber reinforced composite material. . The range of the cover factor of the glass fiber woven prepreg is preferably 99% or less, more preferably 98% or less. If the cover factor of the glass fiber woven prepreg is too large, a conductive path through the conductive filler through the texture of the glass fiber woven prepreg may not be obtained, and the antistatic performance of the glass fiber reinforced composite material may not be sufficiently obtained. .

  The glass fiber fabric prepreg of the present invention can be formed into a prepreg after the glass fabric (A) itself is opened, widened and flattened to increase the cover factor. As a method of opening, widening and flattening the glass fiber fabric (A), JP-A-61-194252, JP-A-3-76862, JP-A-4-163364 or JP-A-5-22590 is disclosed. And so on, so-called water jet punching treatment or air jet punching, which is treated with a high-pressure fluid such as a water jet flow or an air jet flow ejected from a plurality of nozzles arranged in a line in the weft direction of the woven fabric. A method of processing, a method of nipping between rollers, a method of contacting an ultrasonic transmitter, a method of needle punching or brushing, or the like is used.

The cover factor of the glass fiber woven prepreg of the present invention is an element relating to the textured portion (resin rich portion) formed between the woven yarns (glass fiber bundles) of the glass fiber woven fabric, and has an area S1 of the glass fiber woven prepreg. When the area is set, the area defined by the following equation is defined as S2 when the area of the texture formed by the woven yarn in the area S1 is S2. In the present invention, the area S1 is set to an arbitrary 100 cm ² on the plane of the glass fiber woven prepreg, and the cover factor is cut from five test pieces having a size of 10 × 10 cm in the width direction of the woven fabric. It is set as the average value of the obtained individual values.
Cover factor (%) = [(S1-S2) / S1] × 100.

In addition, the glass fiber woven prepreg of the present invention is a glass obtained by heating up to 180 ° C. at a rate of temperature increase of 1.5 ° C./min in an autoclave and curing for 2 hours under a pressure of 0.59 MPa. The volume resistivity in the thickness direction of the fiber reinforced composite material is preferably 10 ⁴ to 10 ¹² Ωcm, more preferably 10 ⁵ to 10 ¹² Ωcm, and even more preferably 10 ⁸ to 10 ¹¹ Ωcm. . When the volume resistivity of the obtained glass fiber reinforced composite material is too high or too low, sufficient antistatic performance may not be obtained. The specific volume resistivity of the glass fiber reinforced composite material here is that the glass fiber fabric prepreg is heated to 180 ° C. at a heating rate of 1.5 ° C./min and cured under a pressure of 0.59 MPa for 2 hours. Sample prepared by cutting out a sample of 50 mm in length and 50 mm in width from this glass fiber reinforced composite material and applying a conductive paste “Dotite” (registered trademark) D-550 (manufactured by Fujikura Kasei Co., Ltd.) on both sides These samples are obtained by measuring the resistance in the thickness direction under a voltage of 200 V using a resistance meter of SM-8220 manufactured by HIOKI Co., Ltd. and obtaining the volume resistivity.

The glass fiber mass fraction of the glass fiber fabric prepreg of the present invention is preferably 40 to 80% by mass, more preferably 50 to 70% by mass. If the glass fiber mass fraction is too low, mechanical properties such as compressive strength of the resulting glass fiber reinforced composite material may be deteriorated. If the glass fiber mass fraction is too high, the impregnation of the epoxy resin composition is poor. And the resulting glass fiber reinforced composite material tends to have a lot of voids, and mechanical properties such as compression strength may be greatly deteriorated. The glass fiber mass fraction here refers to a glass fiber fabric prepreg cut out in a size of 10 × 10 cm, N-methyl-2pyrrolidone (NMP) using an ultrasonic cleaner, and then 2 each with methyl ethyl ketone (MEK). Wash 10 times for 10 minutes and take out only the glass fiber fabric from the glass fiber fabric prepreg. With respect to the mass (W1) of the glass fiber fabric prepreg, the glass fiber mass fraction can be determined from the mass (W2) of the obtained glass fiber fabric using the following formula.
Glass fiber mass fraction (%) = (W2 / W1) × 100.

  In order to form a glass fiber reinforced composite material using the glass fiber woven prepreg of the present invention, a method of heating and curing a matrix resin while applying pressure to the laminate after laminating the glass fiber woven prepreg can be used. . Of course, a glass fiber reinforced composite material can be obtained even when the glass fiber woven prepreg monolayer of the present invention is cured.

  Examples of methods for applying heat and pressure include a press molding method, an autoclave molding method, a bagging molding method, a wrapping tape method, and an internal pressure molding method. Especially for sporting goods, the wrapping tape method and the internal pressure molding method are preferably employed. The The autoclave molding method is preferably employed in space equipment, aircraft primary structure materials, secondary structure materials, and the like that require higher quality and higher performance laminated composite materials. The press molding method is preferably used for various automobile outer plates, railway vehicles, and the like.

  The glass fiber reinforced composite material of the present invention can provide a glass fiber reinforced composite material having excellent antistatic performance and mechanical properties, such as an automobile outer plate, an aircraft primary structure material and secondary structure material, a windmill, It can be suitably used as a structural material for space equipment, railway vehicles, ships and the like. In addition, it can be suitably used for semiconductors, IC trays, notebook computer cases, and the like that are required to exhibit antistatic performance.

  Hereinafter, the glass fiber woven prepreg and the glass fiber reinforced composite material of the present invention will be described more specifically with reference to examples. The production environment and evaluation of the glass fiber woven prepregs of the following examples are performed in an atmosphere of a temperature of 25 ° C. ± 2 ° C. and a relative humidity of 50% unless otherwise specified. Further, the present invention is not limited to these examples.

(1) Viscosity of epoxy resin composition at 80 ° C. Using an epoxy resin composition with a dynamic viscoelasticity measuring device (ARES, manufactured by TA Instruments Inc.), a parallel plate is used, and a temperature rising rate is 2 ° C. The viscosity at 80 ° C. was measured when the temperature was measured from 40 ° C. to 130 ° C. at a strain of 100%, a frequency of 0.5 Hz, and a plate interval of 1 mm.

(2) Flexural modulus of cured epoxy resin After defoaming the epoxy resin composition in vacuum, the temperature rises in a mold set to 2 mm thickness with a 2 mm thick “Teflon (registered trademark)” spacer. The temperature was raised to 180 ° C. at a rate of 1.5 ° C./min and cured for 2 hours to obtain a cured resin product having a thickness of 2 mm. From this, a test piece having a width of 10 mm and a length of 55 mm was cut out, an Instron universal testing machine was used, the span length was 32 mm, the crosshead speed was 2.5 mm / min, and three-point bending was performed according to JIS K7171 (1999). A flexural modulus was obtained.

(3) Volume resistivity of cured epoxy resin After defoaming the epoxy resin composition in a vacuum, the temperature rises in a mold set to 2 mm thick with a 2 mm thick “Teflon (registered trademark)” spacer. The temperature was raised to 180 ° C. at a rate of 1.5 ° C./min and cured for 2 hours to obtain a cured resin product having a thickness of 2 mm. A sample of 50 mm long × 50 mm wide was cut out from this cured resin plate, and a sample in which a conductive paste “Dotite” (registered trademark) D-550 (manufactured by Fujikura Kasei Co., Ltd.) was applied to both sides was prepared. These samples were measured for resistance in the thickness direction under a voltage of 200 V using a resistance meter of SM-8220 manufactured by HIOKI Corporation, and volume specific resistance was obtained.

(4) Glass transition temperature of cured epoxy resin Tg
After defoaming the epoxy resin composition in a vacuum, in a mold set to a thickness of 2 mm with a 2 mm thick “Teflon (registered trademark)” spacer, the temperature is increased to 180 ° C. at a heating rate of 1.5 ° C./min. The temperature was raised and cured over 2 hours to obtain a cured resin having a thickness of 2 mm. Next, this cured resin plate was cut into a length of 60 mm and a width of 10 mm. When measuring the glass transition temperature, this resin cured plate was measured according to SACMA SRM 18R-94 using a dynamic viscoelasticity measuring apparatus (ARES, manufactured by TA Instruments Inc.), and 40 ° C. To 250 ° C. However, the measurement was performed in the Rectangular Torsion mode, the measurement frequency was 1 Hz, and the temperature elevation rate was 5 ° C./min. In the obtained temperature-storage modulus curve, the intersection of the tangent in the glass region and the tangent in the transition region from the glass region to the rubber region was determined, and the temperature at this intersection was taken as the glass transition temperature.

(5) Flexural modulus of thermoplastic resin A thermoplastic resin composition filled in a mold set to a thickness of 2 mm, press-molded using a heating type press molding machine, and a thermoplastic resin having a thickness of 2 mm A molded plate of the composition was obtained. From this, a test piece having a width of 10 mm and a length of 55 mm was cut out, an Instron universal testing machine was used, the span length was 32 mm, the crosshead speed was 2.5 mm / min, and three-point bending was performed according to JIS K7171 (1999). A flexural modulus was obtained.

(6) Volume resistivity of thermoplastic resin A thermoplastic resin composition is filled into a mold set to a thickness of 2 mm, press-molded using a heating press molding machine, and a thermoplastic resin having a thickness of 2 mm. A molded plate of the composition was obtained. From this, a sample of 50 mm in length and 50 mm in width was cut out, and a sample in which conductive paste “Dotite” (registered trademark) D-550 (manufactured by Fujikura Kasei Co., Ltd.) was applied to both sides was prepared. These samples were measured for resistance in the thickness direction under a voltage of 200 V using a resistance meter of SM-8220 manufactured by HIOKI Corporation, and volume specific resistance was obtained.

(7) Glass transition temperature of thermoplastic resin Tg
A thermoplastic resin composition was filled in a mold set to have a thickness of 2 mm, and press-molded using a heating press molding machine to obtain a molded plate of a thermoplastic resin composition having a thickness of 2 mm. From this, it cut out to length 60mm and width 10mm. When measuring the glass transition temperature, this resin cured plate was measured according to SACMA SRM 18R-94 using a dynamic viscoelasticity measuring apparatus (ARES, manufactured by TA Instruments Inc.), and 40 ° C. To 250 ° C. However, the measurement is performed in the Rectangular Torsion mode, the measurement frequency is 1 Hz, and the temperature increase rate is 5 ° C./min. In the obtained temperature-storage modulus curve, the intersection of the tangent in the glass region and the tangent in the transition region from the glass region to the rubber region was determined, and the temperature at this intersection was taken as the glass transition temperature.

(8) Cover factor of glass fiber fabric prepreg This is an element related to the texture (resin rich portion) formed between the yarns (glass fiber bundle) of the glass fiber fabric in the glass fiber fabric prepreg. When the area of area S1 was set, the value defined by the following equation was used, where S2 is the area of the textured portion formed by the woven yarn in area S1. The area S1 is an arbitrary 100 cm ² on the plane of the glass fiber woven prepreg, and the cover factor is 5 pieces of 10 × 10 cm test pieces cut in the width direction of the woven fabric, and the individual measured from the five locations The average value was taken.
Cover factor (%) = [(S1-S2) / S1] × 100
(9) Volume resistivity of glass fiber woven prepreg 24 plies of glass fiber woven prepreg were laminated in the warp direction. This was vacuum-backed and molded in an autoclave at a temperature of 180 ° C. for 2 hours under a pressure of 0.59 MPa at a heating rate of 1.5 ° C./min to produce a laminate. In an autoclave, the temperature was raised to 180 ° C. at a rate of temperature rise of 1.5 ° C./min and cured under a pressure of 0.59 MPa for 2 hours. From this laminate, five samples each having a length of 50 mm and a width of 50 mm were cut out, and a sample in which a conductive paste “Dotite” (registered trademark) D-550 (manufactured by Fujikura Kasei Co., Ltd.) was applied on both sides was prepared. These samples were measured for resistance in the thickness direction under a voltage of 200 V using a resistance meter of SM-8220 manufactured by HIOKI Corporation, and volume specific resistance was obtained.

(10) Conductive filler and average particle diameter of conductive particles Regarding the average particle diameter of the conductive filler and conductive particles, the particles are magnified 1000 times or more with a microscope such as a scanning electron microscope. Images were taken, particles were randomly selected, the diameter of the circle circumscribing the particles was taken as the particle size, and the average value of the particle sizes (n = 50) was obtained.

(11) Glass fiber mass fraction of glass fiber woven prepreg A glass fiber woven prepreg is cut out to a size of 10 × 10 cm, N-methyl-2pyrrolidone (NMP) using an ultrasonic cleaner, and then methyl ethyl ketone (MEK). And washed twice for 10 minutes each, and only the glass fiber fabric was taken out of the glass fiber fabric prepreg. With respect to the mass (W1) of the glass fiber fabric prepreg, the glass fiber mass fraction was measured from the mass (W2) of the obtained glass fiber fabric using the following formula.
Glass fiber mass fraction (%) = (W2 / W1) × 100.

  The materials used in each example and each comparative example are as follows.

<Glass fiber fabric (A)>
Glass fiber fabric, WEA-05E-105-F236N (manufactured by Nittobo Co., Ltd., basis weight 47 g / m ² , vertical density 59/25 mm, weft density 46/25 mm).

<Epoxy resin (B)>
-Bisphenol F type epoxy resin, "Epiclon" (registered trademark) 830 (DIC Corporation).
-Bisphenol A type epoxy resin, “jER (registered trademark)” 825 (manufactured by Mitsubishi Chemical Corporation).
Diglycidyl-p-phenoxyaniline, PxGAN (manufactured by Toray Fine Chemical Co., Ltd.)
N-glycidyl phthalimide, “Denacol (registered trademark)” Ex-731 (manufactured by Nagase ChemteX Corporation).

<Epoxy resin (B1)>
Tetraglycidyldiaminodiphenylmethane, ELM434 (manufactured by Sumitomo Chemical Co., Ltd.).
Triglycidyl-m-aminophenol, MY0610 (manufactured by Huntsman Advanced Materials).

<Epoxy resin curing agent (C)>
-4,4'-diaminodiphenyl sulfone, "Seika Cure (registered trademark)"-S (manufactured by Wakayama Seika Co., Ltd.).

<Conductive filler (D)>
Carbon black, Mitsubishi carbon black # 3030B (manufactured by Mitsubishi Chemical Corporation, particle size: 55 nm).
Carbon black, Mitsubishi carbon black # 3230B (manufactured by Mitsubishi Chemical Corporation, particle size: 23 nm).
Carbon black, carbon ECP (manufactured by Lion Corporation, particle size: 40 nm).

<Conductive particles>
Carbon particles, “NICABEADS (registered trademark)” ICB-2020 (manufactured by Nippon Carbon Co., Ltd., average particle size: 27 μm).

<Thermoplastic resin soluble in epoxy resin (E)>

Polyethersulfone, “Sumika Excel (registered trademark)” PES5003P (manufactured by Sumitomo Chemical Co., Ltd.). <Thermoplastic resin used for press molding>

Polypropylene (PP) resin pellets, “Prime Polypro (registered trademark)” J830HV (manufactured by Prime Polymer Co., Ltd.).
Polyamide 6 (PA6) resin pellet: “Amilan (registered trademark)” CM1001 (manufactured by Toray Industries, Inc.). Example 1
In the kneader, 40 parts by mass of “Epiclon” (registered trademark) 830 as the epoxy resin (B) component, 60 parts by mass of ELM434 as the aromatic epoxy resin (B1) component, and Mitsubishi as the conductive filler (D) component Carbon black # 3030B is mixed with 0.6 parts by mass and 10 parts by mass of PES5003P as a thermoplastic resin (E) component and dissolved, and then 4,4′-diaminodiphenylsulfone as an epoxy resin curing agent (C) component. Was mixed with 45 parts by mass to prepare an epoxy resin composition. Using the obtained epoxy fat composition, the viscosity at 80 ° C., flexural modulus, volume resistivity, and glass transition temperature were measured.
Next, the prepared resin composition was coated on a release paper with a resin basis weight of 17 g / m ² using a knife coater to prepare a resin film. This resin film is superimposed on both sides of the glass fiber fabric, and a heat roll is used to impregnate the epoxy resin composition while heating and pressurizing at 100 ° C. and 1 atm to obtain a glass fiber fabric prepreg having a glass fiber mass fraction of 58%. Produced. Using the produced glass fiber fabric prepreg, the cover factor and the volume resistivity were measured. The results are shown in Table 1. Since it was confirmed that the epoxy resin cured product has a sufficiently high flexural modulus and the volume resistivity obtained from the glass fiber fabric prepreg is sufficiently small, it is a glass fiber fabric prepreg having both excellent compressive strength and antistatic performance. I found out.

(Examples 2 to 11)
An epoxy resin composition, as in Example 1, except that the types and blending amounts of the epoxy resin (B), aromatic epoxy resin (B1), and conductive filler (D) were changed as shown in Table 1. A glass fiber prepreg was prepared. Using the prepared epoxy resin composition, the viscosity, flexural modulus, volume resistivity, and glass transition temperature at 80 ° C. were measured. In addition, the cover factor and the volume resistivity were measured using the produced glass fiber fabric prepreg. The obtained results are shown in Table 1. Since it was confirmed that the epoxy resin cured product has a sufficiently high flexural modulus and the volume resistivity obtained from the glass fiber fabric prepreg is sufficiently small, it is a glass fiber fabric prepreg having both excellent compressive strength and antistatic performance. I found out.

(Examples 12 to 14)
Glass in the same manner as in Example 1 except that the heat roll pressure in Example 12 was changed to 0.3 atm, the heat roll pressure in Example 13 to 1.5 atm, and the heat roll pressure in Example 14 to 2 atm. A fiber woven prepreg was prepared. Using the prepared epoxy resin composition, the viscosity, flexural modulus, volume resistivity, and glass transition temperature at 80 ° C. were measured. In addition, the cover factor and the volume resistivity were measured using the produced glass fiber fabric prepreg. The obtained results are shown in Table 1. Since it was confirmed that the epoxy resin cured product has a sufficiently high flexural modulus and the volume resistivity obtained from the glass fiber fabric prepreg is sufficiently small, it is a glass fiber fabric prepreg having both excellent compressive strength and antistatic performance. I found out.

(Comparative Examples 1-3)
Epoxy resin in the same manner as in Example 1 except that the types and blending amounts of the epoxy resin (B), aromatic epoxy resin (B1), conductive filler (D), and conductive particles are changed as shown in Table 2. Compositions and glass fiber woven prepregs were prepared. Using the prepared epoxy resin composition, the viscosity, flexural modulus, volume resistivity, and glass transition temperature at 80 ° C. were measured. In addition, the cover factor and the volume resistivity were measured using the produced glass fiber fabric prepreg. The obtained results are shown in Table 2. In Comparative Example 1, no conductive filler is blended and the cured epoxy resin has a sufficiently high flexural modulus, but the volume specific resistance obtained from the glass fiber woven prepreg is high and sufficient antistatic performance is obtained. I found that there was no. In Comparative Example 2, although the conductive filler was blended, the viscosity of the epoxy resin composition was extremely high, and a glass fiber woven prepreg could not be produced. In Comparative Example 5, as a result of blending conductive particles having an average particle diameter of 27 μm instead of the conductive filler, the epoxy resin cured product has a sufficiently high flexural modulus, but the volume specific resistance obtained from the glass fiber woven prepreg is high. It was found that sufficient antistatic performance could not be obtained.

(Comparative Example 4)
1 ply of glass fiber fabric is aligned in a 30 cm long x 30 cm wide mold so that “Prime Polypro (registered trademark)” J830HV pellets are 100 parts by mass and Mitsubishi Carbon Black # 3030B is 0.4 parts by mass. The thermoplastic resin composition prepared in the above is filled in a mold, and press-molded under the conditions of 240 ° C. × 10 minutes using a heating press molding machine, and the glass fiber mass fraction is 30 cm in length × 30 cm in width. A glass fiber fabric prepreg was prepared. The cover factor was measured using the obtained glass fiber woven prepreg.

Next, the prepared glass fiber woven prepreg was laminated in a warp direction on a 30 cm long by 30 cm wide mold in a 24 warp direction, and press molded under the conditions of 240 ° C. × 10 minutes using a heating type press molding machine. A laminated body of glass fiber woven prepregs having a mass fraction of 58% and a length of 30 cm and a width of 30 cm was prepared. From this laminate, five samples each having a length of 50 mm and a width of 50 mm were cut out, and a sample in which a conductive paste “Dotite” (registered trademark) D-550 (manufactured by Fujikura Kasei Co., Ltd.) was applied on both sides was prepared. These samples were measured for resistance in the thickness direction under a voltage of 200 V using a resistance meter of SM-8220 manufactured by HIOKI Corporation, and volume specific resistance was obtained.

In addition, a thermoplastic resin composition prepared such that Mitsubishi Carbon Black # 3030B is 0.4 parts by mass with respect to 100 parts by mass of "Prime Polypro (registered trademark)" J830HV pellets is 2 mm in thickness. The set mold was filled and press-molded under the conditions of 240 ° C. × 10 minutes using a heating press molding machine to obtain a 2 mm-thick thermoplastic resin composition molded plate. Using this molded plate, the flexural modulus, volume resistivity, and glass transition temperature were measured. The obtained results are shown in Table 3. Although the volume resistivity obtained from the glass fiber woven prepreg is sufficiently small, the bending elastic modulus of the molded plate of the thermoplastic resin composition is low, and the laminate of the glass fiber woven prepreg made of the thermoplastic resin composition has sufficient compressive strength. It was found that could not be obtained. (Comparative Example 5)
Molded plate of thermoplastic resin composition in the same manner as in Comparative Example 4 except that the type of thermoplastic resin was changed as shown in Table 3 and the conditions of the heating press molding machine were changed to 300 ° C. × 10 minutes. And the glass fiber fabric prepreg was produced. The flexural modulus, volume resistivity, and glass transition temperature were measured using the molded plate of the produced thermoplastic resin composition. In addition, the cover factor and the volume resistivity were measured using the produced glass fiber fabric prepreg. The obtained results are shown in Table 3. Although the volume resistivity obtained from the glass fiber woven prepreg is sufficiently small, the bending elastic modulus of the molded plate of the thermoplastic resin composition is low, and the laminate of the glass fiber woven prepreg made of the thermoplastic resin composition has sufficient compressive strength. It was found that could not be obtained.

Claims (17)

A glass fiber fabric prepreg comprising at least the following components (A), (B), (C), (D), and an epoxy resin composition comprising (B), (C) and (D) The prepreg which contains 0.001-10 mass% of (D) in the thing, and the average particle diameter of (D) is 1 micrometer or less.
(A) Glass fiber fabric (B) Epoxy resin (C) Epoxy resin curing agent (D) Conductive filler The prepreg according to claim 1, wherein the conductive filler (D) is carbon black. The prepreg according to claim 1 or 2, wherein a volume specific resistance of a cured epoxy resin obtained by curing the epoxy resin composition at 180 ° C for 2 hours is from 10 ³ to 10 ¹¹ Ωcm. The prepreg of Claim 3 whose glass transition temperature of the said epoxy resin hardened | cured material is 180 degreeC or more. The prepreg according to claim 3 or 4, wherein the cured epoxy resin has an elastic modulus of 3 GPa or more. The prepreg according to any one of claims 1 to 5, wherein the epoxy resin composition has a viscosity at 80 ° C of 0.1 to 500 Pa · s. The prepreg in any one of Claims 1-6 whose glass fiber fabric weight of a glass fiber fabric (A) is 20-300 g / m < ² >. The prepreg in any one of Claims 1-7 whose glass fiber mass fraction in the said prepreg is 40-80 mass%. The prepreg according to any one of claims 1 to 8, wherein the epoxy resin (B) is an aromatic epoxy resin (B1) having at least one glycidylamine skeleton and having a tri- or higher functional epoxy group. The prepreg in any one of Claims 1-9 in which 50 mass% or more of aromatic epoxy resins (B1) are contained in an epoxy resin (B). The prepreg according to any one of claims 1 to 10, wherein the epoxy resin composition further contains a thermoplastic resin (E) soluble in the epoxy resin (B). The prepreg according to claim 11, wherein the thermoplastic resin (E) is polyethersulfone. The prepreg according to any one of claims 1 to 12, wherein the epoxy resin curing agent (C) is an aromatic amine curing agent containing a diphenylsulfone skeleton. The glass fiber woven fabric (A) according to any one of claims 1 to 13, wherein the glass fiber woven fabric (A) has a woven structure selected from a plain weave, a twill weave, an entangled weave, a patterned weave, an oblique weave, a double weave and a satin weave. Prepreg. The prepreg according to any one of claims 1 to 14, wherein a cover factor of the prepreg is 80% or more. Glass whose volume resistivity in the thickness direction is 10 ⁴ to 10 ¹² Ωcm when cured in an autoclave at a temperature of 180 ° C. for 2 hours under a pressure of 0.59 MPa at a heating rate of 1.5 ° C./min. The prepreg according to any one of claims 1 to 15, wherein a fiber-reinforced composite material is obtained. A glass fiber reinforced composite material formed by molding the prepreg according to claim 1.