JPS63314232A - Epoxy prepreg composition - Google Patents

Abstract

PURPOSE:To obtain the title composition excellent in workability in impregnation and compression moldability, by impregnating a reinforcing fiber with a specified curable resin composition. CONSTITUTION:100-30wt.% total of 100-200pts.wt. solventless liquid epoxy resin (a) of an average epoxy equivalent of 100-400, 5-200pts.wt. powdered epoxy resin (b) of an average epoxy equivalent >=100, an average particle diameter of 50-300mum and an m.p. >=50 deg.C, a polybasic acid anhydride (c) (e.g., methylhexahydrophthalic anhydride) and a cure accelerator (d) (e.g., diethylamine) is mixed with 0-70wt.% resin obtained by dissolving 40-80wt.% epoxy vinyl ester resin and/or unsaturated polyester resin (e) in a polymerizable vinyl monomer to obtain a curable resin composition (A) in which component (b) is dispersed. A reinforcing fiber (B) (e.g., glass fiber) is impregnated with component A and aged at room temperature or higher to dissolve the component B and to thicken it into B-stage.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to an improved and useful epoxy prepreg composition (hereinafter abbreviated as glycileg), and more particularly, to a composition in which a powdered epoxy resin is dispersed. The present invention relates to Silipreg, which is obtained by impregnating a fibrous reinforcing material with a specific curable resin composition, and which has particularly good impregnation workability, compression moldability, and excellent physical properties.

[Conventional technology]

Glyshireg, which is generally made of epoxy resin and fiber reinforcement such as glass fiber or carbon fiber, has a cured product that is heat resistant and
It has excellent physical properties such as chemical resistance, water resistance, adhesion, electrical properties, and mechanical properties, and has low curing shrinkage.Glyshireg itself is easy to handle as a molding material, so it is used for printed circuit boards, aviation, and space. It is also used as a structural material for vehicles.

Among these, prepregs for printed circuit boards mainly use glass fiber as the base material and epoxy resin containing a solvent as the resin. For this reason, a solvent-free solution is desired.

Furthermore, in the case of glycilegs for structural materials, a solvent-free epoxy resin matrix is desired, which can be easily impregnated into glass fibers, carbon fibers, etc., and which has excellent compression moldability and various physical properties.

By the way, as the solvent-free epoxy resin matrix, polyamine-cured epoxy resins, dicyanamide-cured epoxy resins, dibasic acid hydrazide-cured epoxy resins, polybasic acid anhydride-cured epoxy resins, or cured by ring-opening of epoxy groups are used. , so-called ring-opening polymerization cured epoxy resin systems, etc., but the requirements for the epoxy resin system as a matrix for bending prepregs are that it be uniform, and that the resin impregnated into the fibrous reinforcing material must first be impregnated. The viscosity must be sufficiently low to match the viscosity of the product.
Secondly, it has a long pot life, the prepreg itself has good stability, and the prepreg has a high curing speed during molding.

[Problem that the invention seeks to solve]

However, among polyamine-cured epoxy resin systems, those that use aliphatic polyamine as a curing agent generally have a short resin pot life and poor prepreg stability, while aromatic polyamine-cured systems have a long pot life but This is not preferable because the resin system may be non-uniform, or even if it is uniform, the viscosity may be high.

Dicyanamide curing systems and dibasic acid hydrazide curing systems are undesirable because the curing agent and resin tend to be non-uniform systems, and in addition, it is difficult to reduce the viscosity when impregnating the fibrous reinforcing material.

Further, in a curing system based on ring-opening polymerization of an epoxy group, it is difficult to obtain a stable one-stage state and to reduce the viscosity necessary for impregnating a fibrous reinforcing material, which is not preferable.

Furthermore, among polybasic acid anhydride curing systems, when a liquid acid anhydride, which is widely used as a curing agent for such epoxy resins, is used, it gives a relatively low viscosity product and is uniform in composition with the resin. Although the curing system is preferred as a matrix for silipregs because of its long pot life and stable, one-steno state, it is still not sufficient to be suitable for the impregnation of fibrous reinforcements. In order to obtain a low viscosity, it is necessary to use a particularly low viscosity liquid epoxy resin, and even if a particularly low viscosity liquid epoxy resin is used, a resin composition of this and a liquid polybasic acid anhydride is used as a matrix. When using molding, the reaction rate is generally low, so the melt viscosity during hot compression molding becomes too low and the matrix flows out, resulting in poor yield, and the hot compression molding time becomes longer, reducing productivity. The problem is that it gets worse.

Furthermore, in order to use a high viscosity or solid epoxy resin, which is preferable from the viewpoint of various physical properties, it is absolutely necessary to use a so-called diluent in order to lower the viscosity. However, although the use of such a diluent makes it possible to lower the viscosity, on the other hand, physical properties such as heat resistance, moisture resistance, and mechanical properties deteriorate.

[Means for solving problems]

However, from the technical background as described above, the present inventors
As a result of extensive research into prepregs using polybasic acid anhydride-cured epoxy resin systems, especially solvent-free polybasic acid anhydride-cured epoxy resin systems as matrices, we have found that polybasic acid anhydride-cured epoxy resin systems, preferably this Nyxy resin When a curable resin composition in which a powdered epoxy resin is dispersed in a so-called polymer alloy of a polyester resin and an epoxy vinyl ester resin and/or an unsaturated polyester resin is used as a prepreg matrix for the impregnation operation, the impregnation operation can be improved. They found that the prepreg prepared by dissolving the powdered Nixy resin in matrices and dissolving materials, which was then aged at room temperature or higher temperature, had good compression moldability and excellent physical properties, and the present invention I was able to complete it.

That is, the present invention comprises a solvent-free liquid epoxy resin (A), a powdered epoxy resin (B) having a melting point of 50° C. or higher, a polybasic acid anhydride (C), a curing accelerator (B), an epoxy vinyl ester resin, and /or unsaturated polyester resin (g)
) and [: (A) + (B) + (C) +
(D) ) / @) weight ratio is 10010 to 30/7
The present invention provides a prepreg in which a fiber reinforcing material (II) is impregnated with a curable resin composition (I) in which powdered epoxy resin (B) is mixed in a ratio of 0. be.

As the above-mentioned epoxy resin used in the present invention, any one or a mixture of epoxy resins that are solvent-free liquid at room temperature can be used, but usually the average epoxy commercial amount is 100 to 400.
, preferably 100 to 250. Typical examples include epoxy resins obtained from shrimp chlorhydride, all of which are solvent-free liquid at room temperature, and dihydric phenols such as bisphenol A, bisphenol F, and resorcinol; Polyglycidyl ethers of polyhydric alcohols such as polypropylene glycol, neopentyl glycol, glycerin, trimethylolethane, trimethylolpropane or ethylene oxide or propylene oxide adducts of dihydric phenols; anovic acid, heptalacid, tetrahydrophthalic acid , polyglycidyl esters of polycarboxylic acids such as hexahydrophthalic acid or dichoic acid; cyclohexene-based epoxy compounds (3,4-epoxy- 6-methyl-cyclohexyl-3,4-zyp
xy-6-methylcyclohexanecarboxylate, 3
．． 4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 1-epoxyethyl-3,4-epoxycyclohexane, etc.); Epoxidizing cyclointadiene or dicyclopentadiene or their derivatives with peracetic acid etc. cyclopentadiene-based epoxy compounds (cyclopentanoene oxide, dicyclopentatsuene oxide, 2,3-epoxycyclopentyl ether, etc.); limonene oxide; or glycidyl ether ester of hydroxybenzoic acid, etc. Among these, solvent-free liquid epoxy resins obtained from epichlorohydrin, bisphenols, and esters are preferred because they have a good balance in performance and are inexpensive, and solvent-free liquid cyclohexene epoxy compounds are preferred because they provide low viscosity. If necessary, a liquid mixture obtained by dissolving an epoxy resin solid at room temperature in the above solvent-free liquid epoxy resin alone or in a mixture may be used as the epoxy resin (A).

The epoxy resin (B) used in the present invention has a melting point of 5
Epoxy resins that are powdered at 0°C or higher can be used alone or as a mixture, but usually those with an average epoxy equivalent of 100
The average particle size is 50 to 300 μm, preferably the average epoxy equivalent is 170 or more and the average particle size is 100 to 200 μm.
m powdered epoxy resin is used. Typical examples include powdered epichlorohydrin, bisphenol A, bisphenol F, and all have melting points of 50°C or higher.
Epoxy resins obtained from dihydric phenols such as resorcinol, tetrabromobisphenol A, tetrabromobisphenol F, and bisphenol S; polyglycidyl ethers of polyhydric phenols such as phenol, alkylphenols, or brominated phenol/novolac resins;
Collinear epoxy resin consisting of dihydric phenol and novolac resin; polyhydric epoxy resins such as polyglycidyl ethers of the aforementioned polyhydric alcohols, polyglycidyl esters of polycarboxylic acids, aniline, p- (or m-) amine phenols, and diaminodiphenylmethane. Collinear epoxy mJ of polyglydinolamine of amine and glycidyl ether ester of hydroxybenzoic acid with dihydric phenol/monohydric phenol]I? There are triglycitrus isocyanurates, among others, powdered epoxy resins obtained from epichlorohydrin and bisphenol A have a good balance of performance and are inexpensive, and powdered polyhydric phenol polyglycidyl ethers are heat resistant. In addition, a powdered epoxy resin obtained from epichlorohydrin and tetrabromobisphenol A and a powdered brominated polyhydric phenol polyglycidyl ether are preferable because they have excellent flame retardancy.

Typical examples of the polybasic acid anhydride (C) used in the present invention are 7-thalic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, and methyltetrahydrophthalic anhydride. Acid, nanotuccinic anhydride, methylnadic anhydride, trimellitic anhydride, biromellitic anhydride, maleic anhydride, succinic anhydride, itaconic anhydride, citraconic anhydride, dodecenyl anhydride:, 2, phosphoric acid, chlorendic anhydride Acid, penzophenonetetracargenic anhydride, sifuronetatetracarboxylic anhydride, 5-(2,5-dioquinetetrahydrofuryl)-3-methyl-3-cyclohexe 7-1.2
- Dicarnic acid, ethylene glycol bistrimelitate anhydride, glycerin trimellitate anhydride, etc., and these can be used alone or in the form of a mixture of two or more types. Among them, liquid ones are preferred, such as methylhexahydrophthalic anhydride, nadic anhydride, methylnadic anhydride, and the like.

Further, typical curing accelerators (b) used in the present invention include diethylamine, triethylamine, tightusprobylamine, monoethanolamine, jetanolamine, triethanolamine, methylethanolamine, methyljetanolamine, Monoisoglonomotherolamine, nonylamine, dimethylaminopropylamine, dimethylaminopropylamine, α-pennoldiethanolamine; 2,4.6-dolysudimethylaminomethylphenol or its tri-2-ethylhexylate; 2-dimethylaminomethylphenol, Pyridine, piperidine, N-aminopropylmorpholine, 1
, 8-diazabicyclo(5,4,0)undecene-7 or various amines such as salts thereof with phenol, 2-ethylhexanoic acid, oleic acid, nophenylphosphorous acid, or organic phosphorous acids; 2-methylimidazole, 2 - Isopropylimidazole, 2-undecylimidazole, 2-phenylimitasol, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, imidazole and metal salt complexes such as Cu, Ni or Co; 2- Imidazoles such as cyanoethylation type imidazoles obtained by reacting methylimidazole with acrylonitrile or their adducts with trimellitic acid or reactants with dicyandiamide: BF, -monoethanolamine, BF3-pennolamine, BF , -tumethylaniline, BF, -
Triethylamine, BF3-n-hexylamine,
BF', -amine complexes such as BF', -2,6-diethylamine/, BF, -aniline or BF, -piperidine: amine imide compounds starting from 1,1-dimethylhydrazine; phosphorus such as triphenyl phosphite; compounds or organic acid metal salts such as tin octylate.

Furthermore, the epoxy vinyl ester resin preferably used as the resin (2) in the present invention includes epoxy resins and various epoxy resins as listed above as (B), preferably bisphenol type or nogelac tights epoxy resins. Examples include resins in which an epoxy vinyl ester obtained by reacting each of them alone or as a mixture with an unsaturated basic acid as described below in the presence of an esterification catalyst is dissolved in a polymerizable vinyl monomer.

Here, typical unsaturated basic acids include acrylic acid, methacrylic acid, cinnamic acid, crotonic acid, monomethyl maleate, motsputil maleate, motsputyl maleate, undrubic acid, and mono(2-ethylhexyl). These can be used alone or in a mixture of two or more.

Typical polymerizable vinyl monomers include styrene, vinyltoluene, -butylstyrene, chlorstyrene, styrene and its derivatives such as divinylbenzene; 2-ethylhexyl (meth)
AkuUV-1, low boiling ester monomers of (meth)acrylic acid such as lauryl (meth)acrylate, 2-hydroxyethyl (meth)acrylate or 2-hydroxypropyl (meth)acrylate; or trimethylolglopantri(meth)acrylate; ) acrylate, di(meth)acrylate of polyhydric alcohols such as di(meth)acrylate, 1,4-butanediol di(meth)acrylate, or 1,6-hexanediol di(meth)acrylate. These are usually used alone or as a mixture of two or more in a ratio of 60 to 20% by weight (total 100% by weight) based on 40 to 80% by weight of epoxy vinyl ester.
In the present invention, the unsaturated polyester resin preferably used as the resin (g)) is an unsaturated polyester obtained by the reaction of dibasic acids containing unsaturated dibasic acids and polyhydric alcohols. Examples of the polymerizable vinyl monomer used here include the same polymerizable vinyl monomers as mentioned above, and these can be used alone or as a mixture of two or more.
Usually 60 to 40 to 80% by weight of unsaturated polyester
It is used in a proportion of ~20% by weight (total 100% by weight).

Typical unsaturated dibasic acids include maleic acid, m
Hydromaleic acid, 7-malic acid, halogenated maleic anhydride, etc. Other typical acids that can be called saturated dibasic acids include 7-talic acid, 7-talic anhydride, 7-talic anhydride, and halogenated maleic anhydride.
Ogylated phthalic anhydride, in-7thalic acid, terephthalic acid,
Examples include tetrahydrophthalic anhydride, succinic acid, adipic acid, and sebacic acid, while typical polyhydric alcohols include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, diethylene glycol, and 1,3-butylene glycol. , 1,4-butylene glycol, neopentyl glycol, hydrogenated bisphenol/l/A, 1,6-hexanediol, adducts of bisphenol A and ethylene oxide or propylene oxide, glycerin, trimethylolglopane, etc. .

In order to obtain an epoxy vinyl ester resin and an unsaturated polyester resin using each of these raw materials, conventionally known methods may be followed. It is recommended to use a polymerization inhibitor for the purpose of preventing dulling during resin preparation and for adjusting the storage stability or curability of the resulting resin. Examples include hydroquinones such as hydroquinone, pt-butylcatechol, and mono-t-butylhydroquinone; hydroquinone monomethyl ether, di-t-butylhydroquinone;
These include phenols such as p-cresol; quinones such as p-benzoquinone, naphthoquinone, and l)-torquinone; and copper salts such as copper heptenoate.

By the way, both (6) component resins obtained in this way can be sufficiently cured by simply heating without using a catalyst, but if necessary, benzoyl/4'
- oxide, p-menthane hydride 1:I/” -,
Organic peroxides such as oxide, t-butylperbenzoate, 1,1-not-butylperoxy-3,3,5-)limethylcyclohexanone can be used as polymerization initiators; relevant)
The components can be thought of as a resin composition consisting of a resin and a polymerization initiator.

Further, as the resin constituting the component (6), it goes without saying that epoxy vinyl ester resin or unsaturated polyester resin may be used alone, or both types of resin may be used in combination.

And the solvent-free liquid epoxy resin (A) has a melting point of 50°C.
The above powdered epoxy resin (B) and polybasic acid anhydride (C
) and a curing accelerator (b) [
(A) + (B) + (C) + (D) ), an epoxy vinyl ester resin and/or an unsaturated polyester resin (g), and if necessary, a polymerization initiator is also added. The weight ratio of the composition to the component) can be selected appropriately depending on the required properties and working conditions, but if the ratio of the component @:) becomes too large, use epoxy vinyl ester resin or unsaturated polyester resin. The physical properties are close to that of itself, and [(5) + (B) + (C
)+(6)] The characteristics of the polybasic acid anhydride-cured epoxy resin composition, such as low curing shrinkage, are impaired.

Therefore, both components [prison + (B) + (C') +
The weight ratio of CD) ]/(g)) is 10010 to 30/7
0, preferably in the range of 9515 to 60/40.

Here, the solvent-free liquid epoxy resin (A) and the melting point are 50 ° C.
Weight ratio CA)/■) of the above powdered epoxy resin (B)
is usually 10015 to 100/200, preferably 10
The range is 015 to 100150. However, when using a flame-retardant powdered epoxy resin, (A
)/(B) weight ratio is 100/100 to 100/200
A range of is preferred.

The above components C (A) + (B) + (C) An epoxy vinyl ester resin and/or an unsaturated polyester resin as component (E) to the acid anhydride (C),
If necessary, it is also possible to mix the polymerization initiator and then add the remaining component compounds, so the order of blending each component compound is not limited.

Further, it is also possible to add conventional additives such as internal mold release agents or pigments to the curable resin composition (I) constituting the grippreg of the present invention thus obtained.

On the other hand, the fibrous reinforcing material (I
Typical examples of N) include glass fiber, carbon fiber, and aromatic polyamide fiber.
E-glass, C-glass, A-glass, S-glass, etc. exist, but any type can be applied in the present invention.

Next, what about carbon fiber? Liacrylonitrile fiber,
Examples include those manufactured using cellulose fibers, pitch, aromatic hydrocarbons, or carbon black as raw materials, and aromatic polyamide fibers are produced by the reaction of polyfunctional aromatic amines and aromatic polybasic acids. It is made from a polymer having an amide bond, and typical polymers include /+)-p-phenylenetetraphthalamide or poly-p-aminobenzamide.

These fibrous reinforcement materials (It) are classified into rovings, chopped strand mats, continuous mats, cloths, roving cloths, surfaging mats, and chipped strands depending on their shape, but there are no coverings or shapes such as hoisted strands. They are appropriately selected depending on the intended use and performance of the molded product, and two or more types or shapes may be used in combination, if necessary.

The invention! In obtaining repreg, fibrous reinforcement (
The volume ratio of II) is suitably within the range of 30 to 70% of the prepreg.

In order to obtain the prepreg of the present invention, the reinforcing material (n) is impregnated with the resin composition Q) at room temperature or higher temperature to form a sheet, and then sandwiched with a release sheet. Similarly, the resin composition (I) is aged at room temperature or a higher temperature to dissolve the powdered epoxy resin dispersed in the resin composition (I) and thicken it to a B-stage state. Good.

The prepreg of the present invention obtained by such a method is then heated and compression molded to give a desired molded product.
At this time, if necessary, post-curing may be further performed after release from the molding die.

〔Example〕

Next, the present invention will be specifically explained using Examples and Comparative Examples. In the following, parts and parts are all based on weight unless otherwise specified.

Example 1 90 parts of bisphenol A liquid epoxy resin with an epoxy equivalent of 190, an epoxy equivalent of 2700 and a melting point of 147
Powdered bisphenol A with an average particle size of 130 μm at °C
10 parts of type epoxy resin, 80 parts of methyltetrahydrophthalic anhydride and 0.6 parts of pennoldimethylamine, and further methacrylate (70%) of a phenol novolak type epoxy resin having an epoxy equivalent of 182 and styrene monomer (30%). 46 parts of epoxy vinyl ester resin, 0.9 parts of benzoyl/'P-oxide as a radical initiator, and 2 parts of zinc stearate as an internal mold release agent were mixed to disperse a powdered bisphenol A type epoxy resin. A curable resin composition was prepared.

40 parts of this curable resin composition was impregnated at room temperature into 60 parts of Chizonotsubutsutran R glass with a cut length of 1 inch placed on a polyethylene release film (thickness: 50 AuR), and after pressing, the mixture was heated at 40°C. The mixture was aged in an electric heat dryer for 30 hours and the powdered bisphenol A type epoxy resin was dissolved to obtain a tack-free prepreg (volume ratio of 40% of the layered Tubbutsutran P glass).

Three sheets of this prepreg were stacked so that the charge rate was 901fi and fi excellent, and the pressure was 50%, 9 parts cm, and the temperature was 160%.
℃.

After heating and compression molding for 6 minutes, the product was cured for 1 hour in an electric dryer at 170°C to obtain a flat plate with a thickness of 3 mm. Also, the ciano rate is 80! R shadow.

A flat sheet metal was obtained in the same manner as described above except for the following, so that the area was 70 sided and 60 sided. Table 1 shows the physical properties of the curable resin composition (viscosity and impregnability into chopped strand 9 glass). , the physical properties of the prepreg (viscosity and tackiness of the matrix), the physical properties of the molded product (flexural strength of the 90-sided Danfeng molded product at 25°C and 120°C, and the lath content (charge rate) of the molded product) The measurement results are shown below (comparison of glass content in the center and periphery of molded products with an area of 90 to 60).

Example row 2 60 parts of bisphenol AW liquid epoxy resin with an epoxy equivalent of 190, 420 parts of stone 3.4-epoxycyclohexylmethyl-3,4-epoxycyclohexane calfoxylate with an epoxy equivalent of 135, and 420 parts of epoxy equivalent with 45
20 parts of a powdered bisphenol large epoxy resin with a melting point of 155° C. and an average particle size of 150 μm, 90 parts of methyltetrahydrophthalic anhydride, 0.6 parts of 2-ethyl-4-methylimidazole, and further [Polylite FG-
387J [Unsaturated polyester resin manufactured by Dainippon Ink and Chemicals Co., Ltd., styrene monomer content 401:13
420.9 parts of benzoyl/mother oxa and 2 parts of zinc stearate were mixed to obtain a curable resin composition in which powdered bisphenol A type epoxy resin was dispersed.

Hereinafter, Example 1 was repeated except that this curable resin composition was used.
A prepreg and a flat plate were obtained in the same manner as above, and then various physical properties and glass content were measured in the same manner. Measurement results first
Shown in the table.

Example 3 70 resorcinol liquid epoxy resins with an epoxy equivalent of 120, 30 parts of a powdered cresol novolac type epoxy resin with an average particle size of 180 μm and an epoxy equivalent of 220 and a melting point of 95°C, 7 parts of methyl hexahydro anhydride, 1 part of talic acid
19 parts and 0.2-ethyl-4-methylimidazole.
6 parts of the epoxy vinyl ester m fat used in Example 1, 1 part of benzoyl peroxide, and 2 parts of zinc stearate were mixed to obtain a curable resin in which powdered cresol novolak type epoxy resin was dispersed. 40 parts of composition.

Hereinafter, Example 1 was repeated except that this curable resin composition was used.
A prepreg and a flat plate were obtained in the same manner as above, and then various physical properties and glass content were measured in the same manner. Measurement results first
Shown in the table.

Example 4 39 parts of bisphenol A liquid epoxy resin with an epoxy equivalent of 190, an epoxy equivalent of 665 and a melting point of 100
61 parts of a powdered tetrabromobisphenol A type epoxy resin with an average particle size of 130 μm, 50 parts of methyltetrahydrophthalanhydride wI and 0.6 parts of 2-ethyl-4-methylimidazole, and tetrabromobisphenol A with an epoxy equivalent of 370. Type epoxy resin methacrylate (73%) tostyrene monomer (27%),! :
64 parts of epoxy vinyl ester resin, 1 part of benzoyl peroxide, and 2 parts of zinc stearate were mixed to obtain a curable resin composition in which powdered tetrabromobisphenol A type epoxy resin was dispersed.

Hereinafter, Example 1 was repeated except that this curable resin composition was used.
A prepreg and a flat plate were obtained in the same manner as above, and then various physical properties and lath content were measured in the same manner. Measurement results first
Shown in the table.

Comparative Example 1 90 parts of bisphenol A liquid epoxy resin with an epoxy equivalent of 190 and a melting point of 14 with an epoxy equivalent of 2700
Powdered bisphenol A with an average particle size of 130 μm at 7°C
Type epoxy flt fat lo part to txo.

A homogeneous mixture in which the powdered epoxy resin was dissolved was prepared in the same manner as in Example 1, except that the powdered epoxy resin was mixed at ℃ for 2 hours, and then cooled to room temperature and used as a uniform epoxy resin mixture. A curable resin composition was obtained.

This curable resin composition had a high viscosity, and it was difficult to uniformly impregnate 60 parts of rhubarb strand glass with a cut length of 1 inch with 40 parts of this composition. Nevertheless, the prepared prepreg was aged at 40° C. for about 30 hours to obtain a tack-free prepreg with some poor impregnation. Thereafter, a flat sheet metal was obtained in the same manner as in Example 1, and then various physical properties and lath content were measured in the same manner.

The measurement results are shown in Table 1.

Comparative Example 2 A uniform curable resin composition was obtained in the same manner as in PJ 1 except that 10 parts of powdered bisphenol A type epoxy resin having an average particle size of 130 μm was omitted.

Hereinafter, Example 1 was repeated except that this curable resin composition was used.
A prepreg and a flat plate were obtained in the same manner as above, and then various physical properties and glass content were measured in the same manner. Measurement result'f,
Shown in Table 1.

〔Effect of the invention〕

As is clear from the results in Table 1 above, the Glyshireg of the present invention has good impregnating workability and is easy to manufacture, even though it uses an epoxy resin that is solid at room temperature, and has a low viscosity during molding. This has the advantage that even if the charge rate is low, a molded article with a constant fiber reinforcing material content in each region and excellent physical properties can be obtained.

Attorney: Patent Attorney Katsutoshi Takahashi Procedural Amendment (spontaneous) July 29, 1985 Director General of the Japan Patent Office Kunio Ogawa 1, Indication of the case, Patent Application No. 149205 No. 149205 of 1988, 2, Name of the invention: EpoxyPri Greg Composition 3, Relationship with the Amended Person Case Patent applicant: 35-58 Sakashita, Itabashi-ku, Tokyo 174 (28
8) Dainippon Ink Chemical Industry Co., Ltd. Representative Shigekuni Kawamura 4, Representative Address: 103 Tj20, Nihonbashi 3-chome, Nakao-ku, Tokyo, Japan Dainippon Ink Chemical Industry Co., Ltd. Phone: Tokyo (03) 272-4511 (Dainippon Ink Chemical Industry Co., Ltd.) representative)
7゜5, subject of correction −
゛-6. Contents of amendment (I) From line 4 from the bottom of page 9 of the specification to line 4 of page tJlo, “the above-mentioned ~collinear epoxy resin:” has been changed to “aniline, p(m-)aminephenol, A polyglycidyl amine of a polyhydric amine such as diaminodiphenylmethane, a polyglycidyl ether of the above-mentioned polyhydric alcohol, a polyglycidyl sol ester of /+7 cargonic acid or a glycidyl ether ester of hydroxybenzoic acid, and a dihydric phenol alone or in combination. Corrected to ``collinear epoxy resin with mixture of hydric phenols;''.

Claims (1)

[Scope of Claims] A solvent-free liquid epoxy resin (A), a powdered epoxy resin with a melting point of 50°C or higher (B), a polybasic acid anhydride (C), a curing accelerator (D), an epoxy vinyl ester resin, and / or unsaturated polyester resin (E), [(A)+(B
)+(C)+(D)]/(E) weight ratio is 100/0~
A curable resin composition (I
) is impregnated into a fiber reinforcing material (II).