JPH05140264A - Production of thermosetting resin composition and laminated board - Google Patents

Abstract

PURPOSE:To produce the subject compsn. which allows, over a long time, the stable production of a laminated board excellent in the resistance to water absorption and soldering heat by compounding a specific epoxy-vinyl ester resin with a polybasic acid anhydride, a polymn. initiator, and a latent cure accelerator. CONSTITUTION:An epoxy resin is reacted with an unsatd. monobasic acid in a molar ratio of the carboxyl groups of the acid to the epoxy groups of the resin of 0.05-0.6 to give an epoxy-vinyl ester resin, which is compounded with a polybasic acid anhydride, a polymn. initiator, and a latent cure accelerator. An esp. pref. epoxy-vinyl ester resin is one in which the monobasic acid has been combined with a part of epoxy groups of the epoxy resin and which has a high content of molecules having both vinyl and epoxy groups.

Description

TECHNICAL FIELD The present invention relates to a thermosetting resin composition used for a laminated board useful for a printed circuit board and the like and a method for producing a laminated board using the same, and particularly to storage stability. The present invention relates to a thermosetting resin composition excellent in heat resistance and a method for producing a laminated plate obtained by using the same, which is excellent in water absorption, solder heat resistance and the like.

[Conventional technology]

 The glass epoxy laminate used as a printed circuit board is manufactured by heat and pressure molding after passing through a B-staged prepreg, and it has excellent heat resistance and electrical properties as an epoxy resin curing agent. It is known to use polybasic acid anhydrides.

 Since the above heat and pressure molding requires a long time and there is a problem in productivity, the epoxy resin and the epoxy resin curing agent start polymerization with a resin having at least two or more unsaturated groups in one molecule. A method for producing a prepreg in which a molding agent is added to improve the moldability has been proposed (JP-A-62-285929).

[Problems to be Solved by the Invention]

 However, in the above method, since the resin having at least two unsaturated bonds in one molecule is used, the prepreg obtained has a fast curability, but the physical properties of the laminate of the final cured product are high. As a result, there is a problem that the heat resistance is not sufficient and the storage stability of the curable resin composition used is not sufficient.

[Means for Solving the Problems]

 The present inventors have conducted intensive studies in view of such a situation, and as a result, as a result of comparing the epoxy resin and the unsaturated monobasic acid with one epoxy group in the epoxy resin, a carboxyl group in the unsaturated monobasic acid is used. The storage stability of the thermosetting resin composition is improved by using the epoxy vinyl ester resin obtained by reacting the epoxy vinyl ester resin in the ratio of 0.05 to 0.6 in combination with the latent curing accelerator. Therefore, it was found that a laminated plate having excellent water absorption rate and solder heat resistance can be stably manufactured over a long period of time, and the present invention has been completed.

 That is, in the present invention, the number of carboxyl groups in the unsaturated monobasic acid of the epoxy resin and the unsaturated monobasic acid is 0.05 to 0.6 per one epoxy group in the epoxy resin. Epoxy vinyl ester resin (A) obtained by reacting in a ratio, polybasic acid anhydride (B), polymerization initiator (C), and latent curing accelerator (D). A thermosetting resin composition, and an epoxy resin and an unsaturated monobasic acid in which the number of carboxyl groups in the unsaturated monobasic acid is 0.05 with respect to one epoxy group in the epoxy resin. To an epoxy vinyl ester resin (A) obtained by reacting at a ratio of about 0.6, a polybasic acid anhydride (B), a polymerization initiator (C), and a latent curing accelerator (D). After impregnating the fibrous base material with the thermosetting resin composition (I) containing There is provided a process for preparing laminates you characterized thereby.

 The epoxy vinyl ester resin (A) used in the present invention comprises an epoxy resin and an unsaturated monobasic acid in which the number of carboxyl groups in the unsaturated monobasic acid is 0 relative to 1 epoxy group in the epoxy resin. Any of those obtained by the esterification reaction at a ratio of 05 to 0.6 can be used. Among them, esterification is carried out at a ratio of the number of carboxyl groups to one epoxy group of 0.2 to 0.6. The one obtained by reacting is preferable.

 If the number of carboxyl groups in the unsaturated monobasic acid is less than 0.05 per epoxy group in the epoxy resin, use the impregnating resin composition impregnated with a fibrous base material. In the final thermoforming, the contribution of the curing due to the vinyl group-based polymerization that precedes the reaction of the epoxy groups is small, and the resin impregnated during thermoforming is too unfavorable. When the number is more than 0.6, the number of components having both an epoxy group and a vinyl group in one molecule is small, and the number of components having only a vinyl group is increased, so an epoxy compound with a vinyl group added and an epoxy without this group added The crosslinking reaction of the compound via the polybasic acid anhydride (B) and the like is reduced, and the glass transition temperature (Tg) is lowered, which is not preferable.

 Therefore, the content of the epoxy vinyl ester resin used in the present invention is one in which an unsaturated monobasic acid is added to a part of the epoxy groups in the epoxy resin to have both a vinyl group and an epoxy group in one molecule. Among them, many are preferable.

 Usually, as an esterification catalyst of an epoxy resin and an unsaturated monobasic acid, a tertiary amine, a quaternary ammonium salt, an ion exchange resin having a tertiary or quaternary amino group, a trialkylhydrazonium. Examples thereof include phosphorus compounds such as salts, thioethers, sulfonium salts, phosphine derivatives and quaternary phosphonium salts. In the present invention, whichever esterification catalyst is used, it is used as the epoxy vinyl ester resin (A). However, among them, the reaction between the epoxy vinyl ester resin (A) and the polybasic acid anhydride (B), that is, the reaction between the hydroxyl group in the (A) and the acid anhydride group in the (B) is promoted. The epoxy vinyl ester resin obtained by the esterification reaction in the presence of a catalyst, preferably a phosphorus compound, particularly preferably a phosphine derivative contains this. Because significantly improve the storage stability of the curable resin composition comprising Te particularly preferred.

 The esterification reaction is usually carried out in the temperature range of 60 to 140 ° C., preferably 80 to 120 ° C., but is not particularly limited.

 Typical examples of the epoxy resin used for obtaining the above-mentioned epoxy vinyl ester resin (A) include epichlorohydrin or β-methylepichlorohydrin and epoxy resin obtained from bisphenol A, bisphenol F or bisphenol S; phenol or Alkylphenols ・ Polyglycidyl ethers of novolak resins; ethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol, neopentyl glycol, glycerin, trimethylolethane, trimethylolpropane or adducts of bisphenol A with ethylene oxide or propylene oxide. Polyglycidyl ethers of polyhydric alcohols such as; adipic acid, phthalic acid, tetrahydrophthalic acid, hexahydro Polyglycidyl ester acids of polycarboxylic acids such as phthalic acid or dimer acid; Cyclohexane-based epoxide compounds (3,4-epoxy-6-methyl-) obtained by epoxidizing cyclohexane or its derivatives with peracetic acid, etc. Cyclohexyl-3,4-epoxy-6-methyl-cyclohexancarboxylate, 3,4-epoxycyclohexylmethyl-3,4-cyclohexanecarboxylate, 1-epoxyethyl-3,4-epoxycyclohexane, etc.); Cyclopentadiene-based epoxy compounds (cyclopentadiene oxide, dicyclopentadiene oxide, 2,3-epoxycyclopentyl) obtained by epoxidizing cyclopentadiene or dicyclopentadiene or their derivatives with peracetic acid. Ethereal Etc .; limonendioxide; or glycidyl ether ester of hydroxybenzoic acid, etc., which may be used alone or in admixture of two or more.

 Typical of unsaturated monobasic acids used to obtain the epoxy vinyl ester resin (A) are acrylic acid, methacrylic acid, cinnamic acid, crotonic acid, monomethyl maleate, monopropyl maleate. , Monobutylmalate, sorbic acid, mono (2-ethylhexyl) malate, etc., and these can be used alone or in a mixture of two or more kinds.

 Further, when obtaining the epoxy vinyl ester resin (A), a polymerization inhibitor is used for the purpose of preventing gelation during the reaction and adjusting the storage stability or curability of the product. Is recommended.

 Typical examples of such a polymerization inhibitor include hydroquinones such as hydroquinone, pt-butylcatechol and mono-t-butylhydroquinone; phenols such as hydroquinone monomethyl ether and di-t-p-cresol; There are quinones such as p-benzoquinone, naphthoquinone and p-toluquinone; or copper salts such as copper naphthenate.

 The epoxy vinyl ester resin (A) may be used by dissolving it in a solvent of ketones or esters, but it is preferable to use only the polymerizable vinyl monomer (E). Examples of the polymerizable vinyl monomer in this case include styrene and its derivatives such as styrene, vinyltoluene, t-butylstyrene, chlorostyrene or divinylbenzene; ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl ( (Meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, 2-hydroxyethyl (meth) acrylate or 2-hydroxypropyl (meth) Low-boiling ester monomers of (meth) acrylic acid such as acrylate; or trimethylolpropane tri (meth) acrylate, diethylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate Examples include poly (alcohol) (meth) acrylates such as relate or 1,6-hexanedioldi (meth) acrylate. Among them, styrene, vinyltoluene, and (meth) acrylic acid have low boiling points because of their low viscosity. Ester monomers are preferred.

 Typical examples of the polybasic acid anhydride (B) used in the present invention include phthalic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methylhexahydrophthalic anhydride and methyltetrahydrophthalic anhydride. , Nadic anhydride, methyl nadic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, succinic anhydride, itaconic anhydride, citraconic anhydride, dodecenyl succinic anhydride, chlorendic anhydride, benzophenone anhydride Tetracarboxylic acid, cyclopentatetracarboxylic acid anhydride, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid, ethylene glycol bis trimellitate anhydride or glycerin trimellitate anhydride Etc., these are single or two Used in the above mixture. Preferred examples include liquid acid anhydrides such as methylhexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, and methylnadic acid anhydride. Among them, thermosetting resin compositions having excellent storage stability are particularly preferable. Methylhexahydrophthalic anhydride is particularly preferable in that it can be obtained. Further, a solid acid anhydride such as 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid dissolved in a liquid acid anhydride is also preferably used. To be

 Examples of the polymerization initiator (C) used in the present invention include cyclohexanone peroxide, 3,3,5-trimethylcyclohexanone peroxide, methylonexanone peroxide, and 1,1-bis (t-butylperoxy). 3,3,5-Trimethylcyclohexane, cumene hydroperoxide, dicumyl peroxide, lauroyl peroxide, 3,3,5-trimethylhexanoyl peroxide, benzoyl peroxide, di-myristyl peroxydicarbonate, t- Examples thereof include organic peroxides such as butylperoxy (2-ethylhexanoate), t-butylperoxy-3,3,5-trimethylhexanoate, t-butylperoxybenzoate, cumylperoxyoctate.

 Examples of the latent curing accelerator (D) used in the present invention include (a) a frozen latent curing accelerator obtained by mixing an epoxy resin and an amine compound and immediately freezing to stop the reaction. A microcapsule type latent curing accelerator in which an amine compound is microencapsulated, (c) a monocular sieve type latent curing accelerator in which a compound is adsorbed to a monocular sieve, and (d) an amine compound and an epoxy group. The latent curing accelerators are listed even though they are surface-treated with a compound having an isocyanate group as an adduct with a compound that has a compound, and among them, they are easy to handle and have high workability. The latent curing accelerator (d) above is particularly preferable because it does not deteriorate the physical properties.

 Examples of the amine compound used to obtain the latent curing accelerator of (d) above include aliphatic amines such as ethylene diamine, diethylene triamine, triethylene tetramine, tetraethylene pentamine, dipropylene diamine, and diethylaminopropyl amine. , Menthenediamine, isophoronediamine, bis (4-amino-3-methylcyclohexyl) methane, alicyclic amines such as N-aminoethylpiperazine, and aromatic rings such as meta-xylenediamine and tetrachloro-p-xylenediamine Aliphatic amines such as aliphatic amines, metaphenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, and bisaminomethyldiphenylmethane, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-undecylamine. Imidazole, 2-heptadecyl imidazole, 2-phenyl imidazole, 1-benzyl-2-methyl imidazole, 1-cyanoethyl-2-methyl imidazole, 1-cyanoethyl-2-ethyl-4-methyl imidazole and other imidazole compounds The thing etc. are mentioned.

 As the compound having an epoxy group, any compound having one or more epoxy groups can be used. For example, a monoepoxy compound such as an aliphatic glycidyl ether, an aromatic glycidyl ether, a glycidyl alkylate, the above-mentioned epoxy resin and the like. Among them, solventless liquid or solid epoxy resin is preferable.

 The adduct of the amine compound and the epoxy compound can be obtained, for example, by a conventionally known general method.

The reaction ratio of the amine compound and the epoxy compound is such that the number of epoxy groups is 1.0 to 1.5, preferably 1.2 to 1.4 per active hydrogen of the amine compound. Is. The addition reaction may be carried out without a solvent, but a method in which an amine compound is dissolved in an appropriate solvent and an epoxy compound is added dropwise or dividedly is usually used. The solvent is preferably an aromatic solvent or a ketone solvent, and examples thereof include toluene, xylene, methyl ethyl ketone, and methyl isobutyl ketone. When the addition reaction is carried out without solvent, the obtained adduct is crushed to the required particle size before use. When the addition reaction is carried out in a solvent, after completion of the reaction, a method of spray-drying by a spray drying method, a method of removing the solvent and pulverizing, etc. are adopted. The particle size is usually 30 μm or less, preferably 0.1 to 10 μm, particularly preferably 1 to 6 μm.

If the thickness is 30 μm or more, the dispersibility tends to occur.

 Further, as the compound having an isocyanate group, for example, an aromatic or aliphatic monoisocyanate, an aromatic or aliphatic polyisocyanate, a polyisocyanate which is an adduct of polyol and polyisocyanate, or a reaction of polyisocyanate and water is obtained. Examples thereof include buret type polyisocyanate and cyclopolymerization type polyisocyanate. Specific examples thereof include monoisocyanate compounds such as phenyl isocyanate and tolyl isocyanate, tetramethylenediisocyanate, hexamethylene diisocyanate, tolylene diisocyanate and xylylene diisocyanate. , Diphenylmethane diisocyanate, isopropylidene cyclohexyl isocyanate, lysine isocyanate, tolylene diisocyanate and trimethylolpropane Additives, tolylene diisocyanate and pentaerythritol adducts, tolylene diisocyanate and polyethylene glycol adducts, tolylene diisocyanate and polypropylene glycol adducts, and polyisocyanate compounds such as hexamethylene diisocyanate and polyethylene adipate prepolymers. Can be mentioned. Of these, aromatic or aliphatic polyisocyanates and polyisocyanates, which are adducts of polyols and polyisocyanates, are preferred.

 The method of surface-treating an adduct of an amine compound and an epoxy compound with a compound having an isocyanate group is not particularly limited, but for example, a powdery solvent that does not dissolve the above-mentioned adduct, such as toluene, xylene, acetone, methyl ethyl ketone. First, a compound having a predetermined amount of an isocyanate group is dissolved therein, and then the above-mentioned powdery adduct is dispersed therein, followed by surface treatment, and then the solvent is scattered and dried. . The amount of the compound having an isocyanate group used is usually 0.5 to 20 parts by weight, preferably 0.0 to 10 parts by weight, based on 100 parts by weight of the adduct.

 The thermosetting resin composition (I) of the present invention means that each of the components (A) to (D) is used as an essential component, and if necessary, a polymerizable vinyl monomer (E), another solvent, and Means a composition containing additives such as an internal mold release agent, a pigment, a filler, etc., which can be impregnated into a fibrous base material. The solid component does not necessarily have to be dissolved or melted in the liquid component during impregnation and may be used in the form of powder dispersed in the liquid component.

 The amount of the polymerization initiator (C) added is usually 0.1 to 5 parts by weight, preferably 0.5 to 3 parts by weight, based on 100 parts by weight of the epoxy vinyl ester resin (A).

 Further, the addition amount of the latent curing accelerator (D) is usually 0.1 to 10 parts by weight, preferably 0.5 to 5 parts by weight, based on 100 parts by weight of the polybasic acid anhydride (B). .

 The filler added as necessary to the thermosetting resin composition (I) of the present invention is appropriately selected depending on the required performance and working conditions, and examples thereof include aluminum hydroxide, aluminum silicate, Examples include colloidal silica, calcium carbonate, calcium sulfate, mica, talc, titanium dioxide, quartz powder, zirconium silicate, glass powder, asbestos powder, diatomaceous earth, and antimony trichloride.

 There are no particular restrictions on the mixing method and mixing order of the components when obtaining the thermosetting resin composition (I) of the present invention, but after mixing the liquid components, the solid components are mixed. A method of adding in powder form and causing decomposition or dissolution is preferable.

 On the other hand, typical examples of the fibrous base material used in the present invention include glass fibers, carbon fibers and aromatic polyamide fibers, and of these, glass fibers are preferable. Among these, glass fibers include E-glass, C-glass, A-glass, S-glass, etc. from the viewpoint of their raw materials, but in the present invention, any type is applicable. it can.

 These fibrous base materials include roving, chopped strand mat, continuous mat, cloth, non-woven fabric, roving cloth, surfacing mat, and chopped strand depending on their shape. It may be appropriately selected depending on the intended use and performance of the molded product, and if necessary, a mixture of two or more kinds or shapes may be used. Of these, cloth and non-woven fabric are preferable.

 As a method for obtaining a laminate using the thermosetting resin composition (I) of the present invention, for example, a fibrous base material is impregnated with the curable resin composition (I), and a predetermined number of layers are superposed. A method of covering both the upper and lower sides with a metal foil and / or a cover film, preheating as needed, and then applying a heating effect, impregnating the fibrous base material with the thermosetting resin composition (I), and drying. A method may be mentioned in which a polymerizable vinyl monomer is removed in a furnace to be B-staged, and then a predetermined number of the B-staged products are superposed, followed by heating and curing.

The heat curing in the above may be carried out without pressure in a continuous heating furnace, or may be continuously heated and pressed by a continuous double belt press. Alternatively, the pre-heated laminate or the B-staged B-staged product may be cut and heat-press molded by batchwise. The preheating and the B-staging are usually carried out in the temperature range of 70 to 150 ° C, and both of the heat curing are carried out at 130 to 190 ° C. The heat and pressure molding is usually performed under a pressure of 5 to 40 kg / cm ² .

<Example> Next, the present invention will be described more specifically with reference to production examples, examples and comparative examples. All parts and% in the examples are by weight unless otherwise specified.

Production Example 1 [Production of Epoxy Vinyl Ester Resin (A)] Obtained by reacting 273 parts of epoxy resin having an epoxy equivalent of 190 obtained by reaction of bisphenol A and epichlorohydrin with tetrabromobisphenol A and epichlorohydrin. Epoxy equivalent 370 parts of epoxy resin 582 parts, methacrylic acid 107 parts, hydroquinone 0.3 parts and triphenylphosphine 0.4 parts are reacted at 110 ° C. until the acid value reaches 0.2, and then reacted. It was diluted and dissolved with a ethylene monomer to obtain an epoxy vinyl ester resin (A-1) having a resin content of 80% and an epoxy equivalent of 670.

Production Example 2 [Same as above] An epoxy vinyl ester resin (A-2) having a resin content of 80% and an epoxy equivalent of 460 was used in the same manner as in Production Example 1 except that the amount of methacrylic acid used was changed to 54 parts. Obtained.

Production Example 3 [Same as above] Except that 0.4 part of triphenylphosphine was used in place of 0.4 part of triphenylphosphine, the same procedure as in Production Example 1 except that the resin content was 80% and the epoxy equivalent was 665. An epoxy vinyl ester resin (A-3) was obtained.

Production Example 4 [Same as above] Epoxy vinyl ester resin having a resin content of 80% and an epoxy equivalent of 670 in the same manner as in Production Example 1 except that 0.4 part of triphenylphosphine was used instead of 0.4 part of triphenylphosphine. (A-4) was obtained.

Production Example 5 [Production of Latent Curing Accelerator (D)] An epoxy resin having an epoxy equivalent of 190 obtained by the reaction of bisphenol A and epichlorohydrin and 2-methylimidazole are added in xylene at 120 ° C. for 1.5 times. The reaction was carried out for a time to obtain an adduct (reaction mole ratio 1: 2), the solvent was separated, and the product was further dried. Then, it was pulverized to obtain a powder having an average particle size of 4.0 μm.

 100 parts of this powder was dispersed in 250 parts of hexane, 3 parts of xylylene diisocyanate was added with heating and stirring at 60 ° C., stirring was continued for 1 hour, followed by filtration, drying under reduced pressure and surface-treated curing. The accelerator (D-1) was obtained.

Examples 1 to 5 and Comparative Examples 1 to 2 Thermosetting resin compositions (I-1) to (I-5) and (I'-1) to (I'-2) were prepared according to the formulations shown in Table 1. Prepared.

Then, immediately, each of the above resin compositions (I-1) to (I-5) and (I'-1) to (I'-2) was formed into a long glass cloth having a thickness of 0.18 mm and a width of 1050 mm. The resin composition was impregnated so that the content rate was 45%, 8 pieces each were laminated, and 35 μm-thick copper foils were stacked on top of each other and heated in a heating furnace at 110 ° C. for 4 minutes. While carrying it out, and then press-molding it with a double belt press machine heated to 170 ° C for 10 minutes at a pressure of 20 kg / cm ² , cut it into 1000 mm × 1000 mm, and then post-cure at 170 ° C for 50 minutes. 20 sheets of each of laminated plates (II-1) to (II-5) and (II'-1) to (II'-2) having a thickness of 1.6 mm were obtained.

 Furthermore, after the preparation, the thermosetting resin compositions (II-1) to (II-5) and (II'-1) to (II'-) were left to stand at room temperature for 10 hours in a sealed state so as not to absorb moisture. Twenty laminated plates (III-1) to (III-5) and (III'-1) to (III'-2) were obtained in the same manner as above except that 2) was used.

 Then, the obtained laminated plates (II-1) to (II-5), (II'-1) to (II'-2), (III-1) to (III-5) and (III'-1). ) To (III′-2) were used to measure the resin outflow rate, water absorption rate and solder heat resistance during molding in the following manner. The laminated plates (II-1) to (II-1) obtained in Example 1 II-5) and (III-1) to (III-5) show no significant difference in the measurement results, indicating that the thermosetting resin compositions of Examples 1 to 5 have excellent storage stability. However, the laminated plates (II′-1) to (II′-2) and (III′-1) to (III′-2) obtained in Comparative Examples 1 and 2 showed a large difference in the measurement results. Therefore, it was confirmed that the thermosetting resin compositions of Comparative Examples 1 and 2 were inferior in storage stability.

 The measurement results are shown in Table 2.

The resin outflow rate (%) = (W ₀ −W ₁ ) / W ₀ × 100, and the average value was shown.

(W ₀ is the weight of 8 resin-impregnated base materials having a resin composition content of 45% and dimensions of 1000 mm × 1000 mm, W ₁ is a copper foil from a laminate of dimensions 1000 mm × 1000 mm obtained by heat and pressure molding. Water absorption rate (%): Water absorption (%): After cutting the copper foil on one side of the laminated plate cut into 25 mm x 50 mm by etching, a pressure cooker test is performed at 120 ° C and 2 atm for 4 hours. The water absorption rate was calculated based on the following formula and shown as an average value.

(W is the weight of the laminate before the test, and W'is the weight of the laminate after the test.) ・ Solder heat resistance: After wiping off the moisture on the surface of the laminate after the pressure cooker test, JIS It was measured according to C-6481 and evaluated according to the following criteria.

◯: No sample with poor solder heat resistance.

Δ: There is less than 1/4 of the sample with poor solder heat resistance.

X: There are 1/4 or more samples with poor solder heat resistance.

<Effects of the Invention> The use of the thermosetting resin composition of the present invention has the advantage that a long-term impregnation operation can be performed, water-absorbing properties and solder heat resistance are excellent, and a laminated plate with little variation can be obtained. is there.

 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Munekazu Hayashi 4-3-5-2-511 Chiba, Chiba City, Chiba Prefecture (72) Inventor Satoshi Demura 4-4 Tatsumidai Higashi, Ichihara City, Chiba Prefecture

Claims (12)

[Claims] 1. An epoxy resin and an unsaturated monobasic acid, wherein the number of carboxyl groups in the unsaturated monobasic acid is 0.05 to 0.6 with respect to one epoxy group in the epoxy resin. Containing an epoxy vinyl ester resin (A), a polybasic acid anhydride (B), a polymerization initiator (C), and a latent curing accelerator (D). A thermosetting resin composition comprising: 2. The latent curing accelerator (D) is obtained by surface-treating an adduct of an amine compound and a compound having an epoxy group with a compound having an isocyanate group. Composition. 3. The epoxy vinyl ester resin (A) is
It is obtained by reacting an epoxy resin with an unsaturated monobasic acid in the presence of an esterification catalyst that does not promote the reaction between the epoxy vinyl ester resin (A) and the polybasic acid anhydride (B). The composition according to claim 1 or 2. 4. The composition according to claim 3, wherein the esterification catalyst is a phosphine derivative. 5. The composition according to claim 1, wherein the polybasic acid anhydride (B) is methylhexahydrophthalic anhydride. 6. The composition according to claim 5, which is a liquid resin composition further containing a polymerizable vinyl monomer (E) as a reactive diluent and containing no solvent other than the polymerizable vinyl monomer. 7. An epoxy resin and an unsaturated monobasic acid, wherein the number of carboxyl groups in the unsaturated monobasic acid is 0.05 to 0.6 per epoxy group in the epoxy resin. Containing an epoxy vinyl ester resin (A), a polybasic acid anhydride (B), a polymerization initiator (C), and a latent curing accelerator (D). A method for producing a laminated plate, comprising impregnating a fibrous base material with the thermosetting resin composition (I), and then heating and curing the same. 8. The latent curing accelerator (D) is obtained by surface-treating an adduct of an amine compound and a compound having an epoxy group with a compound having an isocyanate group. Manufacturing method. 9. The epoxy vinyl ester resin (A) comprises:
It is obtained by reacting an epoxy resin with an unsaturated monobasic acid in the presence of an esterification catalyst that does not promote the reaction between the epoxy vinyl ester resin (A) and the polybasic acid anhydride (B). The method according to claim 7 or 8. 10. The method according to claim 9, wherein the esterification catalyst is a phosphine derivative. 11. The method according to claim 7, 8, 9 or 10, wherein the polybasic acid anhydride (B) is methylhexahydrophthalic anhydride. 12. The method according to claim 11, which is a liquid resin composition further containing a polymerizable vinyl monomer (E) as a reactive diluent and containing no solvent other than the polymerizable vinyl monomer.