JPH0532765A - Epoxy resin composition and production of laminate - Google Patents

Abstract

PURPOSE:To provide a curable unsaturated resin composition giving fibrous substrates having excellent interlaminar separation strength. CONSTITUTION:The epoxy resin composition comprises a bisphenol type epoxy resin, a tetrabromobisphenol A type epoxy resin, hexahydrophthalic anhydride, a compound having an esteramide group and a methacryloyl group and produced by reacting 2,2-m-phenylene bis(2-oxazole) with methacrylic acid, and styrene. Glass fiber substrates are impregnated with the epoxy resin composition, piled up each other and subsequently thermally cured to form a laminate, which is improved in the interlaminar separation strength, chemical resistance and soldering resistance.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a process for producing a laminate having excellent fibrous base material delamination strength and chemical resistance, and an epoxy resin composition suitable for use in the process.

[0002]

2. Description of the Related Art A glass epoxy resin-based laminate used as a printed circuit board is manufactured by heating and pressurizing after passing through a B-staged prepreg.
It is known that a polybasic acid anhydride having excellent heat resistance and electrical characteristics is used as an epoxy resin curing agent.

Since the above heat and pressure molding requires a long time and there is a problem in productivity, a resin having an ethylenically unsaturated double bond and a polymerization initiator are added to the epoxy resin and the curing agent for the epoxy resin. In addition, a method for producing a prepreg with improved moldability has been proposed (Japanese Patent Laid-Open No. 62-285929).

[0004]

However, although the prepreg obtained in the above method has a high curability,
Regarding the physical properties of the laminate of the final cured product, there is a problem that the delamination strength and chemical resistance are not sufficient.

[0005]

Means for Solving the Problems As a result of intensive studies conducted by the present inventors in view of such circumstances, as a result, an epoxy resin composition containing an esteramide group and a compound (C) having an ethylenically unsaturated double bond. It was found that a laminate having excellent delamination strength and excellent chemical resistance can be obtained by using, and the present invention has been completed.

That is, the present invention is based on the epoxy resin (A).
And a polybasic acid anhydride (B) and a compound (C) having an ester amide group and an ethylenically unsaturated double bond, and an epoxy resin composition (I) and an epoxy resin (A ), A polybasic acid anhydride (B), and a compound (C) having an ester amide group and an ethylenically unsaturated double bond as a fibrous base material (II). It is intended to provide a method for producing a laminated plate, which is characterized by being impregnated and cured.

Epoxy resin composition (I) used in the present invention
As the epoxy resin (A) and polybasic acid anhydride (B)
And a compound (C) having an ester amide group and an ethylenically unsaturated double bond as essential components, usually a polymerization initiator, and if necessary, other curing agent, other resin, polymerizable vinyl monomer, etc. A liquid composition containing the solvent, the filler, the curing accelerator, the additive and the like.

The epoxy resin (A) used here is, for example, an epoxy resin obtained from epichlorohydrin or β-methylepichlorohydrin and bisphenol A, tetrabromobisphenol A, bisphenol F or bisphenol S; phenol or alkylphenol novolac. Resin polyglycidyl ethers; polyglycols of ethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol, neopentyl glycol, glycerin, trimethylolethane, trimethylolpropane or polyhydric alcohols such as ethylene oxide or propylene oxide adduct of bisphenol A Glycidyl ethers; polycarbohydrates such as adipic acid, phthalic acid, hexahydrophthalic acid or dimer acid Polyglycidyl esters of acids; cyclohexene-based epoxy compounds (3,4-epoxy-6-methyl-cyclohexyl-3,4-epoxy-6-) obtained by epoxidizing cyclohexene or a derivative thereof with peracetic acid and the like. Methylcyclohexanecarboxylate, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 1-epoxyethyl-3,4-epoxycyclohexane, etc.), cyclopentadiene or dicyclopentadiene or their derivatives, and peracetic acid, etc. Cyclopentadiene-based epoxy compounds (cyclopentadiene oxide, obtained by epoxidation with
Dicyclopentadiene oxide, 2,3-epoxycyclopentyl ether, etc.), limonenedioxide, diglycidyl ether of tetrabromobisphenol A, glycidyl ether ester of hydroxybenzoic acid, etc., but among them, average epoxy equivalent by itself. Is preferably in the range of 100 to 400, or a mixture of two or more kinds appropriately combined to have an epoxy equivalent of this range, and a solvent-free liquid form at room temperature. .

Examples of the polybasic acid anhydride (B) used in the present invention include phthalic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, nadic acid anhydride, Methyl nadic acid anhydride, trimellitic acid anhydride, pyromellitic acid anhydride, maleic acid anhydride, succinic acid anhydride, itaconic acid anhydride, citraconic acid anhydride, dodecenyl succinic acid anhydride, chlorendic acid anhydride, benzophenone tetracarboxylic acid anhydride, cycloanhydride Pentatetracarboxylic acid, 5- (2,5-dioxotetrahydrofuryl)-
3-methyl-3-cyclohexene-1,2-dicarboxylic acid, ethylene glycol bis trimellitate anhydride, glycerin trimellitate anhydride and the like can be mentioned.
These may be used alone or in the form of a mixture of two or more. Among them, liquid divalent carboxylic acid anhydrides such as methylhexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, and methylnadic nadic acid anhydride are preferable, and an epoxy resin composition having particularly excellent storage stability can be obtained. Phthalic anhydride is most preferred. If necessary, the polybasic acid anhydride (B) may be used in combination with other epoxy resin curing agents.

The composition of the present invention is characterized in that a compound having an ester amide group and an ethylenically unsaturated double bond is added to the composition containing the epoxy resin (A) and the polybasic acid anhydride (B) as essential components. It is contained.

As the compound (C) having an esteramide group and an ethylenically unsaturated double bond of the present invention, any one having an esteramide group and an ethylenically unsaturated double bond in one molecule is preferable. Can also be used [hereinafter, simply referred to as compound (C). ].

This compound (C) can be obtained, for example, by reacting a compound having one or more oxazoline rings with an unsaturated monobasic acid, or from a compound having at least two oxazoline rings and a polyvalent phenol compound to the terminal. Method of obtaining an adduct having an oxazoline ring and then reacting with an unsaturated monobasic acid, obtaining an adduct having an oxazoline ring at the end from a compound having at least two oxazoline rings and a polybasic acid, and then unsaturated monobasic A method of reacting an acid,
Etc. Of these methods and methods are effective methods for obtaining the above-mentioned compound having a high molecular weight.

The compounds having one oxazoline ring include 2-vinyl-2-oxazoline and 2-vinyl-4-.
Methyl-2-oxazoline, 2-vinyl-5-methyl-
2-oxazoline, 2-vinyl-4-ethyl-2-oxazoline, 2-vinyl-5-ethyl-2-oxazoline, 2-isopropenyl-2-oxazoline, 2-isopropenyl-4-methyl-2-oxazoline, 2-isopropenyl-5-methyl-2-oxazoline, 2-isopropenyl-4-ethyl-2-oxazoline, 2-isopropenyl-5-methyl-2-oxazoline, 2-isopropenyl-4,5-dimethyl- 2-oxazoline etc. are mentioned.

The compound having at least two oxazoline rings is, for example, 2,2'-o-phenylenebis (2-oxazoline), 2,2'-m-phenylenebis (2-oxazoline), 2, 2'-p-phenylenebis (2-oxazoline), 2,2'-p-phenylenebis (4-methyl-2-oxazoline), 2,2'-
p-phenylene bis (4,4-dimethyl-2-oxazoline), 2,2′-m-phenylene bis (4-methyl-)
2-oxazoline), 2,2'-m-phenylenebis (4,4-dimethyl-2-oxazoline), 2,2'-
(1,2-ethylene) -bis (2-oxazoline),
2,2 '-(1,4-butylene) -bis (2-oxazoline) and the like can be mentioned.

Typical unsaturated monobasic acids used together with the compound having one or more oxazoline rings to obtain the compound (C) according to the present invention include acrylic acid, methacrylic acid, cinnamic acid, There are crotonic acid, monomethylmalate, monopropylmalate, monobutylmalate, sorbic acid or mono (2-ethylhexyl) malate, and these can be used alone or in a mixture of two or more kinds. At this time, the compound having one or more oxazaline rings and the unsaturated monobasic acid react with each other in the temperature range of 50 to 200 ° C. to form an ester amide group even in the absence of a catalyst. Usually, the reaction ratio of the compound having one or more oxazoline rings and the unsaturated monobasic acid is such that the carboxyl group of the unsaturated monobasic acid is 0.
5 to 2.5, preferably 1 oxazoline ring
The number of unsaturated monobasic acid carboxyl groups is 2.0.

Typical examples of the polyvalent phenol compounds used together with the compound having at least two oxazoline rings to obtain the compound (C) according to the present invention include catechol, resorcinol and hydroquinone. , Bisphenol A, bisphenol F, brominated bisphenol A, phenol novolac resin, cresol novolac resin, bisphenol A novolac resin and the like. The reaction between the compound having at least two oxazoline rings and the polyvalent phenol compound is carried out in the temperature range of 50 to 200 ° C. even in the absence of a catalyst, and the oxazoline ring is added to the hydroxyl group of the polyvalent phenol compound. React in an excess state to form an ester amide group. Preferably, the ratio of the compound having at least two oxazoline rings and the polyvalent phenol compound used is 2
It is the ratio of one hydroxyl group of the polyvalent phenol compound to the number. At least 2 oxazoline rings thus obtained
A reaction product of a compound having an individual and a polyvalent phenol compound,
Further, it is reacted with an unsaturated monobasic acid in the temperature range of 50 to 200 ° C. without a catalyst to form a compound having an esteramide group and an ethylenically unsaturated double bond. In that case, the ratio of the reaction product of the compound having at least two oxazoline rings and the polyvalent phenol compound and the unsaturated monobasic acid is such that the carboxyl group of the unsaturated monobasic acid is 0.5 per one oxazoline ring. However, the number of carboxyl groups of unsaturated monobasic acid is 2.0 per one oxazoline ring.

Further, typical polybasic acids used together with the compound having at least two oxazoline rings to obtain the compound (C) according to the present invention include fumaric acid, adipic acid, sebacic acid and dimer acid. , Polyphthalic acid such as isophthalic acid, terephthalic acid, trimellitic acid and pyromellitic acid, and hydrates of the above polybasic acid anhydride (B). These may be used alone or in admixture of two or more. To use. The reaction of the compound having at least two oxazoline rings with the polybasic acid is carried out in the temperature range of 50 to 200 ° C. even in the absence of a catalyst, and in the state where the oxazoline ring is excessive with respect to the carboxyl group of the polybasic acid. Let
Generate an ester amide group. Preferably, the compound having at least two oxazaline rings and the polybasic acid are used in a ratio of one carboxyl group of the polybasic acid to two oxazoline rings. The thus obtained reaction product of a compound having at least two oxazoline rings and a polybasic acid is further reacted with an unsaturated monobasic acid in the temperature range of 50 to 200 ° C. without a catalyst to produce an ester amide group and an ethylenically unsaturated dicarboxylic acid. A compound having a heavy bond is formed. At that time, the ratio of the reaction product of the compound having at least two oxazoline rings and the polybasic acid and the unsaturated monobasic acid is such that the carboxyl group of the unsaturated monobasic acid is 0.5 to 1 to one oxazoline ring.
The number of the compounds is 2.5, but preferably, when the above compound (C) is obtained in which one oxazoline ring has 2.0 carboxyl groups of unsaturated monobasic acid, it is not suitable for the raw materials as shown above. In the case of reacting with a saturated monobasic acid, hydroquinones such as hydroquinone, pt-butylcatechol, and mono-t-butylhydroquinone; hydroquinone monomethyl ether, di-t-
It is preferable to add a polymerization inhibitor such as phenols such as p-cresol; quinones such as p-benzoquinone, naphthoquinone and p-toluquinone; or copper salts such as copper naphthenate.

The ratio (X) / (Y) of the amount (X) of the compound (C) used and the sum (Y) of the weights of the epoxy resin (A) and the polybasic acid anhydride (B) is 2 / The range of 98 to 70/30 is usually used, but among them, 95/5 to 5 in terms of obtaining a laminated plate excellent in both delamination strength and heat resistance.
The range of 0/50 is preferable. As will be described later, when the resin (E) having an ethylenically unsaturated double bond other than the compound (C) is further used in combination, the weight (Z) of the resin (E) and the amount of the compound (C) used. Ratio ((X) + (Z)} of sum of weights of (X) {(X) + (Z)} and sum of weights of epoxy resin (A) and polybasic acid anhydride (B) (Y) {(X) + (Z)}.
/ (Y) is usually in the range of 2/98 to 70/30, but in particular, it is in the range of 95/5 to 50/50 from the viewpoint that a laminate having excellent delamination strength and heat resistance can be obtained. Is preferred.

Epoxy resin composition (I) of the present invention
Is an epoxy resin (A), a polybasic acid anhydride (B),
As long as it contains the compound (C) as an essential component,
Further, a radical polymerization initiator is usually used to accelerate the polymerization of the compound (C).

Examples of the radical polymerization initiator (D) 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,
5,5-Trimethylhexanoyl peroxide, benzoyl peroxide, di-myristyl peroxydicarbonate, t-butyl peroxy (2-ethyl hexanoate), t-butyl peroxy-3,5,5-trimethyl hexa Examples thereof include organic peroxides such as noate, t-butyl peroxybenzoate, cumyl peroxy octoate.

The mixing method and mixing order of the respective components for obtaining the epoxy resin composition (I) are not particularly limited, but after mixing the liquid components, the solid components are added in powder form. The method of dispersing or dissolving is preferable.

Epoxy resin composition (I) used in the present invention
It is preferable that the resin further contains a resin (E) having an ethylenically unsaturated double bond other than the compound (C). Typical examples of the resin (E) used here include an epoxy vinyl ester resin obtained by an esterification reaction of an epoxy resin with an unsaturated monobasic acid, a dibasic acid containing an unsaturated dibasic acid, and a polybasic acid. There are unsaturated polyester resins obtained by reaction with alcohols, allyl resins such as prepolymers of diallyl phthalate, and the like, and epoxy vinyl ester resins are preferable from the viewpoint of adhesion to metal foil. In the preparation of these resins, the same polymerization inhibitors as described above are used, if necessary, for the purpose of preventing gelation during resin preparation and for adjusting the storage stability or curability of the produced resin.

If necessary, these resins (E) thus obtained contain known solvents and polymerizable vinyl monomers, for example, styrene such as styrene, vinyltoluene, t-butylstyrene, chlorostyrene or divinylbenzene and derivatives thereof. Ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate,
Low boiling point ester monomers of (meth) acrylic acid such as isobutyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, 2-hydroxyethyl (meth) acrylate or 2-hydroxypropyl (meth) acrylate. Or a (meth) polyhydric alcohol such as trimethylolpropane tri (meth) acrylate, diethylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate or 1,6-hexanediol di (meth) acrylate A stable resin solution is obtained by dissolving it in acrylates and the like. Among them, styrene, because of its low viscosity,
Vinyltoluene and low-boiling ester monomers of (meth) acrylic acid are preferred.

Epoxy resin composition (I) used in the present invention
It is preferable to add a known and commonly used curing accelerator for epoxy resin, and a latent curing accelerator that exhibits an accelerating function at a temperature of 50 ° C. or higher is particularly preferable.

If desired, a filler may be added to the epoxy resin composition (I), which is appropriately selected depending on the required performance and working conditions.
Examples include aluminum hydroxide, aluminum silicate, colloidal silica, calcium carbonate, calcium sulfate, mica, talc, titanium dioxide, quartz powder, zirconium silicate, glass powder, asbestos powder, diatomaceous earth, and antimony trioxide. is there.

On the other hand, the fibrous base material (II) used in the present invention
Examples thereof include pulp, glass fiber, carbon fiber, aromatic polyamide fiber, and the like, and among them, glass fiber is preferable. Among these, glass fibers include E-glass, C-glass, A-glass and S-glass from the viewpoint of their raw materials.
Although there are glasses and the like, any kind of glass can be applied in the present invention.

These fibrous base materials (II) include rovings, chopped strand mats, continuous mats, cloths, non-woven fabrics, roving cloths, surfacing mats and chopped strands, depending on their shapes. Is appropriately selected depending on the intended use and performance of the molded product, and may be a mixed use of two or more kinds or shapes if necessary. Of these, cloth and non-woven fabric are preferable.

As a method for obtaining a laminate using the epoxy resin composition (I), for example, a fibrous base material is impregnated with the epoxy resin composition (I),
Laminate a specified number of sheets, and further top and bottom metal foil and /
Alternatively, a method of covering with a cover film, preheating by heating or irradiation with active energy rays, etc., if necessary, and then heat curing, impregnating a fibrous base material with the epoxy resin composition (I),
Examples thereof include a method in which the polymerizable vinyl monomer is removed in a drying furnace to be B-staged, and then a predetermined number of the B-staged products are superposed and heat-cured. When the active energy ray is ultraviolet ray, a known and conventional photopolymerization initiator is usually added.

The above-mentioned heat curing may be carried out in a continuous heating furnace without pressure, or may be continuously heated and pressed by a continuous double belt press. Alternatively, the pre-heated laminated body or the B-staged B-staged product may be cut and heat-press molded by batchwise. Pre-heating and B-staging of
Usually, it is carried out in the temperature range of 70 to 150 ° C, and both of the heat curing are carried out at 100 to 190 ° C. The heat and pressure molding is usually performed at a pressure of 5 to 40 kg / cm ² . Of course, these conditions are merely examples, and the present invention is not limited to these conditions.

The epoxy resin composition (I) of the present invention is not limited to the use of a laminated board, but may be used in, for example, paints, adhesives, sealants, insulating varnishes, castings, fiber reinforced plastics and the like. Also used.

[0031]

EXAMPLES 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 Compound (C)] 2,2′-m-phenylene bis (2-oxazole) 5
46 parts and 172 parts of methacrylic acid are reacted at 100 ° C. for 8 hours in the presence of 0.25 part of hydroquinone, diluted and dissolved with 425 parts of styrene, and each has two ester amide groups and two methacryloyl groups. Compound (C-
1) was obtained. Production Example 2 [Same as above] 2,2′-m-phenylenebis (2-oxazole) 4
35 parts and 233 parts of bisphenol A are reacted at 150 ° C. for 10 hours to obtain an adduct having oxazoline rings at both ends, and then 172 parts of methacrylic acid and 0.25 part of hydroquinone are added thereto, and further at 100 ° C. The mixture was reacted for 10 hours, diluted with 364 parts of styrene and dissolved to obtain a compound (C-2) having an esteramide group and a methacryloyl group at both ends. Production Example 3 [Same as above] 2,2′-p-phenylene bis (2-oxazole) 4
35 parts and 23 parts of bisphenol A are reacted at 170 ° C. for 8 hours to obtain an adduct having oxazoline rings at both ends, and then 172 parts of methacrylic acid and 0.25 part of hydroquinone are added thereto, and the mixture is further added at 100 ° C. for 10 hours. The mixture is allowed to react for a time, diluted and dissolved with 364 parts of styrene, and a compound having an ester amide group and a methacryloyl group at both ends (C
-3) was obtained. Production Example 4 [Same as above] 2,2′-m-phenylene bis (2-oxazole) 4
35 parts and orthocresol novolac resin (melting point: 6
(0 ° C.) 223 parts are reacted at 150 ° C. for 10 hours to obtain an adduct having a terminal oxazoline ring. Then, 172 parts of methacrylic acid and 0.25 part of hydroquinone are added thereto, and the mixture is further reacted at 100 ° C. for 10 hours. , Styrene 364
Partially dissolved to obtain a compound (C-4) having an ester amide group and a methacryloyl group. Production Example 5 [Same as above] 2,2′-m-phenylene bis (2-oxazole) 4
35 parts and 111 parts of resorcinol were reacted at 150 ° C. for 10 hours to obtain an adduct having both-end oxazoline rings, and then 172 parts of methacrylic acid and 0.25 part of hydroquinone were added thereto, and further at 100 ° C. The mixture is reacted for 10 hours, diluted with 304 parts of styrene and dissolved to dissolve the compound having an ester amide group and a methacryloyl group at both ends (C-
5) was obtained. Production Example 6 [Same as above] 100 parts of 2-vinyl-2-oxazoline and 172 parts of methacrylic acid were reacted at 100 ° C. for 8 hours in the presence of 0.096 parts of hydroquinone, and diluted with 29 parts of styrene to dissolve. A compound (C-6) having one ester amide group and one ethylenically unsaturated double bond was thus obtained. Production Example 7 [same as above] 98 parts of maleic anhydride and 18 parts of water were reacted at 100 ° C for 1 hour to obtain maleic acid. To this, 432 parts of 2,2'-m-phenylenebis (2-oxazole) was added, and 12
After reacting at 0 ° C for 6 hours, an adduct having oxazoline rings at both ends was obtained. Then, 172 parts of methacrylic acid and 0.23 part of hydroquinone were added, and the mixture was further reacted at 100 ° C for 10 hours and diluted with 309 parts of styrene. After dissolution, a compound (C-7) having an esteramide group and a methacryloyl group at both ends was obtained. Production Example 8 [Same as above] Methyl tetrahydrophthalic anhydride was obtained by reacting 166 parts of methyltetrahydrophthalic anhydride with 18 parts of water at 100 ° C for 1 hour. To this, 432 parts of 2,2′-m-phenylenebis (2-oxazol) was added, and the mixture was reacted at 120 ° C. for 6 hours to obtain an adduct having oxazoline rings at both ends, and then 172 parts of methacrylic acid. And 0.23 parts of hydroquinone are added, and the mixture is further reacted at 100 ° C. for 10 hours, diluted and dissolved with 338 parts of styrene, and a compound having an ester amide group and a methacryloyl group at both ends (C
-8) was obtained. Examples 1 to 12 43 parts of each epoxy resin composition prepared by blending with the composition shown in Table 1 was added to a long glass cloth having a thickness of 0.18 mm and a width of 1050 mm to obtain a solid content of the epoxy resin composition. Impregnated so that it will be 43%, stack 8 of these,
Further, a copper foil having a thickness of 35 μm is laminated on the upper and lower sides thereof,
Transport in a heating furnace at ℃ for 4 minutes while heating, then 170
20kg / cm with double belt press machine heated to ℃
1000 mm after heat and pressure molding at a pressure of ² for 10 minutes
It was cut into 1000 mm and then post-cured at 170 ° C. for 50 minutes to obtain a laminated plate having a thickness of 1.6 mm. Delamination strength, chemical resistance,
The water absorption rate and the solder heat resistance were measured. The results are shown in Table 1.

Delamination strength: The outermost fibrous base material was peeled from the fibrous base material adjacent to the outermost layer with the copper foil attached, and the angle of the peeling direction with respect to the outermost layer base material removed surface was 9
The peel strength was measured with Tensilon at a speed of 5 cm / min while maintaining the temperature at 0 ° C.

Chemical resistance: The copper foils on both sides of the obtained laminated plate were removed by etching, and the coated foil was immersed in methylene chloride at 40 ° C. for 15 minutes.
It was immersed for 30 minutes and 30 minutes, and the state of the surface of the laminate was visually determined.

Water absorption rate (%): After removing the copper foil on one surface of the laminated plate cut into 25 mm × 50 mm by etching, 120
A pressure cooker test was performed for 4 hours and 6 hours under the conditions of ° C and 2 atm, and the water absorption rate was calculated based on the following formula, and the average value was shown.

[0035] (W is the weight of the laminate before the test,
W'is the weight of the laminated plate after the test. ) Solder heat resistance: After water on the surface of the laminated plate after the above pressure cooker test was thoroughly wiped off, each sample was measured 10 times according to JIS C-6481 and evaluated according to the following criteria.

◯: No sample having 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. Comparative Example 1 A laminated board was obtained in exactly the same manner as in Example 1 except that the compound (C-1) was not used. The delamination strength, chemical resistance, water absorption and solder heat resistance of the copper clad laminate were measured in the same manner. The results are shown in Table 1.

[0037]

[Table 1]

[0038]

[Table 2]

[0039]

[Table 3]

The definitions of the names of the raw materials used in Table 1 are as follows. Epicron 840: A bisphenol type epoxy resin having an epoxy equivalent of 185.

Epiclon 152: Tetrabromobisphenol A type epoxy resin having an epoxy equivalent of 365 and a bromine content of 46%.

Epicron B650: Hexahydrophthalic anhydride. Dicklight UE7016: Dimethyacrylate of tetradibromobisphenol A didiglycidyl ether diluted with styrene. Styrene content rate 27
%, Bromine content 29%.

(All are manufactured by Dainippon Ink and Chemicals, Inc.)

[0044]

INDUSTRIAL APPLICABILITY Since the present invention is an epoxy resin composition containing a compound having an ester amide group and an ethylenically unsaturated double bond as an essential component, it does not exist in a conventional epoxy resin which does not contain it. A particularly remarkable effect that a cured product having excellent delamination strength, chemical resistance and heat resistance can be obtained.

Therefore, when, for example, a laminated board is produced from the epoxy resin composition of the present invention, the obtained fibrous base material has excellent delamination strength, chemical resistance and solder heat resistance.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI Technical display location C08G 59/48 NJE 8416-4J C08J 5/04 CFC 7188-4F // C08L 63:00 8416-4J

Claims (10)

[Claims] 1. An epoxy resin containing an epoxy resin (A), a polybasic acid anhydride (B), and a compound (C) having an ester amide group and an ethylenically unsaturated double bond. Composition (I). 2. The composition according to claim 1, wherein the compound (C) is a compound obtained by reacting a compound having at least one oxazoline ring with an unsaturated monobasic acid. 3. A compound (C) is obtained from a compound having at least two oxazoline rings and a polyvalent phenol compound to obtain an adduct having an oxazoline ring at the terminal, and then reacting this with an unsaturated monobasic acid. The composition according to claim 1, which is a compound obtained by the method. 4. The compound (C) is obtained by obtaining an adduct having an oxazoline ring at a terminal from a compound having at least two oxazoline rings and a polybasic acid, and then reacting this with an unsaturated monobasic acid. The composition of claim 1 which is a compound. 5. A resin (E) having an ethylenically unsaturated double bond other than (C) is further included.
The composition as described. 6. A fibrous base material (II) comprising the composition of claim 1.
A method for producing a laminated plate, which comprises: 7. A fibrous base material (II) containing the composition of claim 2.
A method for producing a laminated plate, which comprises: 8. A fibrous base material (II) comprising the composition of claim 3.
A method for producing a laminated plate, which comprises: 9. A fibrous base material (II) containing the composition of claim 4.
A method for producing a laminated plate, which comprises: 10. A fibrous base material (I
A method for producing a laminated plate, which comprises impregnating with I) and curing.