JP2506006B2 - Epoxy resin composition and method for producing the same - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to modification of epoxy resin, and more particularly to an epoxy resin composition having improved mechanical properties, heat resistance, dielectric constant and the like, and a method for producing the same.

[0002]

2. Description of the Related Art In recent years, epoxy resins have excellent heat resistance, mechanical properties, electrical properties, and adhesive properties, and therefore, in recent years, wiring boards, circuit boards, and circuit boards, semiconductor chips, coils, and electric circuits in which these are multilayered. It is used in a very wide range as a resin for sealing materials, etc., or for adhesives, paints, fiber reinforced resins, etc.

However, the epoxy resin is generally fragile and easily cracks due to stress strain during curing or use, heat or mechanical impact, and the epoxy resin has a high dielectric constant. There is a problem that it cannot be used for various circuit wiring. For such problems, use of a curing agent having a long-chain aliphatic group or a rubber-like property, addition of a compound having an elastomeric property, addition of a plasticizer such as an asphalt substance, glycols, etc. The introduction of highly tough thermoplastic polymers such as polyamide and polycarbonate, the introduction of molecular groups showing rubber elasticity such as polybutadiene, polybutadiene-acrylonitrile copolymer, and polysiloxane, toughening epoxy resins and lowering the dielectric constant, etc. Has been done. (Koichi Ochi, Polymer 38
(3), 200, 1989)

[0004]

However, the above-mentioned substances for modifying an epoxy resin are not sufficiently compatible with the epoxy resin, or the sea-island structure size formed by mixing is large, and sufficient toughness and dielectric constant are not obtained. There is a problem that the effect is not yet obtained, such as not being obtained. It is an object of the present invention to provide an epoxy resin composition having high toughness, low inductivity and heat resistance, which cannot be obtained by conventional epoxy resins.

[0005]

As a result of intensive studies to solve the above problems, the present inventor has an amide skeleton containing a phenolic hydroxyl group in the molecule and contains an aliphatic chain. By reacting a block copolymer with an epoxy resin, it was found that an epoxy resin composition having excellent mechanical properties, electrical properties and heat resistance can be obtained.
The present invention has been completed. That is, the epoxy resin composition of the present invention comprises an epoxy resin and the following general formula (I):

Embedded image (In the formula, m = 0 to 400 integer, n = 1 to 400 integer, n / (m + n) = 0.01 to 1 and l = 1 to 50 integer, Ar ¹ and Ar ³ are divalent aromas. Group, Ar ² is a divalent aromatic group containing a phenolic hydroxyl group, R is hydrogen or an alkyl group having 4 or less carbon atoms, and q is an integer of 1 to 300). −
Modified epoxy resin composed of a reaction product with an aliphatic compound block copolymer (hereinafter referred to as a block copolymer),
An epoxy resin composition containing an unreacted epoxy resin and a curing agent, wherein a phenolic hydroxyl group-containing aramid moiety of the block copolymer is dispersed in the epoxy resin at a molecular level, and an aliphatic moiety of 4 to 0. It is characterized in that it is dispersed in an island structure of 001 μm size.

The first method for producing the epoxy resin composition of the present invention is to mix the epoxy resin with the block copolymer represented by the general formula (I) and heat the mixture to produce a modified epoxy resin. Then, after that, an unreacted epoxy resin and a curing agent are mixed with the modified epoxy resin, and the mixture is hot melt kneaded. In the second method, the epoxy resin and the block copolymer represented by the general formula (I) are mixed and heated to produce a modified epoxy resin, and then the modified epoxy resin and unreacted epoxy resin are mixed. And the curing agent is dissolved in an organic solvent and mixed, and then the organic solvent is removed and dried.

As the epoxy resin used as the modified epoxy resin and the unreacted epoxy resin in the epoxy resin composition of the present invention, any polyfunctional epoxy resin may be used. Examples of such an epoxy resin include glycidyl ethers. , Glycidyl esters, glycidyl amines, linear aliphatic epoxides, alicyclic epoxides, hydantoin type epoxies, and the like. Examples of the glycidyl ethers include glycidyl ether of bisphenol, polyglycidyl ether of phenol novolac, alkylene glycol or glycidyl ether of polyalkylene glycol. As the glycidyl ether of bisphenol, bisphenol A type, bisphenol F type, bisphenol AD type, bisphenol S type, tetramethylbisphenol A type, tetramethylbisphenol F type
Type, tetramethylbisphenol AD type, tetramethylbisphenol S type, tetrachlorobisphenol A
Examples of diglycidyl ethers of dihydric phenols such as phenol type, tetrabromobisphenol A type, and polyglycidyl ethers of phenol novolac include polyglycidyl ethers of novolac resins such as phenol novolac, cresol novolac, and brominated phenol novolac. Examples of the diglycidyl ether of alkylene glycol or polyalkylene glycol include diglycidyl ethers of glycols such as polyethylene glycol, polypropylene glycol and butanediol. The glycidyl esters include, for example, glycidyl ester of hexahydrophthalic acid and glycidyl ester of dimer acid, and the glycidyl amines include, for example, triglycidylaminodiphenylmethane, triglycidylaminophenol, triglycidyl isocyanate. And so on. Furthermore, examples of the linear aliphatic epoxides include epoxidized polybutadiene and epoxidized soybean oil, and examples of the alicyclic epoxides include:
Examples include 3,4-epoxy-6-methylcyclohexylmethylcarboxylate, 3,4-epoxycyclohexylmethylcarboxylate, hydrogenated bisphenol epoxy, and the like. Examples of hydantoin-type epoxies include diglycidyl hydantoin and glycidyl glycidoxyalkyl hydantoin.

The curing agent described below is used in the epoxy resin composition of the present invention. For example, bis (4-aminophenyl) sulfone, bis (4-aminophenyl) methane, 1.5-diaminonaphthalene, p-phenylenediamine, m-phenylenediamine, o-phenylenediamine, 2,6-dichloro-1, 4-benzenediamine,
Aromatic amine compounds such as 1,3-di (p-aminophenyl) propane and m-xylenediamine, ethylenediamine, diethylenetriamine, tetraethylenepentamine, diethylaminopropylamine, hexamethylenediamine, mensendiamine, isophoronediamine, Bis (4-amino-3-methyldicyclohexyl) methane,
Aliphatic amine compounds such as polymethylene diamine and polyether diamine, polyaminoamide compounds, aliphatic acid anhydrides such as dodecyl succinic anhydride, polyadipic acid anhydride, polyazelaic acid anhydride, hexahydrophthalic anhydride, methyl hexa Alicyclic acid anhydrides such as hydrophthalic anhydride, phthalic anhydride, trimellitic anhydride, benzophenone tetracarboxylic acid anhydride, ethylene glycol bis trimellitate, aromatic acid anhydrides such as glycerol tris trimellitate, phenol, Cresol, alkylphenol, catechol, bisphenol A type, bisphenol F type and other novolak resins and their phenolic halides, amino resins, urea resins, melamine resins, dicyandiamide, dihydrazine compounds, imidazolization Things, a Lewis acid and Bronsted acid salts, poly mercaptan compounds, isocyanate and blocked isocyanate compounds include, but like can be mentioned, but not limited thereto. The amount of these curing agents added to the epoxy resin is generally 10 to 2
A range of 00% by weight is preferred.

In the epoxy resin composition according to the present invention, a curing accelerator is used in combination as needed to accelerate the reaction between the epoxy resin and the curing agent. Examples of the curing accelerator in this case include phosphorus-based compounds such as triphenylphosphine and tertiary amine-based compounds such as trimethanolamine, triethanolamine, tetraethanolamine, 1,8-diaza-bicyclo [5,4,0]. -7-Undecene (DBU),
N, N-dimethylbenzylamine, 1,1,3,3-tetramethylguanidine, 2-ethyl-4-methylimidazole, N-methylpiperazine, etc., boron-based, for example,
1,8-diaza-bicyclo [5,4,0] -7-undecenium tetraphenylborate, imidazole, 2-
Ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 1-benzyl-2-methylimidazole, 2
-Heptadecyl imidazole, 2-isopropyl imidazole, 2,4-dimethyl imidazole, 2-phenyl-4-methyl imidazole, 2-methyl imidazoline,
Examples thereof include 2-ethylimidazoline, 2-isopropylimidazoline, 2-phenylimidazoline, 2-undecylimidazoline, 2,4-dimethylimidazoline, 2-phenyl-4-methylimidazoline, and compounds masking these. These curing accelerators may be used in combination of two or more, and the compounding amount is 0.
01 to 10% by weight is preferable.

Block copolymer (I) used in the present invention
Can be produced by the following method. That is, for the dicarboxylic acid component of the aromatic dicarboxylic acid having a divalent aromatic group Ar ¹ and the Ar ² -containing aromatic dicarboxylic acid having a phenolic hydroxyl group in the general formula (I), An aromatic diamine having a divalent aromatic group Ar ³ is added to an excess amount, and these are added, for example, in an organic solvent such as N-methyl-2-pyrrolidone in the presence of a phosphite ester as a catalyst and a pyridine derivative. The mixture is heated and stirred under an inert atmosphere such as nitrogen to polycondense the carboxylic acid group and the amino group. As a result, the obtained solution of the phenolic hydroxyl group-containing polyaramid oligomer having aminoaryl groups at both ends is added with an aliphatic compound having a carboxyl group at both ends, and further subjected to polycondensation reaction to be used in the present invention. The block copolymer (I) is obtained.

In the present invention, A having a phenolic hydroxyl group used for the production of the block copolymer of the general formula (I)
r ² containing aromatic dicarboxylic acids: HOOC-Ar ² -CO
Specific examples of OH include 5-hydroxyisophthalic acid,
4-hydroxyisophthalic acid, 2-hydroxyphthalic acid, 3-hydroxyphthalic acid, 2-hydroxyterephthalic acid can be mentioned. Specific examples of the dicarboxylic acid having a divalent aromatic group Ar ¹ in the general formula (I) include phthalic acid, isophthalic acid, terephthalic acid, 4,4′-biphenyldicarboxylic acid, 3,3′- Methylene dibenzoic acid,
4,4'-methylenedibenzoic acid, 4,4'-oxydibenzoic acid, 4,4'-thiodibenzoic acid, 3,3'-carbonyldibenzoic acid, 4,4'-carbonyldibenzoic acid,
4,4'-sulfonyldibenzoic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,
There are, but not limited to, 6-naphthalenedicarboxylic acid, 2,3-pyridinedicarboxylic acid, 2,6-pyridinedicarboxylic acid, 3,7-dicarboxylic acid diphenyl oxide and the like.

A specific example of the aromatic diamine having a divalent aromatic group Ar ³ used for the production of the block copolymer of the above general formula (I): H ₂ N--Ar ³ --NH ₂ is m-- Phenylenediamine, p-phenylenediamine, metatolylenediamine, 4,4'-diaminodiphenyl ether, 3,3'-dimethyl-4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether,
3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl thioether, 3,3'-dimethyl-
4,4'-diaminodiphenyl thioether, 3,3 '
-Diethoxy-4,4'-diaminodiphenylthioether, 3,3'-diaminodiphenylthioether,
4,4'-diaminobenzophenone, 3,3'-dimethyl-4,4'-diaminobenzophenone, 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,3'-dimethoxy-4,4 ' -Diaminodiphenylmethane, 2,2'-bis (3-aminophenyl) propane, 2,2'-bis (4-aminophenyl)
Propane, 4,4'-diaminodiphenyl sulfoxide, 4,4'-diaminodiphenyl sulfone, benzidine, 3,3'-dimethylbenzidine, 3,3'-dimethoxybenzidine, 3,3'-diaminobiphenyl, p-
Xylylenediamine, m-xylylenediamine, 1,5
-Diaminonaphthalene, 1,8-diaminonaphthalene,
Bisanilinefluorene, bistoluidinefluorene,
2,3-diaminopyridine, 2,5-diaminopyridine, 2,6-diaminopyridine, 2,6-diamino-4
-Methylpyridine, etc., which can be used alone or in combination.

Further, a divalent carboxylic acid of an aliphatic compound having a carboxyl group at both ends and a functional derivative thereof: HOOC used for the production of the block copolymer of the general formula (I)
_{- (CH 2 CHR-) q -COOH} ( where, R represents hydrogen or alkyl group of 4 or less carbon atoms, q is an integer from 1 to 300) Examples of butanedioic acid, propanedioic acid, pentanedioic acid , Hexanedioic acid, heptanedioic acid, octanedioic acid, nonanedioic acid, decanedioic acid, undecanedioic acid, dodecanedioic acid, propadecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid, nonanedecane Examples thereof include diacids, eicosane diacids, hydrogenated polybutadienes and the like.

The epoxy resin composition of the present invention can be manufactured by the following method. That is, the block copolymer represented by the general formula (I) obtained by the above-mentioned method and an epoxy resin are mixed and heated to contain a phenolic hydroxyl group contained in the aramid part of the block copolymer and an epoxide of the epoxy resin. A modified epoxy resin is produced by reacting with a group, and then an unreacted epoxy resin and a curing agent, and if necessary, a curing accelerator and other additives are mixed with the modified epoxy resin. To produce the epoxy resin composition of the present invention. In this case, when mixing the modified epoxy resin with the unreacted epoxy resin, the curing agent, etc., dry-blend each component in a prescribed mixing ratio and then heat-melt it using a heat kneader such as an extruder or a heat roll. The components may be kneaded or dissolved or dispersed in the organic solvent described below at a predetermined mixing ratio and stirred, and then the organic solvent may be removed and dried, but the invention is not limited thereto. The epoxy resin composition of the present invention includes a composition before curing and a composition after curing obtained by mixing a modified epoxy resin, an unreacted epoxy resin and a curing agent.

The organic solvent used in the production of the epoxy resin composition of the present invention includes amide solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone and tetrahydrofuran. Ether-based solvents and the like.

In the present invention, the content of the block copolymer is 0.1 to 30% by weight based on the total amount of the epoxy resin, that is, the epoxy resin which is a modified epoxy resin and the compounding epoxy resin for the epoxy resin composition. It is suitable. When 30% by weight or more of the block copolymer is added to the epoxy resin, not only the toughness of the epoxy resin is not sufficiently obtained, but also the heat resistance is impaired.
In the case of the following additions, the toughness cannot be sufficiently improved.

Other additives can be added to the epoxy resin composition of the present invention, if necessary. For example, natural waxes, synthetic waxes, metal salts of long-chain aliphatic acids, acid amides, esters, paraffins and other mold release agents, silicone rubber, nitrile rubber, butadiene rubber, polysiloxane and other stress relaxation agents. Flame retardants such as chlorinated paraffin, bromotoluene, hexabromobenzene, antimony trioxide, silane coupling agents, titanate coupling agents, aluminum coupling agents, fused silica, crystalline silica, Glass flakes, glass beads, glass balloons, talc, alumina, calcium silicate, calcium carbonate, barium sulfate, magnesia, silicon nitride, boron nitride, ferrite, rare earth cobalt, gold, silver, nickel, copper, lead,
Inorganic fillers or conductive particles such as iron powder, iron oxide, iron sand, graphite and carbon, coloring agents such as dyes and pigments, oxidation stabilizers, light stabilizers, moisture resistance improvers, thixotropy imparting agents,
Diluents, defoamers, other resins, etc. can also be added.

The epoxy resin composition of the present invention is an inorganic fiber such as glass fiber, boron fiber, silicon carbide fiber, alumina fiber, silica-alumina fiber, aramid fiber, polyester fiber, cellulose fiber, carbon fiber or other organic fiber. The fiber-reinforced composite material can also be formed by coating or impregnating fibers or the like. In this case, the mode of use of these fibers may be long fibers or short cut short fibers, it is also possible to arrange the fibers in one direction to produce a composite material, It may be in a shaped state as described above.

In the present invention, the reason why the block copolymer represented by the above general formula (I) improves toughness and lowers the dielectric constant without impairing the heat resistance of the epoxy resin is the above general formula (I). In addition to not only improving the heat resistance and toughness of the epoxy resin matrix by molecularly dispersing the phenolic hydroxyl group-containing aramid moiety of the block copolymer represented by the formula (I),
It is presumed that the aliphatic part of the block copolymer shown in (1) is dispersed as minute islands in the epoxy resin matrix to act as a stress relaxation agent in the matrix and also to lower the dielectric constant. In other words, this improvement in heat resistance and toughness is due to the fact that the phenolic hydroxyl group-containing aramid portion of the block copolymer represented by the general formula (I) has high heat resistance (high glass transition temperature) and rigidity. It is presumed that the stress relaxation property and the lowering of the dielectric constant result from the fact that the aliphatic portion of the block copolymer represented by the general formula (I) is rich in flexibility and has a low dielectric constant.

That is, the phenolic hydroxyl group-containing aramid moiety of the block copolymer represented by the general formula (I) can easily react with the epoxide contained in the epoxy resin, and this reaction causes molecular dispersion in the epoxy resin matrix. Can be made. Further, by block-copolymerizing such an aramid containing a phenolic hydroxyl group and an aliphatic compound having poor compatibility with an epoxy resin,
The aliphatic groups can be dispersed in the epoxy resin matrix in minute island sizes. In this case, the stress relaxation effect can be remarkably improved by dispersing the aliphatic group in a fine island size of 4.0 to 0.001 μm. When the island size exceeds 4 μm, the aliphatic group phase is macroscopically phase-separated, and the stress relaxation effect is not improved. When the island size is less than 0.001 μm, the aliphatic group is contained in the epoxy resin. Since they are dispersed in a molecular dispersion state, the action of the aliphatic group as a stress relaxation agent is reduced.

[0021]

EXAMPLES The present invention will be further described below with reference to examples, but the present invention is not limited thereto. Synthesis Example 1 <Synthesis of phenolic hydroxyl group-containing aramid-aliphatic compound block copolymer (phenolic hydroxyl group contained in aramid portion is 2 mol%)> isophthalic acid 19.60 g (1
18 mmol), 3,4'-diaminodiphenyl ether 26.4 g (132 mmol), 5-hydroxyisophthalic acid 0.41 g (2.3 mmol), lithium chloride 3.9 g, calcium chloride 12.1 g, N-methyl-2.
-240 ml of pyrrolidone and 54 ml of pyridine were added to 4 of 11
The solution was placed in a two-necked round bottom flask and dissolved with stirring, then 74 g of triphenyl phosphite was added and reacted at 90 ° C. for 4 hours to generate a phenolic hydroxyl group-containing aramid oligomer. Hydrogenated polybutadiene (CI-1000 manufactured by Nippon Soda Co., Ltd. having an average molecular weight of about 36) having carboxyl groups at both ends as an aliphatic compound in the produced oligomer.
00) 50.4 g (about 14 mmol) dissolved in 240 ml of pyridine was added and reacted for 4 hours, then cooled to room temperature, and the reaction solution was put into methanol 201 and hydrogenated for use in the present invention. An aramid-hydrogenated polybutadiene block copolymer containing about 2 mol% of a phenolic hydroxyl group having a content of type polybutadiene of 52 wt% was deposited. This block copolymer was washed with methanol and further refluxed with methanol for purification.

The intrinsic viscosity of the obtained block copolymer was 0.40 dl / g (dimethylacetamide solution, 30
℃). Was measured infrared spectrum by diffusion reflection method the block copolymer powder, 1674cm ^-1 in the amide carbonyl group, the absorption corresponding to -O- group in 1183 cm ^-1, terminal methyl group to 2804cm ^-1, 1302cm ^-1
Absorption corresponding to -C-C-H was observed, and it was confirmed that the block copolymer was the phenolic hydroxyl group-containing aramid-aliphatic compound block copolymer in the present invention.

Synthesis Example 2 <Synthesis of Phenolic Hydroxyl Group-Containing Aramid-Aliphatic Compound Block Copolymer (14 Mole% of Phenolic Hydroxyl Group in Aramid Part)> Isophthalic Acid 1 of Synthesis Example 1
9.60 g (118 mmol), 3,4'-diaminodiphenyl ether 26.4 g (132 mmol), 5-
Hydroxyisophthalic acid 0.41 g (2.3 mmol)
And 48 g of hydrogenated polybutadiene having carboxyl groups on both ends were charged with isophthalic acid of 19.93 g (120
mmol), 3,4'-diaminodiphenyl ether 3
0.63 g (153 mmol), 5-hydroxyisophthalic acid 3.64 g (20 mmol) and hydrogenated polybutadiene having a carboxyl group at both ends (C manufactured by Nippon Soda Co., Ltd.)
I-1000, average molecular weight about 1000) 28.0 g except that the same operation was performed to obtain an aramid-hydrogenated polybutadiene block copolymer containing about 14 mol% of phenolic hydroxyl groups used in the present invention. It was deposited. The block copolymer thus obtained has an intrinsic viscosity of 0.82 dl / g.
(Dimethylacetamide solution, 30 ° C.). Was measured infrared spectrum by diffusion reflection method the block copolymer powder, an amide carbonyl group 1675 cm ^-1, the absorption corresponding to -O- group 1185cm ^-1, 280
Terminal methyl group at the 6 cm ^-1, absorption corresponding to -C-C-H in 1308Cm ^-1 was observed, the block copolymer, a phenolic hydroxyl group-containing aramid in the present invention - aliphatic compound block copolymer Was confirmed.

Example 1 After dissolving 24 g of a phenolic hydroxyl group-containing aramid-hydrogenated polybutadiene block copolymer containing 2 mol% of the phenolic hydroxyl group obtained in Synthesis Example 1 in 200 g of dimethylformamide, an epoxy resin was dissolved. (Epicoat 828, bisphenol A type epoxy resin, average molecular weight: 380, epoxy equivalent: 190 ± 5, manufactured by Yuka Shell Co., Ltd.) 24 g, triphenylphosphine 0.08 g as a curing accelerator is added, and the mixture is added at 90 ° C. for 2 hours. It was made to react. After completion of the reaction, the reaction product was poured into water to precipitate the resin, and the washing was repeated with warm water. Further, tetrahydrofuran was added to azeotrope these solvents under reduced pressure, followed by vacuum drying, A modified epoxy resin formed by reacting the phenolic hydroxyl group of the aramid portion of the phenolic hydroxyl group-containing aramid-aliphatic block copolymer with the epoxide group of the epoxy resin was obtained. To the solution obtained by dissolving 1 mg of the obtained modified epoxy resin in about 30 ml of pyridine, 1 g of a color indicator for phenolic hydroxyl group (1 g of anhydrous iron (III) chloride was dissolved in 100 ml of chloroform, and further 8 ml of pyridine was added, followed by precipitation. The product was filtered and the red solution was adjusted to obtain a few drops) and stirred, but no discoloration was observed, and all phenolic hydroxyl groups in this modified epoxy resin reacted with glycidyl groups, and unreacted. It was confirmed that no phenolic hydroxyl group was contained. 3.7 g of the above modified epoxy resin
On the other hand, 96.3 g of unreacted epoxy resin, 12.4 g of bis (4-aminophenyl) methane which is a curing agent, and 1 g of triethanolamine which is a curing accelerator are melted by an extruder and added, and the mixture is uniformly stirred. Mixed in. This mixture was heated at 80 ° C. for 2 hours and then further cured by heating at 180 ° C. for 6 hours to obtain an epoxy resin composition containing 3% by weight of the phenolic hydroxyl group-containing aramid-aliphatic compound block copolymer of the present invention. .

Example 2 With respect to 7.4 g of a modified epoxy resin obtained by reacting the phenolic hydroxyl group of the aramid part of the aramid-aliphatic compound block copolymer containing a phenolic hydroxyl group obtained in Example 1 with the epoxide group of the epoxy resin Unreacted epoxy resin 9
2.6 g, curing agent bis (4-aminophenyl) methane 12.4 g, and curing accelerator trimethanolamine 1 g were melted in an extruder and added, and then stirred to obtain a uniform mixture. . The resulting mixture was heat-cured in the same manner as in Example 1 to give 6 parts of the phenolic hydroxyl group-containing aramid-aliphatic compound block copolymer of the present invention.
An epoxy resin composition containing wt% was obtained.

Example 3 About 14 mol% of the phenolic hydroxyl group obtained in Synthesis Example 2 was used.
24 g of a phenolic hydroxyl group-containing aramid-hydrogenated polybutadiene block copolymer contained, epoxy resin (Epicoat 828, bisphenol A type epoxy resin, average molecular weight: 380, epoxy equivalent: 190 ± 5, manufactured by Yuka Shell Co., Ltd.) 14. 4 g, 0.64 g of triphenylphosphine which is a curing accelerator, and 200 g of dimethylformamide
And the same procedure as in Example 1 to obtain a modified epoxy resin formed by reacting the phenolic hydroxyl group of the phenolic hydroxyl group-containing aramid-aliphatic block copolymer with the epoxide group of the epoxy resin. It was To the solution obtained by dissolving 1 mg of the obtained modified epoxy resin in about 30 ml of pyridine, 1 g of a phenolic hydroxyl group color indicator (anhydrous iron (III) chloride (1 g) was dissolved in 100 ml of chloroform, and further 8 ml of pyridine was added, followed by precipitation. The product was filtered and the red solution was adjusted to obtain a few drops) and stirred, but no discoloration was observed, and all phenolic hydroxyl groups in this modified epoxy resin reacted with glycidyl groups, and unreacted. It was confirmed that no phenolic hydroxyl group was contained. With respect to 4.8 g of the modified epoxy resin, 95.2 g of the epoxy resin and bis (4-aminophenyl) which is a curing agent
12.4 g of methane and 1 g of triethanolamine, which is a curing accelerator, were melted by an extruder and added, and the mixture was stirred and uniformly mixed. This mixture was heated at 80 ° C. for 2 hours and then further cured by heating at 180 ° C. for 6 hours to obtain an epoxy resin composition containing 3% by weight of the phenolic hydroxyl group-containing aramid-aliphatic compound block copolymer of the present invention. .

Example 4 To 9.6 g of a modified epoxy resin obtained by reacting the phenolic hydroxyl group of the aramid part of the aramid-aliphatic compound block copolymer containing a phenolic hydroxyl group obtained in Example 3 with the epoxide group of the epoxy resin And the epoxy resin 9
0.4 g, curing agent bis (4-aminophenyl) methane 12.4 g, and curing accelerator trimethanolamine 1 g were melted and added, and then stirred to obtain a uniform mixture. The resulting mixture was heat-cured in the same manner as in Example 1 to give the phenolic hydroxyl group-containing aramid of the present invention.
An epoxy resin composition containing 6% by weight of the aliphatic compound block copolymer was obtained.

Comparative Example 1 Epoxy resin (Epicoat 828, bisphenol A type epoxy resin, average molecular weight: 380, epoxy equivalent: 1
90 ± 5, made by Yuka Shell Co., Ltd.), 12.4 g of bis (4-aminophenyl) methane which is a curing agent, and 1 g of triphenylphosphine which is a curing accelerator are further melted by an extruder and added and stirred. After obtaining a homogeneous mixture by heating the mixture at 80 ° C. for 2 hours, a further 18
It was heat-cured at 0 ° C. for 6 hours to obtain a comparative epoxy resin composition.

The test pieces obtained in Examples 1 to 4 and Comparative Example 1 were subjected to impact strength, dielectric constant, glass transition temperature (calculated from measurement of dynamic viscoelasticity) and epoxy resin composition by an electron microscope by the following methods. The island size of the aliphatic component in the product was measured. The results are shown in Table-1. As a result, it was shown that the epoxy resin composition of the present invention markedly improved the mechanical properties and the dielectric constant without impairing the heat resistance. Impact strength measurement: Dynestst Feinm
echanic Ralf Koge) using DIN-53453
It was carried out according to. The test piece was 15 × 10 × 2 mm. Measurement of dynamic viscoelasticity: torsional pendulum type viscoelasticity measuring device (RD
-100, manufactured by Resca Co., Ltd.), and the temperature rising rate is 0.7.
It was measured at ° C / min. The test piece is 70 x 7 x 0.7 mm
And Measurement of dielectric constant: Measured at a room temperature of 50 Hz using a DuPont thermal analysis system Model 2970 dielectric constant analyzer.
The test piece was 30 × 30 × 2 mm. Measurement of island size: Using an electron microscope (JSM5300 type, manufactured by JEOL Ltd.), the size of the unevenness of the fracture surface of the test piece subjected to gold vapor deposition was measured.

[0030]

[Table 1]

[0031]

Since the epoxy resin composition of the present invention has improved toughness and dielectric constant without impairing the heat resistance of the epoxy resin, it is an insulating adhesive for circuit boards integrated with a metal foil. , Encapsulant for encapsulating semiconductor elements, powder coating,
It is useful as it can be used in adhesives, anticorrosion paints, etc.

Claims (4)

(57) [Claims] 1. A modified epoxy resin obtained by reacting an epoxy resin with a phenolic hydroxyl group-containing aramid-aliphatic compound block copolymer represented by the following general formula (I), an unreacted epoxy resin and a curing agent. An epoxy resin composition, wherein the phenolic hydroxyl group-containing aramid portion of the block copolymer is molecularly dispersed in the epoxy resin, and the aliphatic portion is dispersed in the epoxy resin in an island structure having a size of 4 to 0.001 μm. An epoxy resin composition characterized by being in a state. Embedded image (In the formula, m = 0 to 400 integer, n = 1 to 400 integer, n / (m + n) = 0.01 to 1 and l = 1 to 50 integer, Ar ¹ and Ar ³ are divalent aromas. Group, Ar ² is a divalent aromatic group containing a phenolic hydroxyl group, R is hydrogen or an alkyl group having 4 or less carbon atoms, and q is an integer of 1 to 300) 2. The phenolic hydroxyl group-containing aramid-
The aliphatic compound block copolymer is incorporated into the epoxy resin in an amount of 0.
1 to 30% by weight is contained.
Epoxy resin composition. 3. An epoxy resin and the following general formula (I): (In the formula, m = 0 to 400 integer, n = 1 to 400 integer, n / (m + n) = 0.01 to 1 and l = 1 to 50 integer, Ar ¹ and Ar ³ are divalent aromas. Group, Ar ² is a divalent aromatic group containing a phenolic hydroxyl group, R is hydrogen or an alkyl group having 4 or less carbon atoms, and q is an integer of 1 to 300). −
Characterized by mixing with an aliphatic compound block copolymer and reacting with heat to form a modified epoxy resin, and then adding an unreacted epoxy resin and a curing agent to the modified epoxy resin and kneading the mixture by heat melting. And a method for producing an epoxy resin composition. 4. An epoxy resin and the following general formula (I): (In the formula, integer of m = 0 to 400, integer of n = 1 to 400, n / m + n = 0.01 to 1, integer of 1 = 1 to 50,
Ar ¹ and Ar ³ are divalent aromatic groups, Ar ² is a divalent aromatic group containing a phenolic hydroxyl group, R is hydrogen or an alkyl group having 4 or less carbon atoms, and q is an integer of 1 to 300. (Shown) is mixed with a phenolic hydroxyl group-containing aramid-aliphatic compound block copolymer and reacted by heating to produce a modified epoxy resin, and then the modified epoxy resin, unreacted epoxy resin and curing agent are mixed. A method for producing an epoxy resin composition, which comprises dissolving and mixing in an organic solvent, removing the organic solvent, and drying.