JP2530530B2 - 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 an epoxy resin, and more particularly to an epoxy resin composition having improved heat resistance, toughness, 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. It is used in a very wide range as a sealing material or a resin for adhesives, paints, fiber reinforced resins and the like.

However, the epoxy resin is generally fragile and easily cracks due to stress strain during curing or use, or due to heat or mechanical impact, and the epoxy resin has a high dielectric constant. There is a problem that it cannot be used for minute circuit wiring in. 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 high toughness thermoplastic polymers such as polyamide, polycarbonate, polybutadiene,
Toughening of the epoxy resin and reduction of the dielectric constant have been carried out by introducing a molecular chain showing rubber elasticity such as polybutadiene-acrylonitrile copolymer and polysiloxane.
(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 the sufficient heat resistance, toughness, There is a problem that a sufficient effect has not yet been obtained, such as the dielectric constant not being obtained. It is an object of the present invention to provide an epoxy resin composition which maintains sufficient heat resistance and has high toughness and a low dielectric constant which cannot be obtained by conventional epoxy resins.

[0005]

As a result of intensive studies to solve the above problems, the present inventor has found that a block copolymer having a polysiloxane and an imide skeleton containing a phenolic hydroxyl group in the molecule is It was found that an excellent epoxy resin composition having high toughness and low dielectric constant can be obtained by reacting a polymer, an epoxy resin and a curing agent, and completed the present invention. 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 200, n = 1 to 200, n / (m + n) = 0.01 to 1.0, Ar ¹ is a tetravalent aromatic organic group, and 4 Each carbonyl group is directly bonded to a different carbon atom, and each pair of carbonyl groups is bonded to an adjacent carbon atom in the Ar ¹ group, Ar ² is a divalent aromatic group, and Ar ³ is a phenolic hydroxyl group. A divalent aromatic group, R may have a substituent, a phenyl group, a phenoxy group, or a carbon number of 1 to 1
Represents a divalent hydrocarbon group of 0, an integer of 1 = 1 to 200,
q = 1 represents an integer of 1 to 40), an epoxy resin modified product obtained by reaction with a phenolic hydroxyl group-containing polyimide-polysiloxane block copolymer (hereinafter, referred to as a block copolymer), an epoxy resin and curing An epoxy resin composition containing an agent, wherein the phenolic hydroxyl group-containing polyimide portion of the block copolymer is molecularly dispersed in the epoxy resin, and the polysiloxane portion is dispersed in an island structure having a size of 5 to 0.001 μm. It is characterized by being in a state.

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

In the epoxy resin composition of the present invention, the epoxy resin modified product and the epoxy resin used as the epoxy resin mixed with the modified product may be any polyfunctional compounds, and examples of such a compound include: , Glycidyl ethers, glycidyl esters, glycidyl amines, linear aliphatic epoxides, alicyclic epoxides, hydantoin type epoxies, and the like. As the glycidyl ethers, for example,
Examples thereof include glycidyl ether of bisphenol, polyglycidyl ether of phenol novolac, alkylene glycol or glycidyl ether of polyalkylene glycol. Examples of the glycidyl ether of bisphenol include bisphenol A type, bisphenol F type, bisphenol AD type, bisphenol S type, tetramethylbisphenol A type, tetramethylbisphenol F type, tetramethylbisphenol AD type, tetramethylbisphenol S type, and tetrachloro. Examples of diglycidyl ethers of dihydric phenols such as bisphenol A type and tetrabromobisphenol A type are polyglycidyl ethers of phenol novolac, for example,
Phenol novolac, cresol novolac, polyglycidyl ether of novolac resin such as brominated phenol novolac, as the diglycidyl ether of alkylene glycol or polyalkylene glycol,
Examples thereof 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, linear aliphatic epoxides include, for example, epoxidized polybutadiene and epoxidized soybean oil, and alicyclic epoxides include, for example, 3,4-epoxy-6-methylcyclohexylmethylcarboxylate, 3,4-epoxy cyclohexyl methyl carboxylate, hydrogenated bisphenol epoxy and the like can be mentioned. Examples of hydantoin-type epoxies include diglycidylhydantoin and glycidylglycidoxyalkylhydantoin.

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, menthenediamine, isophoronediamine, bis (4-amino-3-methyldicyclohexyl) methane,
Aliphatic amine compounds such as polymethylene diamine, 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 bistrimellitate, aromatic acid anhydrides such as glycerol tris trimellitate, phenol, Novolak resins such as cresol, alkylphenol, catechol, bisphenol A and bisphenol F, and halides of these phenol resins, phenol resins, amino resins, urea resins, melamine resins, dicyandiamide, dihydrazine compounds S, imidazole compounds, Lewis acids and Bronsted acid salts, poly mercaptan compounds, isocyanate and blocked isocyanate compounds include, but like can be mentioned, but not limited thereto. Generally, the amount of these curing agents added to the epoxy resin is preferably in the range of 10 to 200% by weight.

In the epoxy resin composition of the present invention, a curing accelerator is used in combination as needed in order to accelerate the reaction between the epoxy resin and the curing agent. In this case, the curing accelerator may be phosphorus-based, such as triphenylphosphine, tertiary amine-based, 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-methylimidazole, 2-methylimidazoline, 2
-Ethyl imidazoline, 2-isopropyl imidazoline, 2-phenyl imidazoline, 2-undecyl imidazoline, 2,4-dimethyl imidazoline, 2-phenyl-4-methyl imidazoline, and the like, or compounds masking these may be mentioned. These curing accelerators may be used in combination of two or more, and the blending amount is based on the epoxy resin,
0.01 to 10% by weight is preferred.

The block copolymer in the present invention is
It can be manufactured by the following method. That is, an aromatic diamine component having a divalent aromatic organic group Ar ³ containing at least a phenolic hydroxyl group, an aromatic tetracarboxylic dianhydride component having a tetravalent aromatic organic group Ar ¹ , and a divalent aromatic. An aromatic diamine component having a group organic group Ar ² is, for example, N
-Polymerization by heating and stirring an aromatic diamine component and an aromatic tetracarboxylic dianhydride component in an organic solvent such as methyl-2-pyrrolidone under an inert atmosphere such as nitrogen at about room temperature to about 80 ° C. To produce a phenolic hydroxyl group-containing polyamic acid, and then to produce a polyamic acid blocked by polysiloxane by polycondensing the phenolic hydroxyl group-containing polyamic acid and polysiloxane under the same conditions as described above. Further, the block copolymer represented by the general formula (I) can be produced by further heating to 180 ° C. or higher to cause imide ring closure. When producing this polyamic acid, by making the aromatic tetracarboxylic dianhydride component an excess amount with respect to the aromatic diamine component, to make both ends of this phenolic hydroxyl group-containing polyamic acid dicarboxylic anhydride groups. You can Such polyamic acid having both ends as dicarboxylic acid anhydride groups can be polycondensed with a polysiloxane having amino groups at both ends.

Examples of the aromatic tetracarboxylic acid anhydride used in the production of the block copolymer represented by the general formula (I) in the present invention include pyromellitic dianhydride, 2,
3,6,7-naphthalenetetracarboxylic dianhydride,
3,4,3 ', 4'-biphenyltetracarboxylic dianhydride, 2,3,2', 3'-biphenyltetracarboxylic dianhydride, 3,4,3 ', 4'-diphenylsulfone tetracarboxylic acid Acid dianhydride, bis (3,4-dicarboxylphenyl) sulfide dianhydride, bis (3,4-dicarboxylphenyl) ethylene glycol dianhydride,
Bis (3,4-dicarboxylphenyl) methane dianhydride, bis (3,4-dicarboxylphenyl) ether dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 3 , 4,3 ', 4'-Dibenzophenone tetracarboxylic dianhydride, 4,4'-biphthalic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, Etc.,
These can be used alone or in combination.

The above-mentioned general formula (I) used in the present invention
Aromatic diamine containing phenolic hydroxyl group used in the production of the block copolymer shown by H ₂ N—Ar ³ —NH
Specific examples of ₂ (wherein Ar ³ has the same meaning as described above) include 1,3-diamino-5-hydroxybenzene,
3,3'-dihydroxybenzidine, 3,3'-diamino-4,4'-dihydroxybiphenyl, 3,3'-dihydroxy-4,4'-diaminodiphenyl oxide,
3,3'-dihydroxy-4,4'-diphenyl sulfone, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, N, N'-bis (2-,
3- or 4-aminophenyl) -5-hydroxyisophthalamide, N, N'-bis (2-, 3- or 4-aminophenyl) -5-hydroxyterephthalamide, N,
N'-bis (2-, 3- or 4-aminophenyl) -2
-Hydroxyphthalamide, N, N'-bis (2-, 3
-Or 4-aminophenyl) -2-hydroxyisophthalamide, N, N'-bis (2-, 3- or 4-aminophenyl) -3-hydroxyphthalamide, N, N'-
Bis (4-amino-3,5'-dimethylphenyl) -5
-Hydroxyisophthalamide, N, N'-bis (4-
Amino-3,5'-dimethylphenyl) -2-hydroxyphthalamide, N, N'-bis (4-amino-3,
5'-dimethylphenyl) -3-hydroxyphthalamide, N, N'-bis (4-amino-n-butyl) -5-
Hydroxyisophthalamide, N, N'-bis (4-amino-n-hexyl) -5-hydroxyisophthalamide, N, N'-bis [4- (4-aminophenoxy) phenyl] -5-hydroxyisophthalamide, N, N '
-Bis [4- (4-aminophenylsulfonyl) phenyl] -5-hydroxyisophthalamide, etc., which can be used alone or in combination.

In the present invention, the aromatic diamine H ₂ N--Ar ² --NH containing no phenolic hydroxyl group, which is used for the production of the block copolymer represented by the general formula (I), is used.
Specific examples of ₂ (wherein Ar ² has the same meaning as described above) include 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'-diaminodiphenylthioether, 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, bisanilinefluorene, bistoluidinefluorene, 2,3-diaminopyridine, 2,5-diaminopyridine, 2 , 6-diaminopyridine, 2,6-diamino-4-methylpyridine, 1,4-diaminonaphthalene,
1,5-diaminonaphthalene, 1,8-diaminonaphthalene, 2,6-diaminonaphthalene, 1,4-bis (p
-Aminophenylisopropylidene) benzene, 1,3
-Bis (p-aminophenylisopropylidene) benzene, 1,3-bis (p-aminophenoxy) benzene,
There are 1,1-bis (4-aminophenyl) cyclohexane and the like, and these can be used alone or in combination.

As the polysiloxane used for producing the block copolymer used in the present invention, those having an amino group at both ends represented by the following formula (II) are applied.

Embedded image Here, Y has 1 to 1 carbon atoms which may have a substituent.
It represents a divalent hydrocarbon group of 0, a phenyl group, or a phenoxy group, and m is an integer of 1 to 200.

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) and an epoxy resin are mixed and heated to react the phenolic hydroxyl group contained in the polyimide part of the block copolymer with the epoxide group of the epoxy resin. An epoxy resin modified product is produced, and then the epoxy resin modified product is mixed with the epoxy resin and the curing agent, and if necessary, a curing accelerator and other additives, and the mixture is mixed. Manufacture things. In this case, when mixing the modified epoxy resin, the epoxy resin, the curing agent, etc., after dry-blending the respective components in a predetermined mixing ratio, heat melting and kneading using a heat kneader such as an extruder or a heat roll. Alternatively, each component may be dissolved or dispersed in an organic solvent described below in 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 epoxy resin, and a curing agent.

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

In the present invention, the content of the block copolymer is 0.1 to 30 with respect to the total amount of the epoxy resin, that is, the epoxy resin that participates in the modified epoxy resin and the compounding epoxy resin for preparing the epoxy resin composition. Weight percent is preferred. When the block copolymer is added to the epoxy resin in an amount of 30% by weight or more, not only the toughness thereof is not sufficiently obtained, but also the heat resistance is impaired, and the addition amount is 0.1% by weight or less. Also in this case, sufficient toughness cannot be obtained.

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 releasing agents, silicone rubber, nitrile rubber, butadiene rubber, polysiloxane and other stress relaxation agents. Flame retardants such as chlorinated paraffin, bromotoluene, hexabromobenzene, and 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,
Iron powder, iron oxide, sand iron, graphite, inorganic fillers such as carbon or conductive particles, colorants such as dyes and pigments, oxidation stabilizers, light stabilizers, moisture resistance improvers, thixotropic agents,
Diluents, defoamers, other resins, etc. can also be added.

The epoxy resin composition of the present invention is not dissolved or dispersed in a solvent and is an inorganic fiber such as glass fiber, boron fiber, silicon carbide fiber, alumina fiber, silica-alumina fiber, aramid fiber, polyester fiber or cellulose. The fiber-reinforced composite material can also be formed by coating or impregnating an organic fiber such as fiber or carbon fiber. In this case, the form of use of such fibers may be long fibers or short cut short fibers, or may be one in which the fibers are arranged in one direction to produce a composite material, such as a woven fabric in advance. It may be in a state of being shaped.

[0020]

In the present invention, the reason why the block copolymer represented by the general formula (I) improves the toughness without lowering the heat resistance of the epoxy resin and lowers the dielectric constant is the phenol of the block copolymer. In addition to improving the heat resistance and toughness of the epoxy resin matrix by the molecular dispersion of the functional hydroxyl group-containing polyimide portion in the epoxy resin matrix, the polysiloxane portion of the block copolymer described above is It is presumed that the dispersion as islands serves as a stress relaxation agent in the matrix and also serves to reduce the dielectric constant. This improvement in heat resistance and toughness is because the block copolymer has high rigidity when the phenolic hydroxyl group-containing polyimide portion is high, and the stress relaxation property and the low dielectric constant are represented by the general formula (I). It is presumed that the polysiloxane portion of the block copolymer shown by 1 is rich in flexibility and has a low dielectric constant.

In the present invention, the phenolic hydroxyl group-containing polyimide 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 the molecule in the epoxy resin matrix. It can be dispersed. Further, by block-copolymerizing such a polysiloxane group having poor compatibility with the phenolic hydroxyl group-containing polyimide and the epoxy resin, the polysiloxane portion can be dispersed in the epoxy resin matrix in a minute island size. In this case, the polysiloxane portion is set to a minute island size of 5
By disperse | distributing to -0.001 micrometer, the stress relaxation effect can be improved significantly. Island size is 5μ
If it exceeds m, the stress relaxation effect is not improved because the polysiloxane phase is macroseparated, and if the island size is smaller than 0.001 μm, the polysiloxane is dispersed in the epoxy resin in a molecular dispersion state. Therefore, the action of the polysiloxane as a stress relaxation agent is reduced.

[0022]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited thereto. Synthesis Example 1 <Synthesis of Phenolic Hydroxyl Group-Containing Polyimide-Polysiloxane Block Copolymer (2 mol% of phenolic hydroxyl group contained in polyimide part)> N, N′-bis (3-aminophenyl) -5-hydroxyisophthalate Amide 0.
28 g (0.78 mmol) and m-phenylenediamine 4.23 g (39.2 mmol) 3,4,3 ',
4'-benzophenone tetracarboxylic acid dianhydride 16
g (50 mmol) with N-methyl-2-pyrrolidone 4
It was dissolved in 50 mg and reacted at room temperature for 6 hours under a nitrogen atmosphere to obtain a polyamic acid solution. In this polyamic acid solution, a polysiloxane having amino groups at both ends (x-2
2-161B, average molecular weight: 3000. Shin-Etsu Chemical Co., Ltd.)
After adding 30 g (10 mmol) and reacting at room temperature for 8 hours, this polyamic acid solution was heated at 200 ° C. for 2 hours to carry out a dehydration cyclization reaction. After allowing to cool, the polymer solution was poured into a large amount of methanol. The precipitated polymer was separated by filtration, the filtered product was washed and dried to obtain a phenolic hydroxyl group-containing polyimide-polysiloxane block copolymer used in the present invention. The block copolymer thus obtained had an intrinsic viscosity of 0.33 dl / g (dimethylacetamide solution, 3
It was 0 degreeC). When the infrared spectrum of the block copolymer powder was measured by the diffuse reflection method, it was 1774 and 1.
The absorption corresponding to the imide group at 722 cm ^-1 is further 126
0 cm ^-1 to Si-CH _3, 1090 in the of 1020 cm ^-1 Si
Absorption corresponding to —O—Si was observed, and it was confirmed that the block copolymer was the phenolic hydroxyl group-containing polyimide-polysiloxane block copolymer in the present invention.

Synthetic Example 2 <Synthesis of Phenolic Hydroxyl Group-Containing Polyimide-Polysiloxane Block Copolymer (14 mol% of phenolic hydroxyl group contained in the polyimide part)> N, N'- of Synthetic Example 1
Bis (3-aminophenyl) -5-hydroxyisophthalamide 0.28 g (0.78 mmol) 2.06
In exactly the same manner except that g (5.7 mmol) was used,
A polyimide-polysiloxane block copolymer containing about 14 mol% of phenolic hydroxyl groups used in the present invention was deposited. The block copolymer obtained had an intrinsic viscosity of 0.34 dl / g (dimethylacetamide solution, 30
℃). When the infrared spectrum of the block copolymer powder was measured by the diffuse reflection method, it was 1775 and 17
Absorption corresponding to imide groups in 26cm ^-1, the Si-CH _3, 1091 and 1019 cm ^-1 to 1262cm ^-1 Si-O-S
Absorption corresponding to i was observed, and it was confirmed that the block copolymer was the phenolic hydroxyl group-containing polyimide-polysiloxane block copolymer referred to in the present invention.

Example 1 24 g of a phenolic hydroxyl group-containing polyimide-polysiloxane block copolymer containing 2 mol% of the phenolic hydroxyl group obtained in Synthesis Example 1 was dissolved in 200 g of dimethylformamide, and then an epoxy resin (Epicoat) was used. 8
28, bisphenol A type epoxy resin, average molecular weight:
380, epoxy equivalent: 190 ± 5, manufactured by Yuka Shell Co., Ltd.)
24 g, triphenylphosphine as a curing accelerator
After adding 0.08 g and reacting at 90 ° C. for 2 hours, the reaction product was poured into water to precipitate a resin, and washing was repeated with warm water. Tetrahydrofuran was further added to the solution under reduced pressure. After azeotroping these solvents, vacuum drying was performed to obtain an epoxy resin modified product in which the phenolic hydroxyl group of the polyimide part of the phenolic hydroxyl group-containing polyimide-polysiloxane block copolymer and the epoxide group of the epoxy resin reacted. . Obtained modified epoxy resin 1 mg
Was dissolved in about 30 ml of pyridine, and 1 g of color indicator of phenolic hydroxyl group (1 g of anhydrous iron (III) chloride was dissolved in 100 ml of chloroform, 8 ml of pyridine was added, and the precipitate was filtered to obtain a red solution. Adjusted and obtained)
After adding several drops of the mixture and stirring, no discoloration was observed, and it was confirmed that all the phenolic hydroxyl groups reacted with the glycidyl groups in this modified epoxy resin, and no unreacted phenolic hydroxyl groups were contained. 12.6 g of the above-mentioned modified epoxy resin, 96.3 g of the epoxy resin, and bis (4-aminophenyl) methane as a curing agent 12.
4 g and 1 g of triethanolamine, which is a curing accelerator, were melted and added, and stirred to be mixed uniformly. After heating this mixture at 80 ° C. for 2 hours, it was further heated at 180 ° C. for 6 hours to give the phenolic hydroxyl group-containing polyimide of the present invention.
An epoxy resin composition containing 3% by weight of a polysiloxane block copolymer was obtained.

Example 2 With respect to 7.4 g of a modified epoxy resin obtained by reacting the phenolic hydroxyl group of the polyimide part of the polyimide-polysiloxane block copolymer containing a phenolic hydroxyl group obtained in Example 1 with the epoxide group of the epoxy resin. Then, 92.6 g of the epoxy resin, 12.4 g of bis (4-aminophenyl) methane as a curing agent, and 1 g of trimethanolamine as a curing accelerator were melted and added, and then stirred to obtain a uniform mixture. . The obtained mixture was heated in exactly the same manner as in Example 1 to obtain an epoxy resin composition containing 6% by weight of the phenolic hydroxyl group-containing polyimide-polysiloxane block copolymer of the present invention.

Example 3 24 g of a phenolic hydroxyl group-containing polyimide-polysiloxane block copolymer containing about 14 mol% of the phenolic hydroxyl group obtained in Synthesis Example 2, 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, triphenylphosphine 0.64 g as a curing accelerator is dissolved in dimethylformamide 200 g, and the same operation as in Example 1 is performed. An epoxy resin-modified product was obtained in which the phenolic hydroxyl group of the polyimide part of the phenolic hydroxyl group-containing polyimide-polysiloxane block copolymer was reacted with the epoxide group of the epoxy resin. A solution of 1 mg of the obtained modified epoxy resin in about 30 ml of pyridine was added to a coloring indicator liquid of phenolic hydroxyl group (1 g of anhydrous iron (III) chloride was added to chloroform 100
It was dissolved in 8 ml of pyridine, 8 ml of pyridine was added, and the precipitate was filtered to obtain a red solution. A few drops were added and stirred, but no discoloration was observed. Confirmed that all of the phenolic hydroxyl groups reacted with the glycidyl group and contained no unreacted phenolic hydroxyl groups. To 4.8 g of the modified epoxy resin, 95.2 g of the epoxy resin, 12.4 g of bis (4-aminophenyl) methane that is a curing agent, and 1 g of triethanolamine that is a curing accelerator are melted and added,
Stir to mix uniformly. This mixture was heated at 80 ° C. for 2 hours and then at 180 ° C. for 6 hours to obtain an epoxy resin composition containing 3% by weight of the phenolic hydroxyl group-containing polyimide-polysiloxane 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 polyimide part of the polyimide-polysiloxane block copolymer containing a phenolic hydroxyl group obtained in Example 3 with the epoxide group of an epoxy resin. Then, 90.4 g of the epoxy resin, 12.4 g of bis (4-aminophenyl) methane that is a curing agent, and 1 g of trimethanolamine that is a curing accelerator are melted and added, and then stirred to obtain a uniform mixture. It was The obtained mixture was heated in the same manner as in Example 1 to obtain 6% by weight of the phenolic hydroxyl group-containing polyimide-polysiloxane block copolymer of the present invention.
The contained epoxy resin composition was obtained.

Comparative Example 1 Epoxy resin (Epicoat 828, bisphenol A type epoxy resin, average molecular weight: 380, epoxy equivalent: 1
90 ± 5, manufactured 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 melted and added to 100 g of the mixture, and stirred to form a uniform mixture. After obtaining this mixture,
After heating at 0 ° C. for 2 hours, it was further heated at 180 ° C. for 6 hours to obtain an epoxy resin composition for comparison.

The resin compositions obtained in Examples 1 to 4 and Comparative Example 1 were subjected to the following methods to obtain impact strength, dielectric constant, glass transition temperature (calculated from measurement of dynamic viscoelasticity) and epoxy resin by electron microscope. The island size of the polysiloxane component in the composition was measured. The results are shown in Table-1. As a result, the epoxy resin composition of the present invention showed a marked improvement in toughness and a low dielectric constant without impairing the heat resistance of the epoxy resin. Impact strength measurement: Dynestat
Feinmechanic Ralf Kogel)
Was used according to DIN-53453. 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 was 70 × 7 × 0.7 mm. Permittivity Measurements: DuPont Thermal Analysis System Model 2970
It measured at room temperature 50 Hz using the dielectric constant analyzer.
The test piece was 30 × 30 × 2 mm. Measurement of island structure size of siloxane component: electron microscope (J
Using a SM 5300 model, manufactured by JEOL Ltd., the size of the irregularities on the fracture surface of the gold vapor-deposited test piece was measured.

[0030]

[Table 1]

[0031]

Industrial Applicability The epoxy resin composition of the present invention has improved toughness and dielectric constant without impairing the heat resistance of the epoxy resin, and thus an insulating adhesive for a circuit board integrated with a metal foil, It is useful for a wide range of applications such as encapsulants for encapsulating semiconductor elements, powder coatings, adhesives, and anticorrosion coatings.

Claims (4)

(57) [Claims] 1. An epoxy resin modified product obtained by reacting an epoxy resin with a phenolic hydroxyl group-containing polyimide-polysiloxane block copolymer represented by the following general formula (I), an epoxy resin, and an epoxy resin containing a curing agent. In the composition, the phenolic hydroxyl group-containing polyimide portion of the block copolymer is molecularly dispersed in an epoxy resin, and the polysiloxane portion is 5 to 0.001 μm.
An epoxy resin composition having a size island structure and being dispersed in an epoxy resin. Embedded image (In the formula, m = 0 to 200, n = 1 to 200, n / (m + n) = 0.01 to 1.0, Ar ¹ is a tetravalent aromatic organic group, and 4 Each carbonyl group is directly bonded to a different carbon atom, and each pair of carbonyl groups is bonded to an adjacent carbon atom in the Ar ¹ group, Ar ² is a divalent aromatic group, and Ar ³ is a phenolic hydroxyl group. A divalent aromatic group, R may have a substituent, a phenyl group, a phenoxy group or a carbon number of 1 to 10
Represents a divalent hydrocarbon group of 1 = 1 to 200, q = 1 to
Indicates an integer of 40) 2. The epoxy resin composition according to claim 1, wherein the epoxy group contains the phenolic hydroxyl group-containing polyimide-polysiloxane block copolymer in an amount of 0.1 to 30% by weight. 3. The following general formula (I): (In the formula, m = 0 to 200, n = 1 to 200, n / (m + n) = 0.01 to 1.0, Ar ¹ is a tetravalent aromatic organic group, and 4 Each carbonyl group is directly bonded to a different carbon atom, and each pair of carbonyl groups is bonded to an adjacent carbon atom in the Ar ¹ group, Ar ² is a divalent aromatic group, and Ar ³ is a phenolic hydroxyl group. A divalent aromatic group, R may have a substituent, represents a phenyl group, or a phenoxy group or a divalent hydrocarbon group having 1 to 10 carbon atoms, an integer of 1 = 1 to 200, q = 1
A phenolic hydroxyl group-containing polyimide-polysiloxane block copolymer represented by the formula:
An epoxy resin characterized by mixing with an epoxy resin and reacting with heat to generate a modified epoxy resin, and then mixing the epoxy resin and a curing agent with the modified epoxy resin and kneading the mixture by heat. A method for producing a composition. 4. The following general formula (I): (In the formula, m = 0 to 200, n = 1 to 200, n / (m + n) = 0.01 to 1.0, Ar ¹ is a tetravalent aromatic organic group, and 4 Each carbonyl group is directly bonded to a different carbon atom, and each pair of carbonyl groups is bonded to an adjacent carbon atom in the Ar ¹ group, Ar ² is a divalent aromatic group, and Ar ³ is a phenolic hydroxyl group. A divalent aromatic group, R may have a substituent, represents a phenyl group, or a phenoxy group or a divalent hydrocarbon group having 1 to 10 carbon atoms, an integer of 1 = 1 to 200, q = 1
Of the phenolic hydroxyl group-containing polyimide-polysiloxane block copolymer represented by the formula (1 to 40) and an epoxy resin are reacted by heating to produce an epoxy resin modified product. A method for producing an epoxy resin composition, which comprises dissolving an epoxy resin and a curing agent in an organic solvent, mixing them, and then removing the organic solvent and drying.