JP2001123132A - Epoxy resin composition adhesive sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an epoxy resin composition adhesive sheet since a conventional used epoxy resin has a problem that it is difficult for the epoxy resin to make a sheetlike material in a semicured state, its film is brittle and inferior in self-supporting properties and an obtained laminate has low heat resistance even if the laminate is compound with an elastomer such as a styrene-butadiene copolymer, etc., and flexibility is improved. SOLUTION: This epoxy resin composition adhesive sheet comprises at least an epoxy resin, a curing agent and a phenolic hydroxy group-containing polyamide-polybutadiene-acrylonitrile block copolymer of the formula (Ar1 and Ar2 are each a bifunctional aromatic group; Ar3 is a phenolic hydroxy group-containing bifunctional aromatic group; X, Y and Z and l, n and m are each an average degree of polymerization; X is 3-7, Y is 1-4, Z is 5-15, m is an integer of 2-300; n/(n+1)>=0.04 and the block units (A) and (B) are each in a range of 1-20) as main components.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an adhesive sheet made of an epoxy resin composition, and more specifically, to contain a specific block copolymer to reduce brittleness when uncured, heat resistance during curing, and adhesiveness. The present invention relates to an improved epoxy resin composition adhesive sheet.

[0002]

2. Description of the Related Art Adhesive sheets containing an epoxy resin as a main component are used in large quantities in the process of manufacturing printed wiring boards and semiconductor packages used in electric and electronic equipment.
Conventionally, glass cloth, glass nonwoven fabric, and kraft paper have been often manufactured by impregnating an epoxy resin composition, using a prepreg in a semi-cured state, and bonding and laminating copper foil on one or both surfaces. In addition, after forming a circuit on both sides of the copper-clad laminate to produce an inner layer substrate, a copper foil is laminated on both sides via a prepreg, and a copper foil of an outer layer is etched to form a multilayer printed wiring board. Are also manufactured. In recent years, with the demand for higher density, lighter weight, and thinner printed wiring boards, printed wiring boards have been manufactured using a single insulating layer of a thermosetting resin composition without using a substrate such as glass cloth. The build-up method of manufacturing has become mainstream. The build-up method is a method in which the insulating layer and the conductor layer of the thermosetting resin composition alone are alternately stacked on the surface of the inner substrate, and the insulating layer can be thinned because no base material is used. This makes it possible to drill holes and to cope with higher densities.

A method of forming an insulating layer by a build-up method includes a method of directly applying a liquid resin composition to a circuit, and a method of applying a resin to one side of a sheet-like thermosetting resin composition or a copper foil in a semi-cured state. Then, there is a method of laminating a resin-cured copper foil in a semi-cured state with a press machine. However, in the case of a method in which a liquid resin composition is applied directly on a circuit, there is a problem in that the resin composition flows and the thickness of the insulating layer tends to vary.
When a copper foil with a resin is used, the thickness of the conductor must be adjusted by etching or the like when producing a fine pattern because the copper foil is thick. Therefore, a method of stacking a sheet of the thermosetting resin composition on the inner layer circuit and then pressing the sheet with a press machine to form an insulating layer has been studied.

[0004] However, the epoxy resin conventionally used as an insulating layer has good adhesiveness to a copper foil and good heat resistance, but it is generally difficult to produce a sheet in a semi-cured state. Or the film was very brittle and it was often difficult to handle it as a self-supporting sheet. Further, a method of forming a sheet by improving flexibility by blending an elastomer such as a styrene-butadiene copolymer has been adopted, but there was a problem that the heat resistance of the obtained laminate was low. Therefore, an epoxy resin composition which can be formed in a sheet shape and has excellent adhesiveness and heat resistance has been demanded.

[0005]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned problems in the prior art. Accordingly, an object of the present invention is to provide a sheet-like epoxy resin composition having excellent adhesiveness and heat resistance.

[0006]

Means for Solving the Problems The present inventors have conducted various studies to solve the above-mentioned problems in the prior art, and as a result, the following general formula (1) was applied to epoxy resin. The present inventors have found that the above problems can be solved by using the phenolic hydroxyl group-containing polyamide-polybutadiene acrylonitrile block copolymer shown above in combination, and have completed the present invention.

[0007]

Embedded image Wherein Ar ¹ and Ar ² represent a divalent aromatic group;
r ³ represents a divalent aromatic group having a phenolic hydroxyl group. X, Y, Z, and 1, n, and m are average polymerization degrees, respectively, where X = 3 to 7, Y = 1 to 4, Z = 5 to 15,
m represents an integer of 2 to 300, and n / (n + 1) ≧ 0.0
4. In addition, each of the block units (A) and (B) exists in the range of 1 to 20. ｝

That is, the epoxy resin composition adhesive sheet of the present invention comprises an epoxy resin composition comprising at least an epoxy resin, a curing agent and a phenolic hydroxyl group-containing polyamide-polybutadiene acrylonitrile block copolymer represented by the general formula (1). Thickness 5-100μm
In the form of a sheet. Hereinafter, the present invention will be described in detail.

[0009]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The epoxy resin used in the present invention is not particularly limited. Examples thereof include glycidyl ethers, glycidyl esters, glycidylamines, linear aliphatic epoxides, alicyclic epoxides, Hydantoin type epoxies and the like can be mentioned. Examples of the glycidyl ether include glycidyl ether of bisphenol, polyglycidyl ether of phenol novolak, alkylene glycol, and glycidyl ether of polyalkylene glycol. Examples of the glycidyl ether of bisphenol include bisphenol A, bisphenol F, bisphenol AD, bisphenol S, tetramethylbisphenol A, tetramethylbisphenol F, and tetramethylbisphenol A.
Glycidyl ethers of dihydric phenols such as D, tetramethylbisphenol S, tetrachlorobisphenol A, and tetrabromobisphenol A, and polyglycidyl ethers of phenol novolak include, for example, phenol novolak, cresol novolak, blocked phenol novolak and the like. As the polyglycidyl ether of the novolak resin, the glycidyl ether of alkylene glycol or polyalkylene glycol includes, for example, glycidyl ether of glycols such as polyethylene glycol, polypropylene glycol and butanediol. Examples of the glycidyl esters include, for example, glycidyl esters of hexahydrophthalic acid and glycidyl esters of dimer acid.
The glycidylamines include, for example, triglycidylaminodiphenylmethane, triglycidylaminophenol, triglycidyl isocyanurate and the like. Further, as linear aliphatic epoxides, for example,
Epoxidized polybutadiene, epoxidized soybean oil and the like, and alicyclic epoxides such as 3,4-
Epoxy-6-methylcyclohexylmethyl carboxylate, 3,4-epoxycyclohexyl carboxylate, hydrogenated bisphenol epoxy, and the like. Examples of the hydantoin type epoxy resin include diglycidyl hydantoin, glycidylglycidoxyalkylhydantoin, and the like. These epoxy resins may be used alone or in combination of two or more.

Further, in the epoxy resin composition adhesive sheet of the present invention, an epoxy resin having high fluidity when heated and exhibiting good adhesive strength to an adherend even at a low temperature is preferably used. . Specifically, it is an epoxy resin having a viscosity value of 100,000 centipoise or less at 25 ° C., for example, a product name “Epicoat” 8 manufactured by Yuka Shell Epoxy Co., Ltd.
01, 802, 806, 807, 815, 819, 82
5, 827, 828, 834, 152, 604, 63
0, 871, 872, 190P, 191P, YX31
0, DX255, trade name “Epototo” manufactured by Toto Kasei Co., Ltd.
YD-115, YD-118P, YD-127, YD-
128, YD-134, YD-8125, ZX-105
9, YDF-8170, YDF-170, YDF-17
5S, YH-434, YH-434L, YD-171,
YD-172, YR-207, YD-716, YR-5
28, YR-570, YH-300, YH-301, Y
H-315, YH-324, YH-325, PG-20
2, PG-207, PP-101, trade names “Epiclon” 840, 840S, 850, manufactured by Dainippon Ink and Chemicals, Inc.
850S, 850CRP, 855, 857, D-59
1,830,830S, 830LVP, 835,835
LV, 520, 703, 705, 707, 720, 72
5,730, TSR-960, 1600-75X, HP
-4032, HP-4032D, GA manufactured by Nippon Kayaku
N, GOT, AK-601, RE-304S, RE-3
10S, Plaxel GL61 manufactured by Daicel Chemical Industries, Ltd.
Praxel GL62, Celloxide 2021, Celloxide 2081, Celloxide 2083, Celloxide 2
085, PUE101T80, PUE106X80, P
UE106M80, PUE201, trade name “ADEKARESIN” manufactured by Asahi Denka Co., Ltd. EP-4100, EP-4100G,
EP-4100E, EP-4300, EP-4340,
EP-4200, EP-4400, EP-4500A,
EP-4510, EP-4520, EP-4520S,
EP-4520TX, EP-4530, EP-490
1, EP-4901E, EP-4930, EP-495
0, EP-4000, EP-4005, EP-400
6, EP-4050, EP-4004, EP-408
0, EP-4092, EP-4023, EP-402
4, EP-4026, EPR-20, EPU-6, EP
U-73, EPU-78-11, EPU-11, EPU
-15, EPU-16A, EPU-16B, EPU-1
7T-6, EPU-4-75X, EPUA-80, and Tetrad X and Tetrad C manufactured by Mitsubishi Gas Chemical Company, but are not limited thereto. These epoxy resins may be used alone or in combination of two or more. You may mix and use.

The viscosity at 25 ° C. is 10
The epoxy resin having a density of 10,000 centipoise or less is used in a proportion of 50% by weight or less in the epoxy resin composition of the present invention. If the number is larger than this, it is difficult to form a sheet, and the object of the present invention cannot be achieved.

The curing agent used in the present invention is not particularly limited as long as it can be used for an epoxy resin. For example, bis (4-aminophenyl) sulfone, bis (4-
Aminophenyl) methane, 1,5-diaminonaphthalene, p-phenylenediamine, m-phenylenediamine, o-phenylenediamine, 2,6-dichloro-1,
Aromatic diamine curing agents such as 4-benzenediamine, 1,3-di (p-aminophenyl) propane, m-xylenediamine, ethylenediaminediethylenetetramine, tetraethylenepentamine, diethylaminopropylamine, hexamethylenediamine, mentediamine, Aliphatic amine-based curing agents such as isophoronediamine, bis (4-amino-3-methyldicyclohexyl) methane, polymethylenediamine, polyetherdiamine, polyaminoamide-based curing agents, dodecyl succinic anhydride, polyadipic anhydride, poly Aliphatic anhydride curing agents such as azelaic anhydride, aromatic acid anhydrides such as ethylene glycol bistrimellitate, glycerol tristrimellitate, phenol compounds and phenol resins, amino resins, urea resins, and melamine resins Guanidines represented by dicyandiamide, dihydrazines, imidazoles, isocyanates, blocked isocyanates, polymercaptos, Lewis acids, Bronsted acid salts, and the like, but are not limited thereto. The curing agents may be used alone or in combination of two or more.

Above all, a curing agent for producing the epoxy resin composition adhesive sheet of the present invention is a latent curing agent which has low activity at room temperature and is cured by heating, and has excellent electrical properties and heat resistance. Novolak-type phenolic resins, which can improve the viscosity, are preferably used. As the novolak type phenol resin, for example, phenol, cresol, alkylphenol, catechol, bisphenol A, bisphenol F, 2,2'-bis (4-hydroxyphenyl) propane, 2,2'-bis (2-methyl-
A product obtained by reacting a compound having a phenolic hydroxyl group such as 4-hydroxyphenyl) propane with formaldehyde using an acid catalyst is exemplified. Specifically, for example, a trade name “Shownol” BRG-
555, BRG-556, BRG-557, BRG-5
58, BRG-559, CRG-951, CKM-24
00, CKM-2432, trade names “Epiclon” N-660, N-665, N-66 manufactured by Dainippon Ink and Chemicals, Inc.
7, N-670, N-673, N-680, N-69
0, N-695, N-665EXP, N-670EX
P, N-740, N-770, N-775, N-865
And the like, but are not limited to these,
These curing agents may be used alone or in combination of two or more.

Further, in the epoxy resin composition of the present invention, a curing accelerator may be used for accelerating the reaction between the epoxy resin and the curing agent. Specific examples of the curing accelerator include phosphorus compounds such as triphenylphosphine,
Tertiary amine compounds such as triethylamine, triethanolamine, 1,8-diaza-bicyclo (5,
Boric acid compounds such as (4,0) -7-undecene, N, N-dimethylbenzylamine, 2-ethyl-4-methylimidazole, N-methylpiperazine, and the like, for example, 1,8-
For example, diaza-bicyclo (5,4,0) -7-undecenium tetraphenylborate is used. Some of these accelerators may be used in combination, and the amount is preferably 0.01 to 10% by weight based on the epoxy resin.

The phenolic hydroxyl group-containing polyamide-polybutadiene acrylonitrile block copolymer (1) of the present invention is obtained by using an aromatic dicarboxylic acid component, an aromatic diamine component and a polybutadiene acrylonitrile copolymer having a carboxyl group at both terminals as raw materials. It can be easily produced by a polycondensation reaction. The condensation reaction between the aromatic dicarboxylic acid and the aromatic diamine can be performed by a known method. For example, the method can be carried out according to the method described in “Polymer Functional Material Series 2 Synthesis and Reaction of Polymer”, p. In particular, when a dicarboxylic acid having a phenolic hydroxyl group is used, a production method by a direct polycondensation reaction using a dehydration catalyst is preferable. Specifically, an excessive amount of an aromatic diamine component is added to an aromatic dicarboxylic acid component, and these components are mixed with N 2 in the presence of a phosphite and a pyridine derivative, for example.
In an organic solvent typified by -methyl-2-pyrrolidone or dimethylacetamide, a solution of a polyamide oligomer having an aminoaryl group at both ends is formed by heat polymerization under an inert atmosphere such as nitrogen. ,
Next, a polybutadiene acrylonitrile copolymer having carboxyl groups at both ends is added to the solution of the polyamide oligomer and polycondensation is performed, whereby the phenolic hydroxyl group-containing polyamide-polybutadiene acrylonitrile block copolymer of the present invention can be obtained. .
Further, lithium chloride or calcium chloride can be added as a stabilizer to the polycondensation reaction, if necessary.

The intrinsic viscosity of the block copolymer used in the present invention is preferably 0.1 to 3.0 dl / g. More preferably, it is set in the range of 0.2 to 2.0 dl / g. When the intrinsic viscosity value is lower than 0.1 dl / g, the film formability is poor, and when blended with the epoxy resin composition,
Cannot be formed into a sheet. 3.0 dl /
When it is higher than g, the compatibility with the epoxy resin is deteriorated, so that it is difficult to mix the epoxy resin composition with the epoxy resin composition, which causes a practical problem. Intrinsic viscosity value is 0.5g / dl sample concentration
Dimethylacetamide solution in Ostwald viscometer N
o. 1 is a measured value at 30 ° C.

The aromatic dicarboxylic acid component used in the phenolic hydroxyl group-containing polyamide-polybutadiene acrylonitrile block copolymer (1) used in the present invention includes, for example, isophthalic acid, terephthalic acid,
4'-biphenyldicarboxylic acid, 3,3'-methylene dibenzoic acid, 4,4'-methylene dibenzoic 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, 2,6-naphthalenedicarboxylic acid, phenylmalonic acid, benzylmalonic acid, phenylsuccinic acid, phenylglutaric acid, homophthalic acid, 1,3-phenylene diacetic acid, 1, 4-phenylene diacetic acid, 4-carboxyphenylacetic acid, 5-bromo-N- (carbomethyl) anthranilic acid, 3,3′-bis (4-carboxylphenyl) propane, bis (4-carboxylphenyl) methane,
3,3'-bis (4-carboxylphenyl) hexafluoropropane, 3,5-dicarboxybenzenesulfonic acid, 3,4-dicarboxybenzenesulfonic acid, 5-
Hydroxyisophthalic acid, 4-hydroxyisophthalic acid, 2-hydroxyisophthalic acid, 4,6-dihydroxyisophthalic acid, 2,5-dihydroxy-1,4-benzenediacetic acid, 4-hydroxy-2,5-dicarboxypyridine, Examples thereof include, but are not limited to, 2-hydroxyterephthalic acid. These may be used alone or in combination.

The block copolymer constituting the present invention is preferably used because the dicarboxylic acid component has a dicarboxylic acid having a phenolic hydroxyl group as a raw material, so that it can be molecularly complex with an epoxy resin.

The aromatic diamine component used in the phenolic hydroxyl group-containing polyamide-polybutadiene acrylonitrile block copolymer (1) used in the present invention includes, for example, m-phenylenediamine, p-phenylenediamine, and m-phenylenediamine. Tolylenediamine, 4,4'-diaminodiphenyl ether, 3,3'-dimethyl-4,
4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylthioether, 3,3'-dimethyl-4,4'-diaminodiphenylthioether, 3,3 '-Diethoxy-4,4'-diaminodiphenyl ether, 1,4-naphthalenediamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine, benzidine, 3,3'-dimethylbenzidine, 3,3'-dimethoxybenzidine 3,3'-dihydroxy-4,4'-diaminobiphenyl, 3,3'-
Diaminobiphenyl, m-xylylenediamine, p-xylylenediamine, 1,3-bis (methaminophenyl) -1,1,3,3-tetramethyldisiloxane,
4,4'-diaminodiphenylsulfoxide, 4,4 '
-Diaminodiphenyl sulfone, 4,4'-bis (3-
Aminophenoxy) diphenylsulfone, 4,4'-bis (4-aminophenoxy) diphenylsulfone, 3,
3'-diaminodiphenyl sulfone, 1,3-bis (4
-Aminophenoxy) benzene, 4,4'-diaminobenzophenone, 3,3'-dimethyl-4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 4,4'-bis (4-aminophenoxy) benzophenone 4,4'-bis (3-aminophenoxy) benzophenone, 4,4'-bis (4-aminophenylmercapto) benzophenone, 2,2'-bis (3-aminophenyl) propane, 2,2'-bis (4-aminophenyl) propane, 2,2'-bis (4-aminophenyl) hexafluoropropane, 2,2'-bis (4-
(4-aminophenoxy) phenyl) hexafluoropropane, 2,2'-bis (4-hydroxy-3-aminophenyl) hexafluoropropane, 2,2'-bis (4- (2-trifluoromethyl-4- Aminophenoxy) phenyl) hexafluoropropane, 2,2'-bis (4- (2-trifluoromethyl-5-aminophenoxy) phenyl) hexafluoropropane, 2,2'-
Bis (4- (3-trifluoromethyl-4-aminophenoxy) phenyl) hexafluoropropane, 2,2 '
-Bis (4- (3-trifluoromethyl-5-aminophenoxy) phenyl) hexafluoropropane, 2,
2'-bis (4- (4-trifluoromethyl-5-aminophenoxy) phenyl) hexafluoropropane,
2,2'-bis (4- (2-nonafluorobutyl-5-
Aminophenoxy) phenyl) hexafluoropropane, 2,2'-bis (4- (4-nonafluorobutyl-
5-aminophenoxy) phenyl) hexafluoropropane, 4,4'-diaminodiphenylmethane, 3,3 '
-Dimethoxy-4,4'-diaminodiphenylmethane,
3,3'-diaminodiphenylmethane, 2,5-diaminopyridine, bis (4-amino-3-methylphenyl)
Methane, bis (4-amino-3,5-dimethylphenyl) methane, bis (4-amino-3-ethylphenyl)
Methane, bis (4-amino-3-ethyl-5-methylphenyl) methane, bis (4-amino-3,5-diethylphenyl) methane, bis (4-amino-3-propylphenyl) methane, bis (4 -Amino-3,5-dipropylphenyl) methane, bis (4-amino-3-isopropylphenyl) methane, bis (4-amino-3,5-diisopropylphenyl) methane, bis (4-amino-
Examples thereof include 2,3-dimethylphenyl) methane and bis (4-amino-2,5-dimethylphenyl) methane, but are not limited thereto. These may be used alone or in combination.

In the polybutadiene acrylonitrile copolymer having a carboxyl group at both ends used in the phenolic hydroxyl group-containing polyamide-polybutadiene acrylonitrile block copolymer (1) used in the present invention, the stereochemical structure of the double bond May have a cis structure or a trans structure. The average degree of polymerization Z is preferably in the range of 5 to 15 in consideration of the physical properties such as the tensile strength and the tensile elasticity of the usually produced block copolymer.
Hycar CTBN manufactured by Ch.
These can be applied.

The phenolic hydroxyl group-containing polyamide-polybutadiene acrylonitrile block copolymer (1) used in the present invention preferably accounts for 20 to 50% by weight of the epoxy resin composition. When the amount is less than 20% by weight, the flexibility of the uncured epoxy resin composition sheet is poor, and when the amount is more than 50% by weight, the adhesiveness of the epoxy resin composition formed into a sheet is impaired, and practical use is not possible. In some cases.

The epoxy resin composition of the present invention comprises an epoxy resin, a curing agent, a phenolic hydroxyl group-containing polyamide-polybutadiene acrylonitrile block copolymer (1), and other necessary curing accelerators, such as acetone, methyl ethyl ketone, methyl isobutyl ketone. Ketone solvents, N, N-dimethylformamide, N, N
A varnish can be easily prepared by dissolving in a solvent such as N-dimethylacetamide, an amide solvent represented by N-methyl-2-pyrrolidone, toluene, or xylene, or a mixed solvent.

The epoxy resin composition adhesive sheet of the present invention is prepared such that the varnish containing the epoxy resin composition is applied to a polyethylene terephthalate film which has been subjected to a release treatment so that the applied thickness after drying is 5 to 100 μm. By coating and completely evaporating the solvent in the drying part, an epoxy resin composition adhesive sheet protected on one side by a polyethylene terephthalate film is obtained. Further, at the stage of passing through the drying part, an epoxy resin composition adhesive sheet protected on both sides is obtained by laminating a polyethylene terephthalate film which has been release-treated on the coated surface.

Furthermore, the laminated form of the epoxy resin composition adhesive sheet of the present invention is not limited to the one described in the above paragraph 0023. For example, an epoxy resin composition adhesive sheet having a substrate disposed on one side, An epoxy resin composition adhesive sheet in which a base material is disposed on both sides, and an epoxy resin composition adhesive sheet in which an epoxy resin composition layer is formed on both surfaces of a base material, may be used. As the base material, copper foil, metal foil represented by aluminum foil, polyimide film, polyethylene terephthalate film, polybutylene terephthalate film,
Examples thereof include a polymer film typified by a polyamide film, but are not limited thereto, and different base materials may be used in combination.

The epoxy resin composition adhesive sheet of the present invention includes an uncured or semi-cured state after drying and a state cured by heating. Drying condition is 100
The reaction is carried out at a temperature of about 200 ° C. for a time period of about 1 to 900 seconds, but can be appropriately adjusted by adjusting the boiling point and the curing state of the solvent used. The curing condition is performed at a temperature of 100 to 200 ° C. for a range of 1 to 180 minutes, and it is possible to select a curing condition suitable for a use purpose such as performing each temperature condition several times. There are no restrictions on it.

Although the epoxy resin composition adhesive sheet of the present invention can be produced by the above method, other additives can be added to the epoxy resin composition as required.
For example, plasticizers such as natural waxes, synthetic waxes and metal salts of long-chain aliphatic acids, acid amides, esters,
Release agents such as paraffins, stress relievers such as nitrile rubber and butadiene rubber, flame retardants such as chlorinated paraffin, bromobenzene, antimony trioxide, silane coupling agents, titanate coupling agents, fused silica, glass Flakes, glass beads, glass balloons, talc,
Alumina, calcium silicate, aluminum hydroxide, calcium carbonate, barium sulfate, magnesia, silicon nitride, boron nitride, ferrite, rare earth cobalt, gold, silver,
Metal powders such as nickel, copper, lead, iron powder, iron oxide, iron sand, etc., inorganic fillers such as graphite, carbon, red iron oxide, graphite, etc. or conductive particles, coloring agents such as dyes and pigments, carbon fiber, glass fiber,
Boron fiber, silicon carbide fiber, alumina fiber,
Inorganic fibers such as silica-alumina fibers, polyamide fibers,
Organic fibers such as polyester fiber, cellulose fiber and carbon fiber, antioxidants, light stabilizers, moisture resistance improvers, thixotropic agents, diluents, defoamers, other resins, tackifiers, antistatic agents , A lubricant, an ultraviolet absorber and the like.

The epoxy resin composition adhesive sheet of the present invention can be used for an insulating layer for printed circuit boards, a sheet adhesive for electronic parts, an adhesive for IC sealing, coating, and the like.
Its usefulness is exhibited.

[0028]

EXAMPLES The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples.

<Synthesis of phenolic hydroxyl group-containing polyamide-polybutadiene acrylonitrile block copolymer> A 2-liter separable flask equipped with a mechanical stirrer, a reflux condenser, a thermometer, a calcium chloride tube, and a nitrogen inlet tube was prepared. 31,52 g of 3,4'-diaminodiphenyl ether (157.4 mmol
l), 3.73 g of 5-hydroxyisophthalic acid (2
0.5 mmol), 20.37 g of isophthalic acid (12
3.0 mmol), 7.8 g of calcium chloride, 2.6 g of lithium chloride, N, N-dimethylacetamide 3
30 g, pyridine 32 g, triphenyl phosphite 7
0 g was charged. Then, put the flask in an oil bath for 95
The mixture was stirred for 2 hours under a nitrogen atmosphere while being heated to ℃ to prepare a solution of a polyamide oligomer having an aminoaryl group at a terminal. Next, an acrylonitrile-butadiene copolymer (G) having carboxyl groups at both ends at x = 5, y = 1, and z = 11 was added to the obtained polyamide oligomer solution.
Goodrich Corp. Hycar CTBN13
00X8) A solution of 50 g (13.89 mmol) dissolved in 195 g of N, N-dimethylacetamide was added,
After further reacting in the reactor for 2 hours, it was cooled to room temperature.
The obtained reaction solution was put into 5 liters of methanol,
The content of the acrylonitrile-butadiene copolymer is about 5
0% by weight of a polyamide-polybutadiene acrylonitrile block copolymer was precipitated. The precipitate was further washed with methanol, purified, and dried to obtain a polyamide-polybutadiene acrylonitrile block copolymer of the present invention in a yield of 98%. The intrinsic viscosity of this block copolymer is 0.57 dl / g at 30 ° C. in a polymer solution concentration of 0.5 g / dl in N, N-dimethylacetamide.
Met. Further, the structure was confirmed by measuring an IR spectrum (KBr tablet method). As a result, an absorption based on an amide carbonyl group was observed at around 1650 cm @ -1 and an absorption based on a nitrile group was observed at around 2240 cm @ -1. It was confirmed that.

Example 1 The following components were stirred and mixed at room temperature to obtain a varnish of the epoxy resin composition of Example 1.・ Epoxy resin (Bisphenol A type epoxy resin, manufactured by Yuka Shell Epoxy Co., Ltd .; Epicoat 828 Epoxy equivalent: 190 ± 5, properties; liquid, viscosity: 12000-15000 cp (25 ° C.)) 55 g Curing agent (4 , 4'-diaminodiphenylmethane) ... 15 g-Phenolic hydroxyl group-containing polyamide-polybutadiene acrylonitrile block copolymer ... 30 g-Curing accelerator (2-ethyl-4-methylimidazole) ... 0.2 g-Solvent (2-butanone) ) ... 50 g (N, N-dimethylformamide) ... 50 g

Example 2 The following ingredients were stirred and mixed at room temperature to obtain a varnish of the epoxy resin composition of Example 2.・ Epoxy resin (cresol novolak type epoxy resin, manufactured by Toto Kasei Kogyo Co., Ltd .; trade name: YDCN-701 Epoxy equivalent: 215 ± 15, properties: solid) 47 g ・ Curing agent (novolak type phenol resin, manufactured by Showa Kogyo Kogyo Co., Ltd.) Brand name: BR G-558 Hydroxyl equivalent: 104) 23 g • Phenolic hydroxyl group-containing polyamide-polybutadiene acrylonitrile block copolymer 30 g • Curing accelerator (2-ethyl-4-methylimidazole) 0.2 g Solvent (2-butanone) 50 g (N, N-dimethylformamide) 50 g

Example 3 The following ingredients were stirred and mixed at room temperature to obtain a varnish of the epoxy resin composition of Example 3.・ Epoxy resin (Dimer acid-based epoxy resin, manufactured by Yuka Shell Epoxy Co., Ltd .; Epicoat 872 Epoxy equivalent: 650 ± 50) ... 60 g ・ Curing agent (Novolac type phenol resin, manufactured by Showa Kogyo Kogyo Co., Ltd.); BRG -558 hydroxyl equivalent: 104) 10 g phenolic hydroxyl group-containing polyamide-polybutadiene acrylonitrile block copolymer 30 g Curing accelerator (2-ethyl-4-methylimidazole) 0.3 g Solvent (2-butanone) ) ... 50 g (N, N-dimethylformamide) ... 50 g

Example 4 The following ingredients were stirred and mixed at room temperature to obtain a varnish of the epoxy resin composition of Example 4. Epoxy resin (Bisphenol A type epoxy resin, manufactured by Yuka Shell Epoxy Co., Ltd .; Epicoat 828 Epoxy equivalent: 190 ± 5, properties; liquid, viscosity: 12000-15000 cp (25 ° C.)) 23 g Epoxy resin (cresol Novolak type epoxy resin, manufactured by Toto Kasei Kogyo Co., Ltd .; YDCN-701 Epoxy equivalent: 215 ± 15, properties: solid) 23 g ・ Curing agent (novolac type phenol resin, manufactured by Showa Kogyo Kogyo Co., Ltd.); BR G -558 hydroxyl equivalent: 104) 24 g phenolic hydroxyl group-containing polyamide-polybutadiene acrylonitrile block copolymer 30 g Curing accelerator (2-ethyl-4-methylimidazole) 0.2 g Solvent (2-butanone) ) ... 50 g (N, N-dimethylformamide) ... 50 g

Example 5 The following ingredients were stirred and mixed at room temperature to obtain a varnish of the epoxy resin composition of Example 5.・ Epoxy resin (Bisphenol A type epoxy resin, manufactured by Yuka Shell Epoxy Co., Ltd .; Epicoat 828 Epoxy equivalent: 190 ± 5, properties; liquid, viscosity: 12000-15000 cp (25 ° C.)) 50 g ・ Curing agent (Novolak) Type phenolic resin, manufactured by Showa Kogyo Kogyo Co., Ltd .; BR G-558, hydroxyl equivalent: 104) ... 27 g-Phenolic hydroxyl group-containing polyamide-polybutadiene acrylonitrile block copolymer ... 12 g-Polyether sulfone (Sumitomo Chemical Industries, Ltd.) Brand name; PES5003P) ··· 11 g · Curing accelerator (2-ethyl-4-methylimidazole) ··· 0.2 g · Solvent (2-butanone) ··· 50 g (N, N-dimethylformamide) ··· 50 g

Example 6 The following components were stirred and mixed at room temperature to obtain a varnish of the epoxy resin composition of Example 6.・ Epoxy resin (Bisphenol A type epoxy resin, manufactured by Yuka Shell Epoxy Co., Ltd .; Epicoat 828 Epoxy equivalent: 190 ± 5, properties; liquid, viscosity: 12000-15000 cp (25 ° C.)) 30 g ・ Curing agent (Novolak) -Type phenolic resin, Showa Kogaku Kogyo Co., Ltd .; trade name; BR G-558, hydroxyl equivalent: 104) ... 15 g-phenolic hydroxyl group-containing polyamide-polybutadiene acrylonitrile block copolymer ... 55 g-curing accelerator (2-ethyl- 4-methylimidazole) 0.1 g Solvent (2-butanone) 50 g (N, N-dimethylformamide) 50 g

Example 7 The following components were stirred and mixed at room temperature to obtain a varnish of the epoxy resin composition of Example 7.・ Epoxy resin (Bisphenol A type epoxy resin, manufactured by Yuka Shell Epoxy Co., Ltd .; Epicoat 828 Epoxy equivalent: 190 ± 5, properties; liquid, viscosity: 12000-15000 cp (25 ° C.)) 50 g ・ Curing agent (Novolak) -Type phenolic resin, manufactured by Showa Kogyo Kogyo Co., Ltd .; trade name: BR G-558, hydroxyl equivalent: 104) ... 27 g-phenolic hydroxyl group-containing polyamide-polybutadiene acrylonitrile block copolymer ... 23 g-curing accelerator (2-ethyl- 4-methylimidazole) ... 0.2 g Solvent (2-butanone) ... 50 g (N, N-dimethylformamide) ... 50 g

Comparative Example 1 The following components were stirred and mixed at room temperature to obtain a varnish of the epoxy resin composition of Comparative Example 1.・ Epoxy resin (cresol novolak type epoxy resin, manufactured by Toto Kasei Kogyo Co., Ltd .; product name: YDCN-701 Epoxy equivalent: 215 ± 15, properties: solid) 67 g ・ Curing agent (novolak type phenol resin, manufactured by Showa Kogyo Kogyo Co., Ltd.) Brand name: BR G-558 Hydroxyl equivalent: 104) 33 g Curing accelerator (2-ethyl-4-methylimidazole) 0.2 g Solvent (2-butanone) 50 g (N, N-dimethylformamide) 50g

Comparative Example 2 The following components were stirred and mixed at room temperature to obtain a varnish of the epoxy resin composition of Comparative Example 2.・ Epoxy resin (Bisphenol A type epoxy resin, manufactured by Yuka Shell Epoxy Co., Ltd .; Epicoat 828 Epoxy equivalent: 190 ± 5, properties; liquid, viscosity: 12000-15000 cp (25 ° C.)) 45 g ・ Curing agent (Novolak) Type phenolic resin, Showa Kogaku Kogyo Co., Ltd., trade name; BR G-558, hydroxyl equivalent: 104) ... 25 g ・ Polyethersulfone (Sumitomo Chemical Co., Ltd., trade name: PES5003P) ... 30 g ・ Curing accelerator (2-ethyl) -4-methylimidazole) ... 0.2 g Solvent (2-butanone) ... 10 g (N, N-dimethylformamide) ... 90 g

Comparative Example 3 The following components were stirred and mixed at room temperature to obtain an epoxy resin varnish of Comparative Example 3.・ Epoxy resin (Bisphenol A type epoxy resin, manufactured by Yuka Shell Epoxy Co., Ltd .; Epicoat 828 Epoxy equivalent: 190 ± 5, properties; liquid, viscosity: 12000-15000 cp (25 ° C.)) 45 g ・ Curing agent (Novolak) Type phenolic resin, trade name, Showa Kogaku Kogyo Co., Ltd .; BR G-558, hydroxyl equivalent: 104) 25 g phenoxy resin (trade name, YP-50, manufactured by Toto Kasei Kogyo Co., Ltd.) 30 g Curing accelerator (2-ethyl) -2-methylimidazole) ... 0.2 g Solvent (2-butanone) ... 20 g (N, N-dimethylformamide) ... 80 g

<Evaluation of Uncured Epoxy Resin Composition Adhesive Sheet> The varnish of each of the above Examples and Comparative Examples was dried on a polyethylene terephthalate (PET) film that had been subjected to a mold release treatment. It was cast to a thickness of about 40 μm and dried at 150 ° C. for 5 minutes using a hot air drier. Next, the epoxy resin composition adhesive sheet was obtained by carefully peeling off the PET film. This sheet was measured for a 0.1% weight loss temperature using a thermogravimeter (TGA). As a result, it was confirmed that all sheets had a temperature of 200 ° C. or higher, and that the solvent was completely removed. did. The cured state was confirmed by evaluating the solvent solubility of this epoxy resin composition adhesive sheet, and the flexibility was evaluated by a bending test. The solubility of the solvent was determined by dispersing 5% by weight of only the adhesive sheet excluding the base material in methyl ethyl ketone and checking the cured state by the solubility. The evaluation results are as shown in Table 1.は indicates dissolution, △ indicates partial dissolution, and × indicates insoluble. The flexibility is evaluated by a bending test in which only the adhesive sheet excluding the base material is bent at 180 degrees. Δ is divided by repetition. X shows that it is broken by the first bending.

[0041]

[Table 1]

<Evaluation of Cured Product of Epoxy Resin Composition Adhesive Sheet> The varnish of the above example was subjected to release treatment of PE.
The film was cast on a T film so as to have a thickness after drying of about 40 μm, and dried at 150 ° C. for 5 minutes in a warm air dryer. Further, after curing by heating at 150 ° C. for 2 hours, PET
By peeling from the film, a cured product of the epoxy resin composition adhesive sheet was obtained. In the cured product of the epoxy resin composition adhesive sheet, the curability was confirmed by evaluating the solvent solubility by the method described above, and the flexibility was evaluated by a bending test by the method. In addition, a dynamic viscoelasticity test (trade name, manufactured by Orientic; Leo Vibron DDV-
(Type II) was used to evaluate the heat resistance (glass transition temperature). The conditions in this case are a frequency of 11 Hz and a heating rate of 3 ° C./mi.
n, the test piece size was 30 mm × 4 mm × 0.04 mm. Table 2 shows the evaluation results. In addition, the mark 硬化 of the curability in Table 2 indicates one having good curability (insoluble in a solvent).

[0043]

[Table 2]

<Evaluation of Adhesive Strength of Epoxy Resin Composition Adhesive Sheet> The varnish of each of Examples and Comparative Examples was dried on a PET film subjected to a release treatment to a thickness of about 40 μm.
Cast in a hot air drier at 150 ° C for 5
Dried for minutes. By peeling off the PET film, an uncured epoxy resin composition adhesive sheet was obtained. This epoxy resin composition adhesive sheet is sandwiched between rough surfaces of two copper foils (trade name: VLP-3EC, manufactured by Mitsui Kinzoku Mining Co., Ltd.) and 10K
Under a pressure of g / cm ^2, the sample was bonded under pressure and heat at a temperature of 150 ° C. to prepare a T-peel test sample. The adhesive strength was measured by a tensile tester (trade name, manufactured by Orientic; Tensilon UCT-500). Table 3 shows the measurement results.

[0045]

[Table 3]

The results of the above Tables 1 to 3 are summarized as follows. From the results in Table 1, the uncured films of Examples 1 to 7 showed excellent flexibility in bending and excellent flexibility, whereas the uncured films of Comparative Examples 1 to 3 caused cracking even with slight bending. It was a very brittle film. From the results in Table 2, the cured film of the sheet of Comparative Example 1 was not flexible. Furthermore, from the results in Table 3, the adhesive strengths of the epoxy resin compositions of Examples 1 to 7 are sufficiently higher than those of Comparative Examples 1 to 3. That is, from these results, the epoxy resin composition containing the phenolic hydroxyl group-containing polyamide-polybutadiene acrylonitrile block copolymer can produce a self-supporting sheet in an uncured state, and has high adhesive strength and heat resistance. It became clear that it had the property.

[0047]

The epoxy resin composition containing the phenolic hydroxyl group-containing polyamide-polybutadiene acrylonitrile block copolymer of the present invention has an uncured state as compared with the epoxy resin composition containing other polymer materials. A self-supporting epoxy resin composition adhesive sheet can be easily produced, and the sheet material has both high adhesive strength and heat resistance.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4J004 AA05 AA07 AA12 AA13 AA16 AA17 AB05 CA06 CA08 CC02 EA05 FA05 4J036 AA01 AD08 DB15 DB22 DB23 DC06 DC10 DC27 DC31 DC35 DC39 DC41 DC46 DD02 DD05 DD07 FB05 FB07 DM19 EB032 EC001 EC061 EC062 EC091 EC092 EC121 EC122 GA05 JA09 KA16 LA01 LA06 LA08

Claims (4)

[Claims] 1. An epoxy resin composition adhesive comprising at least an epoxy resin, an epoxy resin curing agent and a phenolic hydroxyl group-containing polyamide-polybutadiene acrylonitrile block copolymer represented by the general formula (1) as main components. Sheet. Embedded image Wherein Ar ¹ and Ar ² represent a divalent aromatic group;
r ³ represents a divalent aromatic group having a phenolic hydroxyl group. X, Y, Z, and 1, n, and m are average polymerization degrees, respectively, where X = 3 to 7, Y = 1 to 4, Z = 5 to 15,
m represents an integer of 2 to 300, and n / (n + 1) ≧ 0.0
4. In addition, each of the block units (A) and (B) exists in the range of 1 to 20. ｝ 2. The epoxy resin composition adhesive sheet according to claim 1, wherein the proportion of the block copolymer in the epoxy resin composition is 20 to 50% by weight. 3. The method according to claim 2, wherein the epoxy resin is in a liquid state and is heated at 25 ° C.
3. The epoxy resin composition adhesive sheet according to claim 1, wherein the viscosity value of the epoxy resin composition is 100,000 centipoise or less, and the proportion of the epoxy resin composition in the epoxy resin composition is 50% by weight or less. 4. 4. The epoxy resin composition adhesive sheet according to claim 1, wherein the curing agent is a novolak type phenol resin.