JP2001049082A - Epoxy resin composition, its varnish, filmy adhesive using the same and its cured substance - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a soft adhesive excellent in storage stability, bonding strength, resistance, to heat and moisture, stress relaxation and productibility. SOLUTION: The epoxy resin composition comprises an epoxy resin (A), a curing agent (B) and a block copolymer (C) formed from an aromatic polyamide oligomer containing a phenolic hydroxyl group and having amino aryl groups at both the terminals and a polybutadiene/acrylonitrile copolymer having carboxyl groups at both the terminals Desirably, a content of the block copolymer (C) is 5 to 100 pts.wt. per 100 pts.wt. of the epoxy resin.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition having good adhesion to polyimide, a sheet having a layer of this resin composition, and a sheet-like adhesive, and more particularly, to sealing of a semiconductor such as a flip chip. Resin composition that is suitable for use, particularly for bonding polyimide to a semiconductor such as a tape carrier package based on polyimide, and also acting as a sealing material for the semiconductor, and a sheet and a sheet having a layer of this resin composition For adhesives.

[0002]

2. Description of the Related Art Recent technological advances in the information and communication fields have been remarkable as seen in the progress of the Internet. This is due to technological advances and integration of technology in the three fields of computer, communication and broadcasting.
The development of small and high-capacity semiconductor devices is essential for the development of innovative technologies in these fields. It is no exaggeration to say that the development of semiconductor devices is a history of high capacity and miniaturization, and strong demands for high storage capacity and miniaturization have increased the technology of high performance and miniaturization of semiconductors.

In response to the demand for small, high-performance, and low-cost semiconductor devices, a processing method called flip-chip bonding in which a semiconductor bare chip is directly mounted on a substrate, and a mounting area can be made substantially equal to that of a single chip. A CSP (chip size package) processing method in which electrodes are arranged in a plane has become mainstream. In the assembly of a semiconductor device, a surface mounting method in which the entire surface of the semiconductor rises to a solder melting temperature is employed. In the surface mounting, the stress applied to the semiconductor element at the time of soldering is very large, and if the sealing resin composition of the semiconductor contains moisture, the moisture evaporates due to the high temperature of the solder and generates high pressure. In addition, it may cause damage to the semiconductor device.

Conventionally, resin sealing has been performed to absorb stress during processing and protect the semiconductor from the outside. That is, the purpose is to relieve the stress caused by the difference in thermal expansion during the processing of the semiconductor chip with the resin. However, with the rapid trend toward miniaturization of semiconductors, the concept of the role of resin sealing has naturally changed, and it has become necessary to take into account not only the concept of simple sealing but also functions such as adhesiveness.

A liquid adhesive is usually used as an adhesive for attaching a semiconductor to a substrate by a processing method such as the above-mentioned flip chip bonding or CSP, but a tape-like adhesive tape has recently been proposed. On the other hand, in order to reduce the size of a semiconductor device, it is necessary to precisely bond the semiconductor to a substrate or the like, so that dimensional accuracy of the adhesive is required. In the case of a liquid adhesive, since it is liquid, it easily flows, it is difficult to secure dimensional accuracy at the time of bonding, and productivity (workability) is poor. Regardless of liquid or tape, ordinary adhesives need to be quickly cured after application, but this adversely affects the storage stability of the adhesives. There is a problem that must be saved. Further, in assembling a semiconductor device, different materials such as a substrate and a semiconductor must be bonded. However, for example, a polyimide film is often used from the viewpoint of heat resistance as a base material of a tape carrier package that has recently attracted attention as a small semiconductor package, but the conventional adhesive has excellent adhesiveness to polyimide,
Moreover, there is nothing excellent in heat resistance. Further, it is necessary to relieve the stress on the semiconductor due to heat at the time of assembling the semiconductor device and at the time of using the semiconductor device. However, the conventional adhesive loses its flexibility when cured, and cannot sufficiently fulfill the role of stress relaxation. . As described above, the conventional liquid or tape adhesive has problems in terms of dimensional accuracy, storage stability, adhesive strength, heat resistance and stress relaxation.

[0006]

There is a need for a flexible adhesive which is excellent in dimensional accuracy, storability, adhesive strength, stress relaxation, heat resistance, and productivity, corresponding to the miniaturization of semiconductor devices.

[0007]

Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, have found that an adhesive which simultaneously satisfies the above-mentioned properties can be obtained. That is, the present invention provides (1) an epoxy resin (A), a curing agent (B), a phenolic hydroxyl group-containing aromatic polyamide oligomer having aminoaryl groups at both ends, and a polybutadiene / acrylonitrile copolymer having a carboxyl group at both ends. Block copolymer (C) formed from coalescing
Epoxy resin composition containing, as an essential component, (2)
(1) The content of the block copolymer (C) is 5 to 100 parts by weight based on 100 parts by weight of the epoxy resin.
Epoxy resin composition, (3) block copolymer (C)
Is Equation 1

[0008]

Embedded image

(Where x, y, z, l, m and n are the respective average degrees of polymerization, x = 3 to 7, y = 1 to 4; z = 5 to 15; 1 + m is an integer of 2 to 200, and m / (m + 1) ≧ 0.04.) The epoxy resin composition according to (1) or (2), wherein (4) epoxy The epoxy resin composition according to any one of (1) to (3), wherein the resin (A) is a bifunctional epoxy resin, and (5) the epoxy resin (A) is a glycidyl ether type epoxy resin (1). Or (4)
The epoxy resin composition according to any one of the above. (6) The epoxy resin composition according to (5), wherein the glycidyl ether type epoxy resin is a bisphenol A type epoxy resin.
(7) The epoxy resin composition according to (5), wherein the glycidyl ether type epoxy resin is a bisphenol F type epoxy resin. (8) The epoxy resin composition according to (5), wherein the glycidyl ether type epoxy resin is a phenol novolak type epoxy resin. (9) The epoxy resin composition according to (8), wherein the phenol novolak epoxy resin is a novolak epoxy resin having a methyl group in a phenol skeleton. (10) The epoxy resin composition according to (5), wherein the glycidyl ether type epoxy resin is a novolak type epoxy resin having a phenol skeleton and a naphthol skeleton. (11) The epoxy resin composition according to claim 10, wherein the novolak epoxy resin having a phenol skeleton and a naphthol skeleton is a novolak epoxy resin having a methyl group in the phenol skeleton. (12) The epoxy resin composition according to (5), wherein the glycidyl ether type epoxy resin is a novolak type epoxy resin having a phenol skeleton and a biphenyl skeleton. (13) The epoxy resin composition according to (5), wherein the glycidyl ether type epoxy resin is a novolak type epoxy resin having a triphenylmethane skeleton. (14) The epoxy resin composition according to (5), wherein the glycidyl ether type epoxy resin is a novolak type epoxy resin having a dicyclopentadiene skeleton.
(15) The epoxy resin composition according to any one of (1) to (14), wherein the epoxy resin is solid at room temperature.
(16) The epoxy resin composition according to any one of (1) to (15), wherein the curing agent (C) is a phenolic curing agent, and (17) any one of (1) to (16). (18) a varnish composition obtained by dissolving the epoxy resin composition according to (1) in a solvent, (18) the epoxy resin composition according to any one of (1) to (16), on both surfaces or one surface of the planar support. (19) The sheet according to (18), wherein the planar support is a polyimide film.
(20) The sheet according to (18), wherein the planar support is a metal foil, (21) the sheet according to (18), wherein the planar support is a release film, (22) (1) to (16).
A sheet adhesive having release film layers on both sides of a layer of the epoxy resin composition according to any one of the above.

[0010]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The epoxy resin composition of the present invention comprises:
A block formed from an epoxy resin (A), a curing agent (B), a phenolic hydroxyl group-containing aromatic polyamide oligomer having aminoaryl groups at both terminals, and a polybutadiene / acrylonitrile copolymer having a carboxyl group at both terminals. A copolymer (C).

The epoxy resin (A) used in the present invention includes, for example, a polyfunctional epoxy resin which is a glycidyl etherified product of a polyphenol compound, a polyfunctional epoxy resin which is a glycidyl etherified product of various novolak resins, an alicyclic epoxy resin, Examples include a heterocyclic epoxy resin, a glycidyl ester epoxy resin, a glycidylamine epoxy resin, and an epoxy resin in which a halogenated phenol is glycidylated. Here, the polyfunctional epoxy resin is an epoxy resin having two or more glycidyl groups.

Examples of the polyfunctional epoxy resin which is a glycidyl ether compound of a polyphenol compound include bisphenol A, bisphenol F, bisphenol S, 4,4'-biphenylphenol, tetramethylbisphenol A, dimethylbisphenol A, and tetramethylbisphenol F. , Dimethylbisphenol F, tetramethylbisphenol S, dimethylbisphenol S, tetramethyl-4,4'-biphenol, dimethyl-4,4'-biphenylphenol, 1- (4-hydroxyphenyl) -2- [4- (1 , 1-bis- (4-hydroxyphenyl) ethyl) phenyl] propane, 2,
2′-methylene-bis (4-methyl-6-tert-butylphenol), 4,4′-butylidene-bis (3-
Methyl-6-tert-butylphenol), trishydroxyphenylmethane, resorcinol, hydroquinone, pyrogallol, phenols having a diisopropylidene skeleton, phenols having a fluorene skeleton such as 1,1-di-4-hydroxyphenylfluorene, phenol And polyfunctional epoxy resins which are glycidyl etherified products of polyphenol compounds such as polybutadiene.

Examples of polyfunctional epoxy resins which are glycidyl etherified compounds of various novolak resins include, for example, phenol, cresols, ethylphenols, butylphenols, octylphenols, bisphenol A,
Novolak resins, phenol novolak resins containing a xylylene skeleton, phenol novolak resins containing a dicyclopentadiene skeleton, phenol novolak resins containing a biphenyl skeleton, phenol novolak resins containing a fluorene skeleton, etc. made from various phenols such as bisphenol F, bisphenol S, and naphthols. Examples include glycidyl etherified products of various novolak resins.

Examples of the alicyclic epoxy resin include an alicyclic epoxy resin having an aliphatic skeleton such as cyclohexane. Examples of the aliphatic epoxy resin include 1,4-butanediol and 1,6-hexane. Diol,
Glycidyl ethers of polyhydric alcohols such as polyethylene glycol and pentaerythritol are mentioned.

The heterocyclic epoxy resin includes, for example, a heterocyclic epoxy resin having a heterocyclic ring such as an isocyanuric ring and a hydantoin ring. The glycidyl ester-based epoxy resin includes, for example, diglycidyl hexahydrophthalate and the like. Examples of the epoxy resin include carboxylic acids. Examples of the glycidylamine-based epoxy resin include epoxy resins obtained by glycidylation of amines such as aniline and toluidine.

Epoxy resins obtained by glycidylation of halogenated phenols include, for example, brominated bisphenol A, brominated bisphenol F, brominated bisphenol S, brominated phenol novolak, brominated cresol novolak, chlorinated bisphenol S, and chlorinated bisphenol. An epoxy resin obtained by glycidylation of a halogenated phenol such as A is exemplified.

Of these epoxy resins, bisphenol A, bisphenol F, bisphenol S, tetramethyl-4,4'-biphenol, 1- (4-hydroxyphenyl) -2- [4- (1,1-bis- ( 4-Hydroxyphenyl) ethyl) phenyl] propane, resorcinol, glycidyl etherified product of 1,1-di-4-hydroxyphenylfluorene, phenol, cresols, bisphenol A, bisphenol F, bisphenol S, novolak made from naphthols Glycidyl resins of various novolak resins such as resin, phenol novolak resin containing xylylene skeleton, phenol novolak resin containing dicyclopentadiene skeleton, phenol novolak resin containing biphenyl skeleton, and phenol novolak resin containing fluorene skeleton -Telluride, alicyclic epoxy resin having a cyclohexane ring, 1,6-hexanediol,
Glycidyl ethers of polyethylene glycol, triglycidyl isocyanurate, diglycidyl hexahydrophthalate, diglycidyl tetrahydrophthalate, N, N-diglycidylaniline, N, N-
Diglycidyl toluidine, brominated bisphenol A,
Brominated phenol novolak and glycidylated brominated cresol novolak are preferred.

More preferably, bisphenol A, bisphenol F, tetramethyl-4,4'-biphenol,
1- (4-hydroxyphenyl) -2- [4- (1,1
-Bis- (4-hydroxyphenyl) ethyl) phenyl] propane, resorcinol, glycidyl etherified product of 1,1-di-4-hydroxyphenylfluorene,
Glycidyl etherified phenolic novolak resin containing phenol, cresols, bisphenol A, naphthols, phenol novolak resin containing xylylene skeleton, phenol novolak resin containing dicyclopentadiene skeleton, phenol novolak resin containing biphenyl skeleton, and phenol novolak resin containing fluorene skeleton Alicyclic epoxy resin having a cyclohexane ring, hexahydrophthalic acid diglycidyl ester, tetrahydrophthalic acid diglycidyl ester, N, N-diglycidylaniline, N, N-diglycidyltoluidine, brominated bisphenol A, brominated phenol It is a glycidylated product of novolak, particularly preferably bisphenol A, bisphenol F, tetramethyl-4,4′-biphenol, resorcinol or Is a glycidyl etherified product of 1,1-di-4-hydroxyphenylfluorene, diglycidyl hexahydrophthalate, diglycidyl tetrahydrophthalate, N, N-diglycidylaniline, N, N-diglycidyltoluidine, etc. It is a functional epoxy resin. Further, these epoxy resins can be used as one kind or as a mixture of two or more kinds as required, for example, for imparting heat resistance. Among these epoxy resins, which epoxy resin is used is appropriately selected depending on required characteristics, but a bifunctional epoxy resin and a glycidyl ether type epoxy resin are preferable.

More preferably, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, novolak type epoxy resin having phenol skeleton and naphthol skeleton, phenol skeleton and biphenyl skeleton Novolak epoxy resins, novolak epoxy resins having a triphenylmethane skeleton, and novolak epoxy resins having a dicyclopentadiene skeleton. The novolak-type epoxy resin having a phenol skeleton and a naphthol skeleton is more preferably a resin having a methyl group in the phenol skeleton, for example, NC-700.
0 (trade name: manufactured by Nippon Kayaku Co., Ltd.) and NC-7300 (trade name: manufactured by Nippon Kayaku Co., Ltd.). A novolak-type epoxy resin having a phenol skeleton and a biphenyl skeleton is commercially available, for example, as NC-3000P (trade name, manufactured by Nippon Kayaku Co., Ltd.). Novolak-type epoxy resins having a triphenylmethane skeleton are commercially available, for example, as EPPN-501H and EPPN-502H (trade names, manufactured by Nippon Kayaku Co., Ltd.). A novolak epoxy resin having a dicyclopentadiene skeleton is, for example, XD-1000 (trade name: Nippon Kayaku Co., Ltd.)
Commercially available). Further, these epoxy resins can be used as one kind or as a mixture of two or more kinds as required, for example, for imparting heat resistance and flame retardancy.

The curing agent (B) used in the present invention includes acid anhydrides, amines, phenols and imidazoles. Examples of the acid anhydride include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride,
Benzophenone tetracarboxylic anhydride, ethylene glycol trimellitic anhydride, aromatic carboxylic anhydride such as biphenyltetracarboxylic anhydride, azelaic acid, sebacic acid, aliphatic carboxylic anhydride such as dodecane diacid, Tetrahydrophthalic anhydride, hexahydrophthalic anhydride, nadic anhydride, hetonic anhydride,
Alicyclic carboxylic acid anhydrides such as hymic acid anhydrides are exemplified.

Examples of amines used as curing agents include, for example, diaminodiphenylmethane, diaminodiphenylsulfone, diaminodiphenylether, p-phenylenediamine, m-phenylenediamine, o-phenylenediamine, 1,5-diaminonaphthalene, m-xylylenediene Aromatic amines such as amines, ethylenediamine, diethylenediamine, isophoronediamine, bis (4-amino-3-methyldicyclohexyl) methane,
Examples thereof include aliphatic amines such as polyetherdiamine, dicyanamide, and guanidines such as 1- (o-tolyl) biguanide.

Examples of the phenols used as a curing agent in the present invention include bisphenol A, bisphenol F, bisphenol S, 4,4'-biphenylphenol, tetramethylbisphenol A, dimethylbisphenol A, tetramethylbisphenol F, and dimethylbisphenol. F, tetramethylbisphenol S, dimethylbisphenol S, tetramethyl-4,4'-biphenol, dimethyl-4,4'-biphenylphenol, 1- (4-hydroxyphenyl) -2- [4-
(1,1-bis- (4-hydroxyphenyl) ethyl)
Phenyl] propane, 2,2′-methylene-bis (4-
Methyl-6-tert-butylphenol), 4,4 ′
-Butylidene-bis (3-methyl-6-tert-butylphenol), trishydroxyphenylmethane, resorcinol, hydroquinone, pyrogallol, phenols having a diisopropylidene skeleton, 1,1-di-
Phenols having a fluorene skeleton such as 4-hydroxyphenylfluorene, phenolized polybutadiene,
Novolak resins made from various phenols such as phenol, cresols, ethylphenols, butylphenols, octylphenols, bisphenol A, bisphenol F, bisphenol S, naphthols,
Various novolak resins such as xylylene skeleton-containing phenol novolak resin, dicyclopentadiene skeleton-containing phenol novolak resin, biphenyl skeleton-containing phenol novolak resin, fluorene skeleton-containing phenol novolak resin, brominated bisphenol A, brominated bisphenol F, brominated bisphenol S, Halogenated phenols such as brominated phenol novolak, brominated cresol novolak, chlorinated bisphenol S, and chlorinated bisphenol A are exemplified.

The imidazoles used as a curing agent in the present invention include, for example, 2-methylimidazole,
Phenylimidazole, 2-undecylimidazole,
2-heptadecylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-phenylimidazole, 1-benzyl-2-methylimidazole, 1-
Cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-
2-undecylimidazole, 2,4-diamino-6
(2′-methylimidazole (1 ′)) ethyl-s-triazine, 2,4-diamino-6 (2′-undecylimidazole (1 ′)) ethyl-s-triazine, 2,4
-Diamino-6 (2'-ethyl, 4-methylimidazole (1 ')) ethyl-s-triazine, 2,4-diamino-6 (2'-methylimidazole (1')) ethyl-
s-Triazine / isocyanuric acid adduct, 2-methylimidazole isocyanuric acid 2: 3 adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-
3,5-dihydroxymethylimidazole, 2-phenyl-4-hydroxymethyl-5-methylimidazole,
Various imidazoles of 1-cyanoethyl-2-phenyl-3,5-dicyanoethoxymethylimidazole, and those imidazoles and phthalic acid, isophthalic acid,
Salts with polyvalent carboxylic acids such as terephthalic acid, trimellitic acid, pyromellitic acid, naphthalenedicarboxylic acid, maleic acid, oxalic acid and the like can be mentioned. Among these curing agents, which curing agent is used is appropriately selected depending on the properties required for the adhesive, but is preferably an acid anhydride, a phenol, or an imidazole, and particularly preferably a phenol. The amount of the curing agent used is 0.3 to 2.0 in an equivalent ratio of the curing agent to the epoxy group of the epoxy resin.
, Preferably in the range of 0.4 to 1.6, more preferably in the range of 0.5 to 1.3. The curing agents may be used as a mixture of two or more, and the imidazoles are also used as a curing accelerator.

The block copolymer (C) used in the present invention is described in JP-A-6-299133, and comprises a phenolic hydroxyl group-containing aromatic polyamide oligomer having aminoaryl groups at both ends. It is obtained by reacting with a polybutadiene / acrylonitrile copolymer having a terminal carboxyl group.

The phenolic hydroxyl group-containing aromatic polyamide oligomer having aminoaryl groups at both terminals used as a raw material is synthesized by condensation polymerization of an aromatic diamine component and an aromatic dicarboxylic acid component. In the present invention, a phenolic hydroxyl group-containing aromatic polyamide oligomer can be produced by mixing an aromatic diamine or an aromatic dicarboxylic acid having a hydroxyl group into the aromatic diamine component or the aromatic dicarboxylic acid component.
In addition, conversion of both terminal groups of the oligomer to an aminoaryl group can be easily achieved by subjecting the aromatic diamine component to a polycondensation reaction in excess of the aromatic dicarboxylic acid component. Blocking with the polybutadiene / acrylonitrile copolymer having carboxyl groups at both ends synthesized in this manner can be similarly performed by the above-mentioned condensation polymerization. This polycondensation can be carried out by a conventionally known method. That is, the above-mentioned direct dehydration polycondensation polymerization method between the carboxyl group and the amino group, a polymerization method in which the carboxyl group is acid chlorided with thionyl chloride or the like and then reacted with an amine, and a polycondensation catalyst using a phosphite and pyridine are used. Synthetic methods are preferred.

The aromatic diamine used in the production of the phenolic hydroxyl group-containing aromatic polyamide oligomer includes m-phenylenediamine, p-phenylenediamine, m-tolylenediamine, 4,4'-diaminodiphenyl ether, 3,3 '-Dimethyl-4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylthioether, 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'-diaminodiphenylthioether, 2,
2′-bis (3-aminophenyl) propane, 2,2 ′
-Bis (4-aminophenyl) propane, 4,4'-diaminodiphenylsulfoxide, 4,4'-diaminodiphenylsulfone, benzidine, 3,3'-dimethylbenzidine, 3,3'-dimethoxybenzidine ,
3,3'-diaminobiphenyl, p-xylylenediamine, m-xylylenediamine, o-xylylenediamine, 2,2'-bis (3-aminophenoxyphenyl)
Propane, 2,2′-bis (4-aminophenoxyphenyl) propane, 1,3-bis (4-aminophenoxyphenyl) benzene, 1,3′-bis (3-aminophenoxyf) propane, 4,4 ′ -(P-phenylenediisopropylidene) bisaniline;
Species or a mixture of two or more species may be used.

The dicarboxylic acids used for producing the phenolic hydroxyl group-containing aromatic polyamide oligomer of the present invention include, for example, phthalic acid, isophthalic acid, terephthalic acid, 4,4'-oxydibenzoic acid, 4,4 ' -Biphenyldicarboxylic acid, 3,3'-, methylene dibenzoic acid, 4,4'-methylene dibenzoic acid, 4,4'-thiodibenzoic acid, 3,3'-carbonyl dibenzoic acid, 4,4 '
-Carbonyl dibenzoic acid, 4,4'-sulfonyl dibenzoic acid, 1,5-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 1,2-naphthalenedicarboxylic acid, etc. Is not limited to these.

The hydroxyl-containing aromatic dicarboxylic acid or hydroxyl-containing aromatic diamine used to introduce a phenolic hydroxyl group into the aromatic polyamide oligomer of the present invention includes 5-hydroxyisophthalic acid, 4-hydroxyisophthalic acid, and the like. 2-hydroxyisophthalic acid, 3-
Hydroxyisophthalic acid, 2-hydroxyterephthalic acid, 3,3′-dihydroxy-4,4′-dianiline,
2,2-bis (3'-amino-4-hydroxyphenyl) propane, 2,4-dihydroxy-1,5-diaminobenzene, 5-hydroxy-1,3-diaminobenzene and the like can be used. However, the present invention is not limited to these.

The block copolymer (C) used in the present invention, which is formed from a phenolic hydroxyl group-containing aromatic polyamide oligomer having an aminoaryl group at both terminal groups and a polybutadiene / acrylonitrile copolymer containing both terminal carboxyl groups. Is represented by the structure of the formula (1). Considering physical properties such as tensile strength and tensile modulus of the obtained block copolymer, the average degree of polymerization x, y, z,
l, m and n are x = 3-7, y = 1-4, z = 5-1
5, l + m = integer of 2 to 200, m / (m
+1) ≧ 0.04 are preferred.

In the present invention, the phenolic hydroxyl group-containing aromatic polyamide-polybutadiene / acrylonitrile block copolymer (C) is used in an amount of 100 parts by weight of epoxy resin.
2 to 150 parts by weight, preferably 4 to 12 parts by weight based on parts by weight
0 parts by weight, more preferably 5 to 100 parts by weight. 2
If the amount is less than 150 parts by weight, the heat resistance is inferior.

A curing accelerator may be used in the epoxy resin composition of the present invention. Examples of the curing accelerator include 2-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenyl-4-methylimidazole,
1-benzyl-2-phenylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2
-Methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole, 2,4-diamino-6 (2′-methylimidazole (1 ′)) ethyl-s-triazine, 2,4 −
Diamino-6 (2′-undecylimidazole (1 ′)) ethyl-s-triazine, 2,4-diamino-6 (2′-ethyl, 4-methylimidazole (1 ′)) ethyl-s-triazine, , 4-Diamino-6 (2'-methylimidazole (1 ')) ethyl-s
-Triazine / isocyanuric acid adduct, 2-methylimidazole isocyanuric acid 2: 3 adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-
3,5-dihydroxymethylimidazole, 2-phenyl-4-hydroxymethyl-5-methylimidazole,
Various imidazoles of 1-cyanoethyl-2-phenyl-3,5-dicyanoethoxymethylimidazole, and those imidazoles and phthalic acid, isophthalic acid,
Salts with polycarboxylic acids such as terephthalic acid, trimellitic acid, pyromellitic acid, naphthalenedicarboxylic acid, maleic acid and oxalic acid; amides such as dicyandiamide;
Diaza compounds such as diaza-bicyclo (5.4.0) undecene-7 and their phenols, salts with the above-mentioned polycarboxylic acids or phosphinic acids, phosphines such as triphenylphosphine and tetraphenylphosphoniumtetraphenylborate; And phenols such as 2,4,6-trisaminomethylphenol, amine adducts, and microcapsule-type curing accelerators in which these curing agents are microencapsulated. Which of these curing accelerators is used is appropriately selected depending on the characteristics required for the obtained epoxy resin composition.

A filler may be used in the epoxy resin composition of the present invention. As fillers, fused silica, crystalline silica, silicon carbide, silicon nitride, boron nitride, calcium carbonate, magnesium carbonate, barium sulfate, calcium sulfate, mica, talc, clay, alumina, magnesium oxide, zirconium oxide, aluminum hydroxide,
Magnesium hydroxide, calcium silicate, aluminum silicate, lithium aluminum silicate, zirconium silicate, barium titanate, glass fiber, carbon fiber, molybdenum disulfide, asbestos and the like, preferably fused silica,
Crystalline silica, silicon nitride, boron nitride, calcium carbonate,
Barium sulfate, calcium sulfate, mica, talc, clay, alumina, aluminum hydroxide. The particle size of these fillers is 80% by weight or more, preferably 85% by weight or more, and more preferably 90% by weight or more, when the average particle size is 20 μm or less. When the content is less than 80% by weight, when the epoxy resin composition is formed into a film, there is a problem in smoothness such as a rough surface. These fillers may be used alone or in a combination of two or more.

In the epoxy resin composition of the present invention, a flame retardant, a coloring agent, a coupling agent, a leveling agent and the like can be appropriately added according to the purpose. Examples of the flame retardant include inorganic flame retardants such as antimony trioxide, antimony pentoxide, tin oxide, tin hydroxide, molybdenum oxide, zinc borate, barium metaborate, red phosphorus, aluminum hydroxide, magnesium hydroxide, and calcium aluminate; Brominated flame retardants such as bromobisphenol A, tetrabromophthalic anhydride, hexabromobenzene, decabromobiphenyl ether, and brominated phenol novolak; and phosphoric flame retardants such as tris (tribromophenyl) phosphate. Further, the colorant is not particularly limited, phthalocyanine, azo, disazo, quinacridone, anthraquinone,
Flavantron, perinone, perylene, dioxazine,
Inorganic pigments such as condensed azo and azomethine organic dyes, titanium oxide, lead sulfate, chrome yellow, zinc yellow, chrome vermillion, valve shell, cobalt purple, navy blue, ultramarine blue, carbon black, chrome green, chromium oxide, and cobalt green Is mentioned.

As coupling agents, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyl Trimethoxysilane, N- (2-
(Aminoethyl) 3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) 3-aminopropylmethyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, vinyltrimethoxysilane, N Silane-based cups such as-(2- (vinylbenzylamino) ethyl) 3-aminopropyltrimethoxysilane hydrochloride, 3-methacryloxypropyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane Ring agent, isopropyl (N-ethylaminoethylamino) titanate, isopropyl triisostearoyl titanate, titanium di (dioctyl pyrophosphate) oxyacetate, tetraisopropyl di (dioctyl phosphate) Site) titanate, neoalkoxy tri (p-N- (β- aminoethyl) aminophenyl)
Titanium-based coupling agents such as titanate, Zr-acetylacetonate, Zr-methacrylate, Zr-propionate, neoalkoxy zirconate, neoalkoxytris neodecanoyl zirconate, neoalkoxytris (dodecanoyl) benzenesulfonyl zirconate, neoalkoxy Tris (ethylenediaminoethyl) zirconate, neoalkoxytris (m-aminophenyl) zirconate, ammonium zirconium carbonate, Al-acetylacetonate, Al-methacrylate, zirconium such as Al-propionate, or an aluminum-based coupling agent. Preferred is a silicon-based coupling agent. By using a coupling agent, a cured product having excellent moisture resistance reliability and a small decrease in adhesive strength after moisture absorption can be obtained.

As the leveling agent, acrylates such as ethyl acrylate, butyl acrylate and 2-ethylhexyl acrylate having a molecular weight of 4000 to 12 are used.
000 oligomers, epoxidized soybean fatty acid, epoxidized aviethyl alcohol, hydrogenated castor oil, titanium-based coupling agent, modified silicone, anionic / nonionic surfactant, and the like.

In order to prepare the epoxy resin composition of the present invention, for example, an epoxy resin (A), a curing agent (B), a phenolic hydroxyl group-containing aromatic polyamide oligomer having aminoaryl groups at both terminals and a carboxyl group at both terminals. A block copolymer (C) formed from a polybutadiene / acrylonitrile copolymer having a group, if necessary, a curing accelerator, a filler, a coupling agent, a flame retardant, a colorant,
The compounding ingredients such as a leveling agent are mixed using a Henschel mixer, a planetary mixer or the like, and then uniformly dispersed using a two-roll, kneader, extruder, sand grinder, or the like to obtain the epoxy resin composition of the present invention.
When the obtained product is a solid, the mixture is solidified by cooling and finely pulverized to obtain the epoxy resin composition of the present invention.

The varnish of the epoxy resin composition of the present invention comprises:
It is obtained by dissolving the above-described epoxy resin, curing agent, and phenolic hydroxyl group-containing aromatic polyamide-polybutadiene / acrylonitrile block copolymer in a solvent.
Further, the epoxy resin composition once dispersed by the above method may be dissolved in a solvent. As the solvent used, for example, γ-butyrolactones, N-methylpyrrolidone (N
MP), N, N-dimethylformamide (DMF),
Amide solvents such as N, N-dimethylacetamide, N, N-dimethylimidazolidinone, sulfones such as tetramethylene sulfone, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, ethylene glycol diethyl ether, propylene glycol diethyl ether, propylene glycol monomethyl ether Examples thereof include ether solvents such as monoacetate, tetrahydrofuran, and dioxane; ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone; and aromatic solvents such as toluene and xylene. An amide-based or sulfone-based solvent is preferable because a varnish having a relatively high concentration is possible. Further, the solid content concentration in the obtained varnish is usually 10 to 80% by weight, preferably 20 to 70% by weight, and more preferably 30 to 65% by weight. The film with an adhesive in which the epoxy resin composition of the present invention is used as an adhesive layer can be obtained by subjecting the varnishes described above to various coating methods such as gravure coating, screen printing, metal masking, and spin coating. It is obtained by coating and drying so that the thickness after drying becomes a predetermined thickness, for example, 20 to 100 μm, and which coating method is used depends on the type, shape,
It is appropriately selected depending on the size and the thickness of the coating film. As the base material of the film used, for example, polyamide, polyamide imide, polyarylate, polyethylene terephthalate, polybutylene terephthalate, polyetheretherketone, polyetherimide, polyetherketone,
It is a film or a copper foil made of various polymers such as polyketone, polyethylene and polypropylene and / or a copolymer thereof, and particularly preferably a polyimide or a copper foil.

The sheet-like adhesive of the present invention is prepared by applying the above-mentioned film with the adhesive or the epoxy resin composition of the present invention to a predetermined thickness, for example, 20 to 100 μm by using a roll, a press or the like.
m, and used as a sheet. Further, the varnishes described above are coated on a release paper by various coating methods such as a gravure coating method known per se, screen printing, a metal mask method, and a spin coating method, and then another release paper is stacked on the coated surface, By drying, a sheet-like adhesive having release paper layers on both sides of the adhesive layer is obtained. These are further cut,
The semiconductor device is cut into a desired shape and size according to a predetermined shape and size of the semiconductor by cutting or punching or the like, so that a small semiconductor device can be accurately bonded to a substrate.

[0039]

Next, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples. In the examples and comparative examples, “parts” means parts by weight.

Synthesis Example 1 (Synthesis of Block Copolymer (C)) Phenolic hydroxyl group-containing aromatic polyamide-polybutadiene / acrylonitrile block copolymer (hereinafter referred to as BPA)
M, synthesis of 14 mol% of phenolic hydroxyl groups contained in the aromatic polyamide moiety) 19.93 g (120 mmol) of isophthalic acid, 3,
30.63 g (153 mmol) of 4'-oxydianiline, 3.64 g (20 mmol) of 5-hydroxyisophthalic acid, 3.9 g of lithium chloride, calcium chloride 1
2.1 g, 240 ml of N-methyl-2-pyrrolidone and 54 ml of pyridine were placed in a 1-liter four-necked round-bottomed flask and dissolved by stirring.
g was added and reacted at 90 ° C. for 4 hours to produce a phenolic hydroxyl group-containing aromatic polyamide oligomer. Polybutadiene / acrylonitrile copolymers with carboxyl groups at both ends (Hycar CTBN, BF Goodr
Made by ich. The acrylonitrile component contained in the polybutadiene acrylonitrile part is 17 mol% and the molecular weight is about 36.
00) A solution obtained by dissolving 48 g in 240 ml of N-methyl-2-pyrrolidone was added, and the reaction was further carried out for 4 hours. After cooling to room temperature, the reaction solution was poured into 20 liters of methanol to prepare the polybutadiene used in the present invention. An aromatic polyamide-polybutadiene / acrylonitrile block copolymer containing about 14 mol% of a phenolic hydroxyl group having a content of the acrylonitrile copolymer part of 50 wt% was precipitated. The precipitated polymer was further purified by washing with methanol and refluxing methanol. The intrinsic viscosity of this polymer was 0.85 dl / g (dimethylacetamide, 30 ° C.). When the infrared spectrum of the polymer powder was measured by the diffuse reflection method, the absorption was based on the amide carbonyl group at 1,674 cm -1, the absorption based on the C-H bond of the butadiene portion at 2,856-2975 cm -1, and the nitrile group at 2,245 cm -1. Absorption was observed.

Example 1 20 parts by weight of BPAM and NM were placed in a 300 ml four-necked flask.
105 parts by weight of P was charged and stirred at room temperature for 24 hours to obtain a block copolymer solution. 100 parts by weight of the epoxy resin 1, 16.2 parts by weight of the curing agent 1, 1 part by weight of 2MZ-A, and 50 ml of NMP were added to a 500 ml four-necked flask to give 1 part.
The solution was stirred at 00 ° C. for 3 hours to form a solution. After the solution was cooled to room temperature, the previously prepared solution of the block copolymer was added and stirred at room temperature for 30 minutes to obtain a varnish of the present invention. The varnish thus obtained was applied to a polyimide film using an applicator so that the film thickness after drying was 25 μm, and dried to obtain a film with an adhesive of the present invention. A polyimide film was laminated at 120 ° C. on the adhesive layer of the film with the adhesive thus obtained, and was heated and cured at 150 ° C. for 3 hours. The test piece was allowed to stand at 85 ° C. and 85% RH for 24 hours (moisture / heat resistance test), and the adhesion before and after the treatment was observed. Table 1 shows the results.

Examples 2 to 5 Varnishes and test pieces made of the epoxy resin composition of the present invention were prepared in the same manner as in Example 1 using the raw materials shown in Table 1, and subjected to a moisture resistance test. Table 1 shows the results.

Comparative Example 1 100 parts by weight of epoxy resin 1, 16.2 parts by weight of curing agent 1, 2 parts by weight of MZ-A, and 50 ml of NMP were added to a 500 ml four-necked flask, and stirred at 100 ° C. for 3 hours to form a solution. . After the solution was cooled to room temperature, the previously prepared solution of the block copolymer was added and stirred at room temperature for 30 minutes to obtain a varnish of the present invention. The varnish thus obtained was applied to a polyimide film using an applicator so that the film thickness after drying was 25 μm, and dried to obtain a film with an adhesive of the present invention. A polyimide film was laminated at 120 ° C. on the adhesive layer of the film with the adhesive thus obtained, and was heated and cured at 150 ° C. for 3 hours. The test piece was allowed to stand at 85 ° C. and 85% RH for 24 hours (moisture / heat resistance test), and the adhesion before and after the treatment was observed. Table 1 shows the results.

Example 6 20 parts by weight of BPAM, 100 parts by weight of epoxy resin 2,
Curing agent 1 at 90 ° C. using two rolls of 11.2 parts by weight
And disperse uniformly. Further, 1 part by weight of 2MZ-A was added to obtain an epoxy resin composition of the present invention. The epoxy resin composition thus obtained was formed into an adhesive sheet of the present invention having a thickness of about 0.5 mm using a press, and a polyimide film was laminated on both sides of the sheet at 120 ° C. and cured by heating at 150 ° C. for 3 hours. The test piece was subjected to the conditions of 85 ° C. and 85% RH for 24
After leaving it for a while (moisture and heat resistance test), the adhesion before and after the treatment was observed.
Table 1 shows the results.

Example 7 The composition shown in the column of Example 7 in Table 2 as an epoxy resin composition was dissolved in a mixed solvent of 1 part by weight of MEK and 1 part by weight of N-methyl-2-pyrrolidone (NMP) to obtain 50% by weight. Was prepared. . The varnish thus obtained was applied to a polyimide film using an applicator so that the film thickness after drying was 25 μm, and dried to obtain a film with an adhesive of the present invention. The polyimide film was placed at 120 ° C. on the adhesive layer of the polyimide film with the adhesive thus obtained.
After lamination, 200 ° C x 5MP using a press
Heat curing was performed for 1 hour under the condition of a. 85 ° C
It was left for 24 hours under a condition of 85% RH (moisture and heat resistance test), and the adhesion before and after the treatment was observed. Table 1 shows the results.

Examples 8 to 10 Varnishes and test pieces made of the epoxy resin composition of the present invention were prepared in the same manner as in Example 7 using the raw materials shown in Table 2 and subjected to a moisture resistance test. Table 2 shows the results.

Comparative Example 2 A varnish and a test piece made of the epoxy resin composition of the present invention were prepared in the same manner as in Example 7 using the raw materials shown in Table 2 and subjected to a moisture resistance test. Table 2 shows the results.

The adhesion test of the examples was performed by the following method.
The test piece obtained in the example was cut to a width of 10 mm, and the peel strength was measured using a Tensilon tester (manufactured by Toyo Baldwin). The unit is N / cm. The higher the number, the better.

Table 1 Example Comparative Example 1 2 3 4 5 6 1 Epoxy resin 1 100 100 100 50 100 Epoxy resin 2 50 100 Epoxy resin 3 50 Epoxy resin 4 50 Curing agent 1 16.2 16.2 16.2 11.2 16.2 Curing agent 2 97.9 Curing Agent 3 26.4 BPAM 20 10 40 20 20 20 20 2MZ-A 1 1 1 1 1 1 1 NMP 255 236 367 360 255 255 255 Contact adhesion Before moisture and heat resistance test 5 4.5 4 5 6 25 0.4 After moisture and heat resistance test 5 4.5 4 5 6 25 0.2

Table 2 Example Comparative Example 7 8 9 10 2 Epoxy resin 5 100 Epoxy resin 6 100 100 Epoxy resin 7 100 Epoxy resin 8 100 Hardener 1 53.8 22.3 Hardener 4 60.9 60.9 Hardener 5 56.7 TPP 1 1 1 1 1 BPAM 154 161 87 122 0 Adhesion Before moisture and heat resistance test 10 11 10 12 0.1 After moisture and heat resistance test 10 11 10 12 0

The components in Tables 1 and 2 are as follows. Epoxy resin 1: Bisphenol A type epoxy resin (Epomic R-302 manufactured by Mitsui Chemicals) Epoxy resin 2: Bisphenol A type epoxy resin (Epomic R-304 manufactured by Mitsui Chemicals) Epoxy resin 3: Epoxy resin containing biphenyl skeleton (Nippon Kayaku) NC-3000P) Epoxy resin 4: Dicyclopentadiene skeleton-containing epoxy resin (Nippon Kayaku XD-1000) Epoxy resin 5: Cresol novolak type epoxy resin
(EOCN1020 manufactured by Nippon Kayaku Co., Ltd .; epoxy equivalent: 195) Epoxy resin 6: a novolac type epoxy resin having a phenol skeleton and a naphthol skeleton (N
C-7000; epoxy equivalent: 235) Epoxy resin 7: Novolak type epoxy resin having a triphenylmethane skeleton (EPPN- manufactured by Nippon Kayaku Co., Ltd.)
502H; epoxy equivalent: 171) Epoxy resin 8: bisphenol F type epoxy resin (Epototo YDF-2001; epoxy equivalent 470, manufactured by Toto Kasei Co., Ltd.) Curing agent 1: phenol novolak resin (PN, manufactured by Nippon Kayaku
-100) Curing agent 2: phenolic hydroxyl group bisphenol A at both ends
Epoxy resin modified product (TH-4000 manufactured by Toto Kasei) Curing agent 3: o-cresol novolak resin (OCN-100 manufactured by Nippon Kayaku) Curing agent 4: Novolac resin having a phenol skeleton and a naphthol skeleton (Nippon Kayaku Co., Ltd.) Kayahard NHN;
(Hydroxyl equivalent: 143) Curing agent 5: Novolak type epoxy resin having triphenylmethane skeleton (Kayahard TP manufactured by Nippon Kayaku Co., Ltd.)
M: hydroxyl equivalent: 97) BPAM: phenolic hydroxyl group-containing aromatic polyamide-
Polybutadiene / acrylonitrile block copolymer (Nippon Kayaku) NMP: N-methyl-2-pyrrolidone 2MZ-A: Imidazole-based curing accelerator (Shikoku Chemicals) TPP: Triphenylphosphine

[0052]

According to the present invention, as is clear from the results of the wet heat resistance test shown in Tables 1 and 2, a sealing resin composition having excellent adhesion and excellent wet heat resistance was obtained.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C09J 7/02 C09J 7/02 Z 163/00 163/00 F term (Reference) 4F071 AA42 AA75 AC09 AC11 AC12 AC13 AE03 AH12 BA01 BA02 BA03 BB02 BC01 BC02 BC07 4J002 BL01Y BP03Y CC03X CD00W CD02W CD05W CD06W CD07W CD12W CD13W CL00Y EF126 EJ036 EL136 EN036 EN076 ER026 EU116 FD010 FD090 FD130 FD14 A04 02 FD146 FD146 FD146 FD146 FD146 FD146 DA102 DB061 DB071 DB081 DB091 DB261 DB291 DH022 GA03 GA06 GA09 JA05 JA27 JA33 JA42 JA64 JA70 JA74 JB04 JB07 JB12 JB18 JC12 KA03 KA06 MA07 MA09 PC02 PC08 4J040 DM012 EB052 EC021 EC061 EC071 EC081 HC09GAB EC071 EC091 EC091 EC091 EC261 EC051 HC22 HD16 JA09 JB02 KA16 LA06 LA08 MA04 NA20 PA23

Claims (22)

[Claims] 1. An epoxy resin (A), a curing agent (B), a phenolic hydroxyl group-containing aromatic polyamide oligomer having aminoaryl groups at both ends and a polybutadiene / acrylonitrile copolymer having carboxyl groups at both ends. An epoxy resin composition containing the formed block copolymer (C). 2. The epoxy resin composition according to claim 1, wherein the content of the block copolymer (C) is 5 to 100 parts by weight based on 100 parts by weight of the epoxy resin. 3. The block copolymer (C) has the formula 1 (Where x, y, z, l, m, and n are average polymerization degrees, respectively; x = 3-7, y = 1-4, z = 5-1)
5, 1 + m = integer of 2 to 200, m / (m + 1)
≧ 0.04. The epoxy resin composition according to claim 1 or 2, which is a copolymer represented by the following formula: 4. The epoxy resin composition according to claim 1, wherein the epoxy resin (A) is a bifunctional epoxy resin. 5. The epoxy resin composition according to claim 1, wherein the epoxy resin (A) is a glycidyl ether type epoxy resin. 6. The epoxy resin composition according to claim 5, wherein the glycidyl ether type epoxy resin is a bisphenol A type epoxy resin. 7. The epoxy resin composition according to claim 5, wherein the glycidyl ether type epoxy resin is a bisphenol F type epoxy resin. 8. The epoxy resin composition according to claim 5, wherein the glycidyl ether type epoxy resin is a phenol novolak type epoxy resin. 9. The epoxy resin composition according to claim 8, wherein the phenol novolak epoxy resin is a novolak epoxy resin having a methyl group in a phenol skeleton. 10. The epoxy resin composition according to claim 5, wherein the glycidyl ether type epoxy resin is a novolak type epoxy resin having a phenol skeleton and a naphthol skeleton. 11. The novolak epoxy resin having a phenol skeleton and a naphthol skeleton is a novolak epoxy resin having a methyl group in the phenol skeleton.
The epoxy resin composition according to 0. 12. The epoxy resin composition according to claim 5, wherein the glycidyl ether type epoxy resin is a novolak type epoxy resin having a phenol skeleton and a biphenyl skeleton. 13. The epoxy resin composition according to claim 5, wherein the glycidyl ether type epoxy resin is a novolak type epoxy resin having a triphenylmethane skeleton. 14. The epoxy resin composition according to claim 5, wherein the glycidyl ether type epoxy resin is a novolak type epoxy resin having a dicyclopentadiene skeleton. 15. The epoxy resin composition according to claim 1, wherein the epoxy resin is solid at room temperature. 16. The epoxy resin composition according to claim 1, wherein the curing agent is a phenolic curing agent. 17. A varnish composition obtained by dissolving the epoxy resin composition according to any one of claims 1 to 16 in a solvent. 18. A sheet having a layer of the epoxy resin composition according to claim 1 on both sides or one side of a planar support. 19. The sheet according to claim 8, wherein the planar support is a polyimide film. 20. The planar support is a metal foil.
Sheet. 21. The sheet according to claim 18, wherein the planar support is a release film. 22. A sheet adhesive having a release film layer on both sides of the epoxy resin composition layer according to any one of claims 1 to 16.