JPH0774263B2 - Epoxy resin composition - Google Patents

Description

TECHNICAL FIELD The present invention relates to an epoxy resin composition having excellent heat resistance and molding processability, and a semiconductor device coated with the composition and sealed.

[Conventional technology]

Compositions based on epoxy resins have a wide range of applications in laminates, moldings, paints and adhesives. These compositions essentially require an epoxy resin and a curing agent, and most systems utilize a crosslinking reaction with the curing agent by ring opening of the epoxy group. In order to improve the heat resistance of the cured product in these systems, the use of a highly crosslinkable curing agent, a curing agent having a high heat resistant bond such as an imide bond, or an additive has been studied. However, in these systems, deterioration of molding processability such as a decrease in fluidity during molding and a decrease in curability is a problem.

The above-mentioned conventional techniques, for the purpose of improving heat resistance, a high degree of cross-linking, as a means for introducing a high heat-resistant bond, the main focus of the study is on a curing agent, for epoxy resins, an attempt to polyfunctionalize, or a hydantoin ring, There are few examples of studies on the introduction of heterocycles such as imide rings, but few studies on the crosslinking of these main skeletons themselves have been found. By the way, in recent years
Glycidyl ethers and glycidyl esters having a Schiff bond in the main skeleton have been studied (Abstracts of the 34th Summer Summer Seminar of Polymers, 121, 1986). It is known that the epoxy compound exhibits liquid crystallinity.

[Problems to be solved by the invention]

However, regarding the curing of the liquid crystal itself and the use of the cured product for sealing semiconductor devices,
Nothing is known so far.

An object of the present invention is to provide an epoxy resin composition having excellent heat resistance and molding processability, and a semiconductor device which is coated and sealed with the composition and has excellent reliability.

[Means for solving problems]

Briefly describing the present invention, the present invention relates to an epoxy resin composition, which is represented by the following general formula: (In the formula, X ₁ and X ₂ are the same or different, and are —O— or Of the glycidyl group-terminated schiff compound and a curing agent.

The curing agent used in the present invention is represented by the general formula described below.
It is at least one compound selected from the group of compounds represented by II, III, V and VI.

The present inventors, by orienting an epoxy compound exhibiting liquid crystallinity in a liquid crystal state, at the same time as curing agent cross-linking of the epoxy group, a Schiff bond and a cross-linking reaction with an addition-polymerizable group, resistance, We have found an epoxy resin composition with excellent moldability.

In the present invention, examples of the glycidyl group-terminated Schiff compound represented by the general formula I include the following.

Among the compounds of formula I above, in particular: as well as However, it is useful for exerting the effect of the present invention.

One or more compounds of the above formula I can be used in combination.

What can be used together in the resin composition of the present invention is described below.

As an effective curing agent for the resin composition of the present invention, a compound represented by the general formula I
I: [Wherein Y ₁ and Y ₂ are (P is a direct bond, -CH ₂ -, -O -, - CO -, - S -, - SO 2 -, Is one of the ), , Which may be the same or different from each other. Z ₁ and Z ₂ are —NH ₂ , —NH—C≡.
N, -OH, -OC-N, -COOH, -C≡N, -C≡C
H, (D is a group containing an ethylenically unsaturated double bond), which may be the same or different from each other].

Examples of these compounds include and so on. The above compounds may be used alone or in combination depending on the purpose and application.

Further, among the compounds of the above formula II, in particular, Or However, it is effective in exerting the effect of the present invention.

Further, in the present invention, the general formula III: [In the formula, R represents an alkylene group, an arylene group, or a divalent organic group substituted with them] N, N '
-As the substituted bismaleimide compound, for example, N, N '
-Ethylene bismaleimide, N, N'-hexamethylene bismaleimide, N, N'-dodecamethylene bismaleimide, N, N'-m-phenylene bismaleimide, N, N'-4,
4'-diphenyl ether bismaleimide, N, N'-4,
4'-diphenylmethane bismaleimide, N, N'-4,4 '
-Meta-xylene bismaleimide, N, N'-diphenylcyclohexane bismaleimide and the like can be mentioned, and two or more kinds of them can be mixed and used.
Furthermore, mono-substituted maleimide, tri-substituted maleimide,
A mixture of tetra-substituted maleimide and the substituted bismaleimide can also be used as appropriate.

Among these N, N′-substituted bismaleimide-based compounds, particularly, the compound represented by the general formula IV: (In the formula, R _{1 to} R ₄ represent hydrogen, a lower alkyl group, a lower alkoxy group, chlorine or bromine, and may be the same or different from each other. R ₅ and R ₆ are hydrogen, a methyl group, An etherimide compound represented by an ethyl group, a trifluoromethyl group or a trichloromethyl group) is excellent in imparting flexibility to a cured product and improving molding processability.

Examples of the ether imide compound represented by the general formula IV include 2,2-bis [4- (4-maleimidophenoxy) phenyl] propane and 2,2-bis [3-methyl-4- (4 -Maleimidophenyloxy) phenyl] propane, 2,2-bis [3-chloro-4- (4-maleimidophenoxy) phenyl] propane, 2,2-bis [3-bromo-4- (4-maleimide) Phenyloxy) phenyl] propane, 2,2-bis [3-ethyl-4- (4-maleimidophenoxy) phenyl] propane, 2,2-bis [3-propyl-4- (4-maleimidophenoxy) Si) Phenyl]
Propane, 2,2-bis [3-isopropyl-4- (4-
Maleimidophenoxy) phenyl] propane, 2,2-bis [3-n-butyl-4- (4-maleimidophenoxy) phenyl] propane, 2,2-bis [3-sec-butyl-4- ( 4-maleimidophenoxy) phenyl] propane, 2,2-bis [3-methoxy-4- (4-maleimidophenoxy) phenyl] propane, 1,1-bis [4-
(4-maleimidophenoxy) phenyl] ethane, 1,1
-Bis [3-methyl-4- (4-maleimidophenoxy) phenyl] ethane, 1,1-bis [3-chloro-4-
(4-maleimidophenoxy) phenyl] ethane, 1,1
-Bis [3-bromo-4- (4-maleimidophenoxy) phenyl] ethane, bis [4- (4-maleimidophenoxy) phenyl] methane, bis [3-methyl-4-
(4-maleimidophenyloxy) phenyl] methane, bis [3-chloro-4- (4-maleimidophenoxy) phenyl] methane, bis [3-bromo-4- (4-maleimidophenoxy) phenyl] Methane, 1,1,1,3,3,3-hexafluoro-2,2-bis [4- (4-maleimidophenoxy) phenyl] propane, 1,1,1,3,3,3-hexachloro -2,2-bis [4- (4-maleimidophenoxy) phenyl] propane, 3,3-bis [4- (4-maleimidophenoxy) phenyl] pentane, 1,1-bis [4-
(4-maleimidophenoxy) phenyl] propane, 1,
1,1,3,3,3-hexafluoro-2,2-bis [3,5-dibromo-4- (4-maleimidophenoxy) phenyl] propane, 1,1,1,3,3,3 -Hexafluoro-2,2-bis [3-
Methyl-4- (4-maleimidophenoxy) phenyl]
There is propane etc.

Further, in order to enhance the photocurability of the composition of the present invention, the combined use of a bis [2- (aminobenzoyl) ethenyl] benzene compound is extremely effective. For example, and so on. Also derived from the above compounds, for example And so on.

Further, 4,4'-diaminocinnamanilide compounds and derivatives of these compounds are also effective as curing agents. For example, and so on. The above compounds may be used alone or in combination.

Further, in order to enhance the photocurability of the composition of the present invention and improve the adhesion of the cured product to inorganic substances and metals, general formula V or VI: The combined use of the hydroxy-schiff compound represented by [Y ₁ , Y ₂ , Z ₁ and Z ₂ are the same as those in the general formula II] is highly effective. As such a compound, for example, And compounds corresponding to formula VI. These may be used alone or in combination depending on the purpose and application.

Also, the general formula VII: [In the formula, Y ₁ , Y ₂ , and Z ₁ and Z ₂ have the same meanings as those in the formula II], for example, a dihydroxy Schiff compound, Is also effective.

Also the following Are also useful.

Further, the epoxy resin composition of the present invention may be used in combination with a conventionally generally known epoxy resin as appropriate.

Examples of the epoxy resin include diglycidyl ether of bisphenol A, butadiene diepoxide, 3,4-epoxycyclohexylmethyl- (3,4-epoxy) cyclohexanecarboxylate, vinylcyclohexanedioxide and 4,4'-di (1 , 2-Epoxyethyl) diphenyl ether, 4,4 '-(1,2-epoxyethyl) biphenyl, 2,2-bis (3,4-epoxycyclohexyl) propane, diglycidyl ether of resorcin, diglycol of phloroglysin Glycidyl ether, diglycidyl ether of methyl phloroglucin, bis- (2,3-epoxycyclopentyl) ether, 2- (3,4-epoxy) cyclohexane-5,5-spiro (3,4-epoxy) -cyclohexane- m-dioxane, bis- (3,4-epoxy-6-methylcyclohexyl) adipate, N, N ' Bifunctional epoxy compounds such as m-phenylene bis (4,5-epoxy-1,2-cyclohexane) dicarboximide, triglycidyl ether of para-aminophenol, polyallylglycidyl ether, 1,3,5-tri (1,3) 2-epoxyethyl) benzene, 2,2 ', 4,4'-tetraglycidoxybenzophenone, tetraglycidoxytetraphenylethane, phenol formaldehyde novolac polyglycidyl ether, glycerin triglycidyl ether, trimethylol Trifunctional or higher functional epoxy compounds such as propane triglycidyl ether are used.

The above compounds may be used alone or in combination depending on the use and purpose.

Further, the following alicyclic epoxy compound can also be used in combination. For example [In the formula, m and n are 1 to 50, and 50> m + n> 1. ]
and so on.

Examples of the epoxy compound having at least one terminal vinyl group or allyl group and at least one terminal epoxy group (ethylene oxide group) in one molecule include those represented by the general formula: (In the formula, R ₇ is H or CH ₃ ) is a monomer having a structure, and glycidyl acrylate, glycidyl methacrylate, β-methylglycidyl acrylate, β-methylglycidyl methacrylate and the like are typical examples.

Also, the general formula (In the formula, R ₈ and R ₉ represent H or CH ₃ , and R ₁₀ is Or an ethylenically unsaturated epoxy monomer having 6 to 12 carbon atoms, which represents a direct bond), or an olefinic unsaturated monoepoxide. Also, the general formula (In the formula, R ₁₁ is H, or a lower alkyl group having 1 to 4 carbon atoms, or CH ₂ Cl, and v is an integer of 1 to 9,
w is an integer of 0 to 10), for example, (2-allyloxy) ethylene glycidyl ether, 4-butenyl glycidyl ether and the like.

Also Or general formula (In the formula, one of R _{12 to} R ₁₇ represents hydrogen, a methyl or an allyl group, and the other R represents hydrogen).

There is also vinylcyclohexene monoxide.

A conventionally known curing agent is used in combination with the epoxy resin composition of the present invention. For example, Hiroshi Kakiuchi: Epoxy resin (Showa 45
, September, pp. 109-149, Lee, Neville (Le
e, Neville): Epoxy Resins
New York City, Matsuglow Hill Book Company, Inc. (Mc Graw-Hill Book Compa
ny Inc) (published in 1957), pages 63-141, PE Brunis, Epoxy Resins Technology, Interscience Publi, New York City.
shers) (published in 1968) pages 45 to 111 and the like, for example, aliphatic polyamines, aromatic polyamines,
Amines, including secondary and tertiary amines, carboxylic acids,
Esters such as merimellitic acid triglyceride, carboxylic acid anhydrides, aliphatic and aromatic polyamide oligomers and polymers, boron trifluoride-amine complexes, phenol resins, melamine resins, urea resins,
Examples include synthetic resin initial condensates such as urethane resins, dicyandiamide, carboxylic acid hydrazides, and polyaminomaleimides.

One or more of the above-mentioned curing agents can be used depending on the application and purpose.

In particular, a novolak type phenol resin is suitable as a curing agent component of the above-mentioned semiconductor encapsulating material from the viewpoints of adhesion of the cured resin to the metal insert, workability during molding, and the like.

Further, the above-mentioned, N, N'-substituted maleimide compound,
By adding to the epoxy resin composition of the present invention, the molding material for semiconductor encapsulation produced is improved in heat resistance of a semiconductor element, for example, improved in glass transition point and reduced in thermal expansion coefficient to the element. It is useful for stressing and improving high temperature strength.

A molding material for semiconductor encapsulation using poly-p-hydroxystyrene or a poly-p-hydroxystyrene copolymer as a curing agent can improve the heat resistance of a cured product, and thus a resin-encapsulated semiconductor device. It is effective in achieving heat resistance reliability and moisture resistance reliability. When the epoxy resin composition of the present invention is used as a material for coating and / or encapsulating a semiconductor device, the above-mentioned novolak type phenol resin, N, N'-substituted maleimide compound, poly-p-hydroxystyrene is used. You may use together 1 type or more of a system polymer.

Further, a known aromatic diamine may be added to the epoxy resin composition of the present invention depending on the purpose and application. Examples are 2,2-bis (4-aminophenyl) propane, 4,4'-diaminodiphenylmethane, benzidine, 3,3'-dichlorobenzidine, 4,4'-diaminodiphenyl sulfide, 4 , 4'-Diaminostilbene, 3,3 '
-Diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl ether, 1,5-diaminonaphthalene, 4,4'-diaminodiphenyldiethylsilane, 4,4'-diamino Diphenyldiphenylsilane, 4,4'-diaminodiphenylethylphosphine oxide, 4,4'-diaminodiphenylphenylphosphine oxide, 4,4'-diaminodiphenyl N-
There are methylamines, 4,4'-diaminodiphenyl N-phenylamines and mixtures thereof.

Further, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethoxy-4,4'-diaminodiphenylmethane. Ethenylmethane, 3,3'-diethoxy-4,4'-diaminodiphenylmethane, 3,3'-dichloro-4,4'-diaminodiphenylmethane, 3,3'-dibromo-4,4'-diamino Diphenylmethane, 3,3'-dicarboxy-4,4'-diaminodiphenylmethane, 3,3'-dihydroxy-4,4'-diaminodiphenylmethane, 3,3'-di (aminosulfonyl)-
4,4'-diaminodiphenylmethane, 3,3'-dimethyl-
4,4'-diaminodiphenyl ether, 3,3'-diethyl-4,4'-diaminodiphenyl ether, 3,3'-dimethoxy-4,4'-diaminodiphenyl ether, 3,3'-diethoxy -4,4'-diaminodiphenyl ether, 3,3 '
-Dichloro-4,4'-diaminodiphenyl ether, 3,
3'-dibromo-4,4'-diaminodiphenyl ether,
3,3'-dicarboxy-4,4'-diaminodiphenyl ether, 3,3'-dihydroxy-4,4'-diaminodiphenyl ether, 3,3'-di (aminosulfonyl) -4,4 ' −
Diaminodiphenyl ether, 3,3'-dimethyl-4,4 '
-Diaminodiphenyl sulfide, 3,3'-diethyl-
4,4'-diaminodiphenyl sulfide, 3,3'-dimethoxy-4,4'-diaminodiphenyl sulfide, 3,3'-
Diethoxy-4,4'-diaminodiphenyl sulfide,
3,3'-dichloro-4,4'-diaminodiphenyl sulfide, 3,3'-dibromo-4,4'-diaminodiphenyl sulfide, 3,3'-dicarboxy-4,4 ' -Diaminodiphenyl sulfide, 3,3'-dihydroxy-4,4'-diaminodiphenyl sulfide, 3,3'-di (aminosulfonyl) -4,4'-diaminodiphenyl sulfide, 3,3′−
Dimethyl-4,4'-diaminodiphenyl sulfone, 3,3 '
-Diethyl-4,4'-diaminodiphenyl sulfone, 3,
3'-diethoxy-4,4'-diaminodiphenyl sulfone, 3,3'-chloro-4,4'-diaminodiphenyl sulfone, 3,3'-dicarboxy-4,4'-diaminodiphenyl sulfone, 3,3'-dihydroxy-4,4'-diaminodiphenyl sulfone, 3,3'-di (aminosulfonyl) -4,
4'-diaminodiphenyl sulfone, 2,2-bis (3-ethyl-4-aminophenyl) propane, 2,2-bis (3
-Methoxy-4-aminophenyl) propane, 2,2-bis (3-bromo-4-aminophenyl) propane, 2,2
-Bis (3-chloro-4-aminophenyl) propane,
2,2-bis (3-carboxy-4-aminophenyl) propane, 2,2-bis (3-hydroxy-4-aminophenyl) propane, 2,2-bis [3- (aminosulfonyl) -4-aminophenyl] propane , 3,3'-dimethyl-4,4'-diaminobenzophenone, 3,3'-dimethoxy-4,4'-diaminobenzophenone, 3,3'-dichloro-4,4'-diaminobenzophenone Non, 3,3'-dibromo-
4,4'-diaminobenzophenone, 3,3'-dicarboxy-4,4'-diaminobenzophenone, 3,3'-dihydroxy-4,4'-diaminobenzophenone, 3,3'- Di (aminosulfonyl) -4,4'-diaminobenzophenone, 3,
3'-diaminodiphenyl methane, 3,3'-diaminodiphenyl ether, 3,3'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfone, 2,2-bis (3-aminophenyl) Propane, 3,3'-diaminobenzophenone, 2,4-diaminotoluene, 2,6-diaminotoluene, 1-isopropyl-2,4-diaminotoluene, 2,4-diaminoanisole, 2,4-diaminomono There are chlorobenzene, 2,4-diaminofluorobenzene, 2,4-diaminobenzoic acid, 2,4-diaminophenol, 2,4-diaminobenzenesulphonic acid, and phenylenediamine.

Of these, preferred diamines are m-phenylenediamine, p-phenylenediamine, 4,4'-oxydianiline, 3,3'-sulfonyldianiline, 4,4'-diaminobenzophenone, 4, 4'-methylenedianiline and 4,4-
It is diaminostilbene. The above amine compounds are 1
It is also possible to use a combination of more than one type.

Further, in the present invention, a conventionally known carboxylic acid dianhydride can be used in combination. For example, 3,3 ', 4,4'-benzophenone tetracarboxylic acid dianhydride, pyromellitic acid dianhydride, 2,3,6,7-naphthalene tetracarboxylic acid dianhydride, 3,3', 4 , 4'-diphenyltetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 2,2 ', 3,3'-diphenyltetracarboxylic dianhydride, 2, 2-bis (3,4-dicarboxyphenyl) propane dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, naphthalene- 1,2,4,5-tetracarboxylic dianhydride, naphthalene-1,4,5,8-tetracarboxylic dianhydride, decahydronaphthalene-1,4,5,8-tetracarboxylic dianhydride 4,8-dimethyl-1,2,3,5,6,7-hexahydronaphthalene-1,2,5,6-tetracarboxylic dianhydride,
2,6-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,7-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,3,6, 7-tetrachloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, phenanthrene-1,8,9,10-tetracarboxylic dianhydride, cyclopentane-1,2,3,4-tetra Carboxylic dianhydride, pyrrolidine-2,3,4,5-tetracarboxylic dianhydride, pyrazine-2,3,5,6-tetracarboxylic dianhydride, 2,2-bis-
(2,3-dicarboxyphenyl) propane dianhydride, 1,1
-Bis (2,3-dicarboxyphenyl) ethane dianhydride, 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride, bis (2,3-dicarboxyphenyl) methane dianhydride, Bis (3,4-dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, benzene-1,2,3,4-tetracarboxylic dianhydride and thiophene-2 There are 3,3,4,5-tetracarboxylic dianhydride and others. Among these, preferred dianhydrides are 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, pyromellitic dianhydride and 1,4,5,8-naphthalenetetracarboxylic dianhydride, These are 3,3 ', 4,4'-biphenyltetracarboxylic acid dianhydride and 3,3', 4,4'-diphenylethertetracarboxylic acid dianhydride.

Also, aliphatic tetracarboxylic dianhydrides such as m-phenylene bis (succinic anhydride) p-phenylene bis (succinic anhydride) m-phenylene bis (glutaric anhydride) p-phenylene bis (glutaric anhydride) and so on.

Further, in the present invention, a cured product having excellent heat resistance can be provided by blending the glycidyl group-terminated Schiff compound represented by the general formula I with a polyfunctional isocyanate compound.

Methane diisocyanate, butane-1,1-diisocyanate, ethane-1,2-diisocyanate, butane-1,2-diisocyanate, transvinylene diisocyanate, as a polyfunctional isocyanate compound in the present invention,
Propane-1,3-diisocyanate, butane-1,4-diisocyanate, 2-butene-1,4-diisocyanate,
2-methylbutane-1,4-diisocyanate, pentane-1,5-diisocyanate, 2,2-dimethylpentane-1,
5-diisocyanate, hexane-1,6-diisocyanate, heptane-1,7-diisocyanate, octane-1,8
-Diisocyanate, nonane-1,9-diisocyanate, decane-1,10-diisocyanate, dimethylsilane diisocyanate, diphenylsilane diisocyanate, ω, ω'-1,3-dimethylbenzene diisocyanate, ω, ω'-1,4- Dimethylbenzene diisocyanate, ω, ω′-1,3-dimethylcyclohexane diisocyanate, ω, ω′-1,4-dimethylcyclohexane diisocyanate, ω, ω′-1,4-dimethylbenzene diisocyanate, ω, ω′-1, 4-dimethylnaphthalene diisocyanate, ω, ω'-1,5-dimethylnaphthalene diisocyanate, cyclohexane-1,3-diisocyanate, cyclohexane-1,4-diisocyanate,
Dicyclohexylmethane-4,4'-diisocyanate,
1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 1, -methylbenzene-2,4-diisocyanate, 1-methylbenzene-2,5-diisocyanate, 1-methylben-2,6-diisocyanate, 1 -Methylbenzene-3,5-diisocyanate, diphenyl ether-4,4'-diisocyanate, diphenyl ether-2,4'-diisocyanate, naphthalene-1,4-diisocyanate, naphthalene-1,5-diisocyanate,
Biphenyl-4,4'-diisocyanate, 3,3'-dimethylbiphenyl-4,4'-diisocyanate, 2,3'-dimethoxybiphenyl-4,4'-diisocyanate, diphenylmethane-4,4'-diisocyanate, 3,3'-dimethoxydiphenylmethane-4,4'-diisocyanate, 4,
Bifunctional isocyanate compounds such as 4'-dimethoxydiphenylmethane-3,3'-diisocyanate, diphenylsulfide-4,4'-diisocyanate, diphenylsulfone-4,4'-diisocyanate, polymethylene polyphenyl isocyanate , Triphenylmethane triisocyanate, tris (4-phenylisocyanate thiophosphonate), 3,3 ′, 4,4′-diphenylmethanetetraisocyanate, and other trifunctional or higher functional isocyanate compounds are used.

In order to maintain the storage stability of the resin composition containing at least the glycidyl group-terminated Schiff compound represented by the general formula I of the present invention and the polyfunctional isocyanate compound,
It is preferable to use a diisocyanate compound having a uretdione ring in the molecule.

The diisocyanate compound having a uretdione ring in the molecule means at least one uretdione ring in the molecule. Having the general formula: Here, R ₁₈ , R ₁₉ and R ₂₀ each represent an aromatic group, and may be different from each other or partly or wholly the same, and X is-.
Indicates an NCO group.

Examples of such a compound include 1,3-bis (3-isocyanato-o-tolyl) -2,4-uretdione and 1,3
-Bis (3-isocyanato-p-tolyl) -2,4-uretdione, 1,3-bis (3-isocyanate-4-methoxyphenyl) -2,4-uretdione, 1,3-bis [4
-(4-isocyanatophenylmethyl) phenyl]-
There are 2,4-uretdione and uretdione compounds synthesized from 2,4-tolylene diisocyanate and diphenylmethane-4,4'-diisocyanate. These compounds may be used alone or in combination. In addition, the compound having the uretdione ring is As described above, it is decomposed to produce an isocyanate group according to the number of uretdione rings. Such a cleavage reaction of the uretdione ring proceeds at about 140 to 150 ° C. in the case of tolylene diisocyanate dimer, for example. Since the characteristics of the coating film of the present invention are significantly influenced by the amount of the compound having a uretdione ring, which is blended with the polyfunctional epoxy compound, the selection of the blending amount is very important. In the present invention, the equivalent ratio of total isocyanate groups including isocyanate groups formed by cleavage of the uretdione ring of the compound having a uretdione ring to 1 equivalent of the epoxy group of the polyfunctional epoxy compound is within the range of 1.0 to 4.0. It is characterized by being blended as it is. This is because if the equivalent ratio is less than 1.0, the heat resistance of the coating film decreases, and if it exceeds 4.0, the flow properties of the powder deteriorate and the aesthetic appearance of the coating film is significantly impaired.

When the coating film is heat-cured, it is important to select a catalyst that accelerates the cleavage of the uretdione ring and accelerates the curing reaction between the epoxy group and the isocyanate group or between the isocyanate groups so that the curing can be performed in a short time. Ordinary amines and imidazoles accelerate the cleavage of the uretdione ring and the curing reaction at a relatively low temperature, whereby the reaction with water as described above easily occurs and the storage stability of the powder cannot be obtained.

Furthermore, various catalysts can be added for the purpose of accelerating the curing reaction of the epoxy resin composition.
For example, tertiary amines such as triethanolamine, tetramethylbutanediamine, tetramethylpentanediamine, tetramethylhexanediamine, triethylenediamine and dimethylaniline, oxyalkylamines such as dimethylaminoethanol and dimethylaminopentanol, and tris (dimethylamino). Amines such as methyl) phenol and methylmorpholine can be applied.

For the same purpose, as a catalyst, for example, cetyltrimethylammonium bromide, cetyltrimethylammonium chloride, dodecyltrimethylammonium iodide, trimethyldodecylammonium chloride, benzyldimethyltetradecylammonium chloride, benzylmethylpalmitylammonium chloride, (allyldodecyl) Quaternary ammonium salts such as trimethylammonium bromide, benzyldimethylstearylammonium bromide, stearyltrimethylammonium chloride and benzyldimethyltetradecylammonium acetate can be applied.

Dicyandiamide or a derivative thereof, for example, Alternatively, And the following formula (In the above formula, X ₃ , X ₄ are direct bonds, —CH ₂ —, —O—, —S
It is either-or -NH-, and may be the same or different from each other. The Y is a direct bond, -CH ₂ -, -O -, - CO -, - S -, - SO 2 -, - N = CN -, - CH
= CH-, -N = N-, And the like) are useful as a curing agent or curing accelerator for the epoxy resin composition of the present invention.

Furthermore, 2-undecyl imidazole, 2-methyl imidazole, 2-ethyl imidazole, 2-heptadecyl imidazole, 2-methyl-4-ethyl imidazole,
1-butylimidazole, 1-propyl-2-methylimidazole, 1-benzyl-2-methylimidazole,
Imidazole such as 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-azine-2-methylimidazole and 1-azine-2-undecylimidazole Compounds or alternatively, triphenylphosphine tetraphenylborate, triethylamine tetraphenylborate, N-methylmorpholine tetraphenylborate, pyridine tetraphenylborate, 2-ethyl-4-methylimidazole tetraphenylborate and 2-ethyl- Tetraphenylboron salts such as 1,4-dimethylimidazole tetraphenylborate are useful as curing accelerators. In addition, 1,8-diazo-bicyclo (5.4.0) undecene-7 or 1,5
Also useful are bicyclic amidines such as -diazo-bicyclo (4.3.0) nonene-5, and derivatives of bicyclic amidines.

Further, in the present invention, a metal chelate compound may be used as a curing accelerator. For example, Or Or [Wherein, R _21, R ₂₂ is _{H, CH 3, C 2 H} 5, C 3 H 7, C 4 H 9, -C
(CH ₃ ) ₃ , , Which may be the same or different. R ₂₃ is H, CH ₃ , C ₂ H ₅ , Is one of the R ₂₄ and R ₂₅ are H, CH ₃ , -OH, -OC
It is one of H ₃ and may be the same or different. M is a metal. X is an alcoholate group.
m has a valence of 0 to 3, and n has a valence of 1 to 4. Further, 1 valence <m + n <4 valence. ] It is a compound represented by these.
In the above formula, M is preferably Al, Zr, Fe, Ni, Pb, Cu or the like. The metal chelate compounds may be used alone or in combination with other promoters.

The above-mentioned curing accelerator may be used in a weight ratio of 100 to an epoxy compound containing at least a glycidyl group-terminated Schiff compound, preferably 0.01 to 20.

In the present invention, a catalyst is used as a cross-linking agent to complete the cross-linking with a compound having an unsaturated double bond. Examples of such a catalyst include benzoyl peroxide, parachlorobenzoyl peroxide, and 2,4-
Dichlorobenzoyl peroxide, cabrylyl peroxide, lauroyl peroxide, acetyl peroxide, methyl ethyl ketone peroxide, cyclohexanone peroxide, bis (1-hydroxycyclohexyl peroxide), hydroxyheptyl peroxide, tertiary butyl hydroperoxide, p -Menthane hydroperoxide, cumene hydroperoxide, di-tertiary butyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-di (tertiary butyl peroxide) hexane, 2,5- Dimethylhexyl-2,5-di (peroxybenzoate), tertiary butyl perbenzoate, tertiary butyl peracetate, tertiary butyl peroctoate,
Organic peroxides such as tertiary butyl peroxyisobutyrate and di-tertiary butyl perphthalate are useful, and one or more of them may be used in combination.

In the present invention, the above-mentioned polymerization catalyst may be used in combination with known accelerators such as mercaptans, sulfites, β-diketones, metal chelates, and metal soaps. In order to improve the storage stability of the resin composition at room temperature, for example, quinones such as p-benzoquinone, naphthoquinone and phenanthraquinone, hydroquinone, p-tertiary butyl catechol and 2,5-diquinone. -Third
Known polymerization inhibitors such as phenols such as secondary butylhydroquinone and nitro compounds and metal salts can be used if desired.

Further, various materials are blended with the resin composition of the present invention depending on its use. That is, for example, in the use as a molding material, zircon oxide, silica, alumina, aluminum hydroxide, titania, zinc white, calcium carbonate, magnesite, clay, kaolin, talc, silica sand, glass, fused silica glass, asbestos, Inorganic fillers such as mica, various whiskers, carbon black, graphite and molybdenum disulfide, release agents such as higher fatty acids and waxes, and coupling such as epoxysilane, vinylsilane, borane and alkoxy titanate compounds. The agent is blended. If necessary, a flame retardant-imparting agent such as a halogen-containing compound, antimony oxide and a phosphorus compound can be used.

Further, known polymers such as various polymers such as polystyrene, polyethylene, polybutadiene, polymethylmethacrylate, polyacrylic acid ester, acrylic acid ester-methacrylic acid ester copolymer, phenol resin, epoxy resin, melamine resin or urea resin may be used. Pledgets can be used.

It can also be used as a solution such as varnish. As the solvent used at that time, N-methyl-2
-Pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, N, N-dimethylformamide, N-
There are methylformamide, dimethylsulfoxide, N, N-diethylacetamide, N, N-dimethylmethoxyacetamide, hexamethylphosphoramide, pyridine, dimethylsulfone, tetramethylsulfone, dimethyltetramethylenesulfone, and the like, and phenol solvent groups. Examples include phenol, cresol and xylenol.

The above may be used alone or in admixture of two or more.

〔Example〕

Hereinafter, the present invention will be described in more detail with reference to Examples.
The present invention is not limited to these examples.

Examples 1 to 7 have the following formulas as glycidyl group-terminated Schiff compounds 100 parts by weight of the compound represented by the formula (1) to (E) 5 types were mixed in the predetermined amounts shown in Table 1 to prepare 7 types of blended compositions.

The composition contained 6 parts by weight of dicyandiamide as a curing accelerator and aluminum chelate AL as a coupling agent.
CH-TR (Kawaken Huaine Chemical Co., Ltd.) 2.0 parts by weight, epoxysilane KBM403 (Shin-Etsu Chemical Co., Ltd.) 1.0 parts by weight, and fused silica glass powder (spherical 1 to 3 μm average particle size) as a filler 80% by weight It was blended so that Then, the blended composition was mixed in a Henschel mixer to obtain a fine powder composition.

Then, the composition was subjected to transfer molding under the conditions of 180 to 185 ° C., 70 kg / cm ² , and 2 minutes to obtain various measurement test pieces. First
The table shows the glass transition temperature of the cured product, the flexural strength at 180 ° C, and the flexural strength retention after standing at 225 ° C for 30 days. In addition, the cracking status of the cured product after standing at 270 ° C. for 5 days is also shown.

Examples 8 to 14 As the glycidyl group-terminated Schiff compounds, the above formula (A) is used.
50 parts by weight of the compound represented by the formula and 50 parts by weight of bisphenol A type epoxy DER332 (manufactured by Dow) are taken as a curing agent, and the following F to K: The above 6 types were blended in the predetermined amounts shown in Table 2 to obtain 7 types of blends. 2.0 parts by weight of imidazole 2E4MZ-CN (manufactured by Shikoku Kasei) as a curing accelerator, and triethylamine tetraphenyl porate 2.
Epoxysilane KBM with 0 part by weight as a coupling agent
2.0 parts by weight of 303 (manufactured by Shin-Etsu Chemical Co., Ltd.), 2.0 parts by weight of Hoechst wax E (manufactured by Hoechst Japan Co., Ltd.) as a release agent, 40% by weight of fine powder spherical fused silica as a filler, and 1 to
40% by weight of spherical alumina having an average particle size of 3 μm was compounded. Next, the mixture was heated and mixed with a cokneader and then cooled to obtain a molding resin composition. The properties of these compositions were measured using the same methods as in Example 1. The results are shown in Table 2.

Examples 15 to 28 As glycidyl group-terminated Schiff compounds, Taking three types, as a curing agent, novolak type phenol resin (Hitachi Chemical Co., Ltd .: HP-607
N), 2,2-bis- [4- (4-maleimidophenoxy) phenyl] propane, poly-p-hydroxystyrene polymer, M resin (Maruzen Petrochemical Co., Ltd.), Were mixed with the respective prescribed amounts shown in Table 3 to prepare 14 kinds of blends.

Separately, in the composition, 1.5 parts by weight of triphenylphosphine and 1.0 part by weight of triethylamine tetraphenylborate as curing accelerators, 2 parts by weight of epoxysilane KBM303 (manufactured by Shin-Etsu Chemical Co., Ltd.) as a coupling agent, and a flame retardant material. As an addition type imide coat red phosphorus 5.5 parts by weight, as a releasing agent calcium stearate 1.0 part by weight and Hoechst wax E (manufactured by Hoechst Japan Co., Ltd.) 1 part by weight, as a filler, fused silica glass powder 80% by weight, as a colorant 2.0 parts by weight of carbon black (manufactured by KYABOT) was added.

Next, the composition was kneaded with a 2-inch roll having a diameter of 8 inches at 80 to 90 ° C. for 7 minutes and then coarsely pulverized to obtain a resin composition.

Using the resin composition, a transfer molding machine in which a mold loaded with a 1M bit D-RAM memory LSI was set,
The LSI was resin-sealed under conditions of 0 ° C., 70 kg / cm ² , and 1.5 minutes.

The obtained resin-encapsulated memory LSI was subjected to a standing test (PCT) in a 121 ° C., 2 atmospheric pressure supersaturated water vapor atmosphere. The moisture resistance reliability of the resin-sealed LSI was judged by the degree of disconnection failure due to corrosion of Al wiring on the element after a predetermined PCT leaving time.

Example 29 As a bisphenol A type epoxy resin, 60 parts by weight of Ep1001 (manufactured by Ciel) and 40 parts by weight of Ep828 (manufactured by Ciel) were taken. A system in which 100 parts by weight of the glycidyl ether group-terminated schiff compound represented by the above formula was added was dissolved in a mixed solution of methyl ethyl ketone and dimethylformamide in an equal amount to prepare a varnish solution having a concentration of 45% by weight (6 parts by weight of dicyandiamide catalyst).

This varnish solution was applied to a 0.1 mm thick glass fiber cloth (epoxysilane KBM303) using a coating-drying device (coating machine).
(Treatment) and then dried at 110 ° C. for 10 minutes to obtain a B-stage prepreg having a resin content of 43% by weight.

10 sheets of this prepreg are piled up, 35 μm-thick electrolytic copper foil is placed on the outside, sandwiched between two steel plates, and 160 ° C by a hot plate press, 50 kg / cm ² for 2 hours at + 200 ° C. It was heated and pressed for 2 hours to obtain a double-sided copper clad laminate having a thickness of 1.0 mm.

The performance of this copper clad laminate is shown in Table 4.

Table 4 Bending strength (180 ℃) 59kg / mm ² Volume resistivity (160 ℃) 1.5 × 10 ¹⁵ Ω ・ cm Thermal expansion coefficient 1.7 × 10 ^-5 ℃ ^-1 Beer strength (100 ℃, 90 ° direction) 2.1 kg / cm Solder heat resistance (280 ° C., 60 seconds immersion) No blistering Example 30 Method for producing heat resistant prepreg As a glycidyl machine terminal syrup compound, the above Example 29 was used.
With the same compounds used in Was dissolved in dimethylacetamide and 1000 ml of 8% by weight varnish solution (5.0 parts by weight of dicyandiamide catalyst was added)
Was adjusted. Then, a glass fiber cloth (WF-230 manufactured by Nitto Boseki Co., Ltd.) was immersed in the varnish solution. The needle-containing prepreg sheet was heated and dried at 100 to 110 ° C. for about 2 hours to obtain a prepreg. The resin content of the prepreg was 46% by weight.

Next, stack 6 sheets of the obtained prepreg at 150-160 ℃, 50kg ・
Compression molding was performed under the condition of f / cm ² for 2 hours. The tensile strength of the molded product is 19.7kg / cm ² (140 ℃) (ASTM.D-638), and the bending strength is
18.5kg / cm ² (140 ℃) (ASTM.D−790), Izod impact strength (with notch) is 6.3kg ・ cm / cm ² (25 ℃) (ASTM.D-2
56)

Example 31 Manufacturing method of sliding member A porous layer obtained by sprinkling Cu90 to Sn10 alloy powder (passed through 32 mesh) on the surface of a steel strip having a thickness of 1 mm and sintering at 810 to 830 ° C for 40 minutes in a reducing atmosphere. Was formed to a thickness of about 350 μm.

After sintering, after exemplifying to room temperature, 35 parts by weight of graphite, 15 parts by weight of PTFE on the porous layer, 35 parts by weight, 15 parts by weight of the mixed powder was sprayed from the hopper, and as a preforming step, the first pressure roller, 100 kg / cm ² and the second pressure roller, 200 kg / cm ² were pressed at 160 ° C. for 1 hour, and further As the molding process, at the furnace temperature of 230 ℃, the third pressure roller, 3
00kg / cm ^2, the fourth pressure roller, and cured by pressing the 400 kg / cm ^2, to form a film having a thickness of about 450 [mu] m.

As a result of performing a thrust load resistance test on the plate-like sliding member thus obtained under the following test conditions, under high speed conditions, a low friction coefficient of 0.05 to 0.03 is shown, and it is also excellent in load resistance. I found out that

-Test conditions-Slip velocity V = 278m / min Load P = 10kg / cm ² cumulative load is applied every 10 minutes, and 450kg / cm ^{2 is} completed.

Counterpart material S45C lubricated, completely unlubricated.

Example 32 As a glycidyl group-terminated Schiff compound, the compound (a)
As a curing agent, Was dissolved in dimethylformamide to prepare a 2 wt% solution. Next, on a polyethylene terephthalate film having a sufficiently washed conductive conductive film, using a spinner, after uniformly coating at 3500 rpm, dried at 120 ℃ for 15 minutes to evaporate dimethylformamide, orientation 650 Å film thickness A control film was formed. This film was rubbed with a felt in a certain direction to prepare a substrate film having an orientation control film.

The alignment control films of the two films thus formed were arranged so as to face each other, and these films were adhered with an adhesive made of a polyester adhesive to form a liquid crystal display element. A phenylcyclohexane-based liquid crystal (ZLI-1132, manufactured by Merck & Co., Inc.) was placed between the orientation control films of this element, and the orientation of the liquid crystal was examined between two orthogonal polarizing plates. Indicated.

Example 33 Sumiepoxy ESA-011 (bisphenol A type epoxy resin manufactured by Sumitomo Chemical Co., Ltd., epoxy equivalent: 480) 80 parts by weight, glycidyl group-terminated Schiff compound (a), 20 parts by weight methyl ethyl ketone 40 parts by weight, N-methylpyrrolidone 40 26 parts by weight of dicyandiamide and 20 parts by weight of 1,2,3-benzotriazole (B7A) were added and dissolved uniformly to obtain an epoxy resin composition. A glass cloth (KS-1600 plain weave manufactured by Kanebo Glass Fiber Co., Ltd.) was impregnated with the composition and air-dried.
A prepreg was obtained by heating at 130 ° C for 25 minutes in a constant temperature bath.

Six layers of prepreg were press-molded under the conditions of 160 ° C., 100 kg / cm ² and 20 minutes, and further post-cured in a constant temperature bath at 180 ° C. for 60 minutes to obtain a laminated plate. Further, a copper-clad laminate was obtained from copper foil (Furukawa Electric Co., Ltd., 32 μm) and 6 layers of prepreg under the same conditions as above.
The peel strength of these obtained laminated plates was measured in accordance with JIS-C-6481.

As a result, it was 21 kg / m at room temperature, and the peel strength after immersion in solder (280 ° C, 20 seconds) was 1.7 kg / m.

Example 34 As a Schiff compound having a glycidyl group, the above (ii) was dissolved in toluene to prepare a 1% by weight resin solution. The element structure when the solution is used as a multi-layer (two-layer) wiring insulating film is shown in FIGS. 2 and 3. That is, FIGS. 2 and 3 are partial cross-sectional views of the element portion of the semiconductor device according to the present invention, in which reference numeral 3-I is a first layer protective coating resin, 3-II is a second layer protective coating resin, 4-I is the first layer wiring, 4-II is the second layer wiring, 7 is the thermal oxide film, and 8 is the Si element substrate.

The structure of the element is such that after forming the SiO ₂ insulating layer and the polysilicon layer (7) and the first layer aluminum wiring (4-I) on the Si element substrate (8), the above resin coating material is applied. After using (using a spinner) and baking (250 ° C., 60 minutes) (3-I), a positive resist was applied and patterning of through holes was performed. After that, plasma etching was performed using CF ₄ —O ₂ as a reaction gas. Then, the positive resist was removed by plasma etching using O ₂ as a reaction gas.

Next, after forming the second layer aluminum wiring (4-II), the resin solution was further applied and baked (the same as the above conditions). (3-II Layer) Incidentally, FIG. 3 shows a case (5 layers) in which a polyimide resin (Hitachi Kasei: PIQ) is used as the coating resin for the second layer.

An LSI product for memory (1M bit D-RAM memory) (shown in FIG. 1) in which the semiconductor device of the present invention is resin-packaged with an epoxy resin composition using a phenol novolac resin as a curing agent is 85 Even after 2500 hours of bias application at 85 ° C and 85% relative humidity, there was no disconnection failure due to corrosion of Al wiring, and an LSI with excellent moisture resistance reliability was obtained. FIG. 1 is a sectional view of a semiconductor device according to an embodiment of the present invention. Reference numeral 1 is a lead wire, 2 is a semiconductor element, 3 is a protective coating resin, and 6 is a molding resin.

The epoxy resin composition used for the above LSI is as follows.

Epoxy resin composition for encapsulation Novolak type epoxy resin 100 parts by weight Phenols to formaldehyde resins 55 parts by weight Imidazole catalyst 3 parts by weight Fused silica glass powder 480 parts by weight Epoxysilane 2 parts by weight Hoxtowax 2 parts by weight Carbon black 1 part by weight The above-mentioned compounded composition was heated on 70-80 ° C with a two-roll
After kneading for 10 minutes, coarse pulverization was performed to prepare a sealing resin composition.

As a method of sealing the above-mentioned coated semiconductor element, in addition to resin sealing, sealing using a can, a solder-fusion ceramic, a glass-fusion ceramic, or the like can be adopted.

〔The invention's effect〕

As described above, according to the present invention, an epoxy resin composition having excellent heat resistance and molding processability is provided, and by using this composition, a semiconductor device having particularly high humidity resistance reliability under constant temperature and high humidity. The remarkable effect of being provided is exhibited.

[Brief description of drawings]

FIG. 1 is a sectional view of a resin-molded semiconductor device according to an embodiment of the present invention, and FIGS. 2 and 3 are sectional views of a multi-layer LSI element which is an example of the semiconductor device of the present invention. 1: lead wire, 2: semiconductor element, 3: protective coating resin, 3-I: first layer coating resin, 3-II: second layer coating resin, 4-I: first layer wiring, 4-II: second layer 2-layer wiring, 5: Polyimide resin, 6: Mold resin, 7: Thermal oxide film, 8: Si element substrate

Front Page Continuation (72) Inventor Toshikazu Narahara 4026 Kuji Town, Hitachi City, Ibaraki Prefecture Hitachi Research Laboratory, Hitachi Co., Ltd. (56) References JP-A 64-56721 (JP, A) JP-A 58-206579 ( JP, A) JP 64-56720 (JP, A) JP 63-10617 (JP, A)

Claims (1)

[Claims] 1. The following general formula I: (In the formula, X ₁ and X ₂ are the same or different, and are —O— or A glycidyl group-terminated Schiff-based compound represented by the following general formula II: A Schiff compound represented by the following general formula III: An N, N′-substituted bismaleimide compound represented by the following general formula V or VI: At least one compound selected from the group consisting of hydroxy-schiff compounds represented by the formula: wherein Y ₁ and Y ₂ are (P is a direct bond, -CH ₂ -, -O -, - CO -, - S -, - SO 2 -, Is one of the ), , Which may be the same or different from each other. Z ₁ and Z ₂ are —NH ₂ , —NH—C≡.
N, -OH, -OC-N, -COOH, -C≡N, -C≡C
H, (D is a group containing an ethylenically unsaturated double bond.), And they may be the same or different from each other. Further, in the formula, R represents an alkylene group, an arylene group, or a divalent organic group substituted with these), and an epoxy resin composition.