JPH0855940A - Thermosetting resin composition - Google Patents

Abstract

PURPOSE:To obtain thermosetting polyimide resin composition which is excellent in heat resistance and low in viscosity by a method wherein polyimide resin composition is made to contain specific bismaleimide compound. CONSTITUTION:Thermosetting resin composition contains bismaleimide compound represented by a formula I (Q is hydrocarbon radicals 4 to 20 in number of carbon atoms containing a cycloaliphatic structure, R1, R2, R3, R4, Ri, and Rj denote halogen atoms and hydrocarbon radicals or halogen-containing hydrocarbon radicals 1 to 6 in number of carbon atoms respectively, a, b, c, d, e, and f are integers larger than zero but smaller than 4 respectively and so set as to satisfy formulas, a+b<=4, c+d<=4, and c+d<=4) and monomaleimide compound represented by a formula II (Q2 is hydrocarbon radicals 4 to 20 in number of carbon atoms containing a cycloaliphatic structure, R1, R2, Ri, and Rj denote halogen atoms and hydrocarbon radicals or halogen-containing hydrocarbon radicals 1 to 6 in number of carbon atoms respectively, a, b, c, and d are integers larger than zero but smaller than 4 respectively and so set as to satisfy formulas, a+b<=4, c+d<=4) as integral components. By this setup, polyimide thermosetting resin composition excellent in heat resistance and low in viscosity can be obtained.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermosetting resin composition which is particularly useful as a sealing material for electronic parts, and an electronic part molded and sealed with the composition.

[0002]

2. Description of the Related Art Conventionally, electrical and electronic parts such as semiconductors, which are molded and sealed with epoxy resin, have been widely used. This epoxy resin has been widely put into practical use because it is economically advantageous as compared with the hermetic sealing method using glass, metal, or ceramic. However,
In recent years, the usage conditions of electronic parts have tended to become severe. For example, as the mounting method shifts from conventional insertion mounting to surface mounting, the sealing material itself is exposed to the solder bath temperature. As a result, the heat resistance of the sealing material has become an important characteristic. Recently, thermosetting polyimide resin encapsulation has been proposed for the purpose of obtaining high heat resistance.

[0003]

However, although the electronic encapsulation component molded and encapsulated using a polyimide resin has excellent heat resistance, it has a major drawback in terms of moisture resistance, which is a characteristic of a thermosetting polyimide resin. have. N, N'-
It is possible to reduce the moisture absorption rate by introducing a hydrophobic group into a compound such as diphenylmethane bismaleimide. However, such a maleimide compound has a high melt viscosity and thus has a low flowability and poor workability. For example, it is difficult to add a resin component for improving performance while ensuring sufficient flowability. An object of the present invention is to provide a polyimide-based thermosetting resin composition having excellent heat resistance and low viscosity, and an electronic component molded and encapsulated with the composition.

[0004]

Means for Solving the Problems As a result of intensive investigations, the present inventors have found that a resin composition containing a specific bismaleimide compound is suitable for the above purpose, and completed the present invention. That is, the present invention is as follows. [1] General formula (1)

[0005]

[Chemical 3] (In the formula, Q represents a hydrocarbon group having an alicyclic structure and having 4 to 20 carbon atoms. R ₁ , R ₂ , R ₃ , R ₄ , R _i and R _j are each a halogen atom and 1 to 6 carbon atoms. Represents a hydrocarbon group or a halogen-containing hydrocarbon group having 1 to 6 carbon atoms, and a, b, c, d, e and f are each an integer of 0 or more and 4 or less, a + b ≦ 4, c + d ≦ 4, e + f ≦ 4 And a bismaleimide compound represented by the general formula (2)

[0006]

[Chemical 4] (In the formula, Q ₁ represents a hydrocarbon group having an alicyclic structure and having 4 to 20 carbon atoms. R ₁ , R ₂ , R _i , and R _j are each a halogen atom,
It represents a hydrocarbon group having 1 to 6 carbon atoms or a halogen-containing hydrocarbon group having 1 to 6 carbon atoms, and a, b, c, and d each are an integer of 0 or more and 4 or less, and satisfy a + b ≦ 4 and c + d ≦ 4. And a monomaleimide compound represented by the formula (1) as an essential component.

[2] A thermosetting resin composition containing each component of the thermosetting resin composition and a curing accelerator as essential components.

[3] A thermosetting resin composition containing the components of the thermosetting resin composition described in [1] or [2] above, an epoxy resin, and an epoxy resin curing agent as essential components.

[4] A thermosetting resin composition containing the components of the thermosetting resin composition described in [3] and a filler as essential components. [5] An electronic component molded and sealed with the thermosetting resin composition according to [4].

The present invention will be described in detail below. The thermosetting resin composition containing the bismaleimide compound represented by the general formula (1) and the monomaleimide compound represented by the general formula (2) is synthesized, for example, according to the following steps. First, an alicyclic hydrocarbon Q ₂ having 4 to 20 carbon atoms, which has two ethylenic double bonds in the molecule,

General formula (3)

[Chemical 5] (In the formula, R ₁ , R ₂ , R ₃ , and R ₄ are each a halogen atom,
It represents a hydrocarbon group having 1 to 6 carbon atoms or a halogen-containing hydrocarbon group having 1 to 6 carbon atoms, and c, d, e, and f each are an integer of 0 or more and 4 or less and satisfy c + d + e + f ≦ 4. ) By reacting with a phenol compound represented by the general formula (4)

[0012]

[Chemical 6] (In the formula, Q represents a hydrocarbon group having an alicyclic structure and having 4 to 20 carbon atoms. R ₁ , R ₂ , R ₃ , and R ₄ are each a halogen atom, a hydrocarbon group having 1 to 6 carbon atoms, or Represents a halogen-containing hydrocarbon group having 1 to 6 carbon atoms, and c, d, e, and f are each 0 or more 4
The following integers satisfy c + d ≦ 4 and e + f ≦ 4. ) And a bisphenol compound represented by the general formula (5)

[0013]

[Chemical 7] (In the formula, Q ₁ represents a hydrocarbon group having an alicyclic structure and having 4 to 20 carbon atoms. R ₁ and R ₂ are each a halogen atom and 1 to 6 carbon atoms.
Represents a hydrocarbon group or a halogen-containing hydrocarbon group having 1 to 6 carbon atoms, c and d are each an integer of 0 or more and 4 or less, and c + d ≦ 4
Meet ) Is synthesized with a monophenol compound represented by.

An alicyclic hydrocarbon Q ₂ having 4 to 20 carbon atoms having two ethylenic double bonds in the molecule and the general formula (3)
For the reaction with the phenol compound represented by, a known Friedel-Crafts reaction in which an olefin compound and a phenol are reacted in the presence of a catalyst such as a Lewis acid, a Bronsted acid, a heteropoly acid, or an acidic ion exchange resin is used. To be The _two ethylenic double bonds in the molecule of Q ₂ are linked to phenol unless the molecular structure is symmetrical and equivalent.
Friedel-Crafts Reaction speed is different. By taking advantage of this difference, it is possible to react one double bond of Q ₂ and leave the other without reacting with phenol by adjusting the reaction conditions such as temperature, catalyst, charged amount of raw material, and dropping rate. It is possible. By setting the optimum reaction conditions according to the characteristics of Q ₂ , the mixing ratio of bisphenol and monophenol can be adjusted.

Specific examples of the phenol compound used here include phenol, cresol, xylenol, trimethylphenol, ethylphenol, propylphenol, butylphenol, amylphenol, hexylphenol, methylpropylphenol, methylbutylphenol, and methylhexylphenol. Examples thereof include one or more phenols such as chlorophenol, chlorocresol, chloroxylenol, bromophenol, bromocresol, bromoxylenol, and the like, with phenol, cresol, xylenol, and methylbutylphenol being preferred.

Specific examples of Q ₂ include limonene,
Dipentene, cyclobutadiene, cyclopentadiene,
Examples thereof include dicyclopentadiene, tricyclopentadiene, tetracyclopentadiene, cyclohexadiene, vinylcyclohexene, tetrahydroindene, hexahydronaphthalene, etc. Among them, limonene, dipentene and dicyclopentadiene are preferable.

Q ₁ represents a residue after one double bond of Q ₂ has reacted with the phenols by Friedel-Crafts reaction. Q represents a state in which two double bonds of Q ₂ are reacting with phenols. For example, when Q ₂ is dipentene, Q represents a menthane group, and when Q ₂ is dicyclopentadiene, Q represents a dicyclopentane group. A mixture of the compounds of the general formulas (4) and (5) and the general formula (6)

[0018]

Embedded image (In the formula, X represents a fluorine, chlorine, bromine, iodine or nitro group, R _i and R _j are each a halogen atom, a hydrocarbon group having 1 to 6 carbon atoms or a halogen-containing hydrocarbon group having 1 to 6 carbon atoms. And a and b are each an integer of 0 or more and 4 or less, and satisfying a + b ≦ 4), by reacting with a nitrobenzene compound represented by the general formula (7).

[0019]

[Chemical 9] (In the formula, Q represents a hydrocarbon group having an alicyclic structure and having 4 to 20 carbon atoms. R ₁ , R ₂ , R ₃ , R ₄ , R _i and R _j are each a halogen atom and 1 to 6 carbon atoms. Represents a hydrocarbon group or a halogen-containing hydrocarbon group having 1 to 6 carbon atoms, and a, b, c, d, e and f are each an integer of 0 or more and 4 or less, a + b ≦ 4, c + d ≦ 4, e + f ≦ 4 And a dinitro compound represented by the general formula (8)

[0020]

[Chemical 10] (In the formula, Q ₁ represents a hydrocarbon group having an alicyclic structure and having 4 to 20 carbon atoms, and has the same carbon number as Q represented by the general formula (7). R ₁ , R ₂ , R _i , R _j represents a halogen atom, a hydrocarbon group having 1 to 6 carbon atoms or a halogen-containing hydrocarbon group having 1 to 6 carbon atoms, and a, b, c and d are each an integer of 0 or more and 4 or less, a + b ≦ 4, A mixture of nitro compounds represented by c + d ≦ 4 is synthesized.

Specific examples of the nitrobenzene compound of the general formula (6) include p-fluoronitrobenzene, p-chloronitrobenzene, p-bromochloronitrobenzene, p-iodonitrobenzene, m-dinitrobenzene and o-chloronitrobenzene. However, p-chloronitrobenzene and m-dinitrobenzene are preferable. The above general formula (7)
The mixture of the dinitro compound of formula (8) and the nitro compound of formula (8) is reduced by a method such as reduction with hydrogen in the presence of a catalyst to give a compound of formula (9)

[0022]

[Chemical 11] (In the formula, Q represents a hydrocarbon group having an alicyclic structure and having 4 to 20 carbon atoms. R ₁ , R ₂ , R ₃ , R ₄ , R _i and R _j are each a halogen atom and 1 to 6 carbon atoms. Represents a hydrocarbon group or a halogen-containing hydrocarbon group having 1 to 6 carbon atoms, and a, b, c, d, e and f are each an integer of 0 or more and 4 or less, a + b ≦ 4, c + d ≦ 4, e + f ≦ 4 And a diamino compound represented by the general formula (1
0)

[0023]

[Chemical 12] (In the formula, Q ₁ represents a hydrocarbon group having an alicyclic structure and having 4 to 20 carbon atoms. R ₁ , R ₂ , R _i , and R _j are each a halogen atom,
It represents a hydrocarbon group having 1 to 6 carbon atoms or a halogen-containing hydrocarbon group having 1 to 6 carbon atoms, and a, b, c, and d each are an integer of 0 or more and 4 or less, and satisfy a + b ≦ 4 and c + d ≦ 4. ) A mixture of monoamino compounds represented by

In the general formulas (1) to (10), R ₁ to
Specific examples of R ₄ , R _i and R _j are a hydrogen atom; a halogen atom such as fluorine, chlorine, bromine and iodine; methyl, ethyl,
A butyl, amyl, or hexyl straight-chain or branched alkyl group; a cyclohexyl group; a C1-C6 hydrocarbon group such as a phenyl group; one or more hydrogen atoms of these hydrocarbon groups are substituted with halogen atoms. Groups.

Typical examples of the diamino compound represented by the general formula (9) are as follows. Bis [4- (4-aminophenoxy) phenyl] menthane, bis [2- (4-aminophenoxy) phenyl] menthane, 1- [2- (4-aminophenoxy) phenyl] -8- [4- (4- Aminophenoxy) phenyl] menthane, bis [4- (3-aminophenoxy) phenyl] mentane, bis [2- (3-aminophenoxy) phenyl] mentane, 1- [2- (3-aminophenoxy) phenyl] -8 -[4- (3-aminophenoxy) phenyl] menthane, bis [4- (4-aminophenoxy) -3-methylphenyl) mentane, bis [4
-(4-aminophenoxy) -3,5-dimethylphenyl] menthane, bis [4- (4-aminophenoxy) -3
-Butyl-6-methylphenyl] menthane, bis [4-
(4-amino-5-methylphenoxy) -3-methylphenyl] menthane, bis [4- (4-amino-5-methylphenoxy) -3,5-dimethylphenyl] mentane, bis [4- (4-amino -5-methylphenoxy) -3-butyl-6-methylphenyl] menthane, bis [2- (4-aminophenoxy) -3-methylphenyl] mentane, 1-
[2- (4-aminophenoxy) -3-methylphenyl]
-8- [4- (4-aminophenoxy) -3-methylphenyl] menthane, bis [4- (4-aminophenoxy) phenyl] dicyclopentane, bis [2- (4-aminophenoxy) phenyl] dicyclo Pentane, [2- (4-aminophenoxy) phenyl]-[4- (4-aminophenoxy) phenyl] dicyclopentane, bis [4- (3-aminophenoxy) phenyl] dicyclopentane, bis [2
-(3-aminophenoxy) phenyl] dicyclopentane, [2- (3-aminophenoxy) phenyl]-[4-
(3-Aminophenoxy) phenyl] dicyclopentane, bis [4- (4-aminophenoxy) -3-methylphenyl) dicyclopentane, bis [4- (4-aminophenoxy) -3,5-dimethylphenyl] Dicyclopentane, bis [4- (4-aminophenoxy) -3-butyl-6
-Methylphenyl] dicyclopentane, bis [4- (4-
Amino-5-methylphenoxy) -3-methylphenyl]
Dicyclopentane, bis [4- (4-amino-5-methylphenoxy) -3,5-dimethylphenyl] dicyclopentane, bis [4- (4-amino-5-methylphenoxy)
-3-butyl-6-methylphenyl] dicyclopentane,
Bis [2- (4-aminophenoxy) -3-methylphenyl] dicyclopentane, [2- (4-aminophenoxy)
Examples include -3-methylphenyl]-[4- (4-aminophenoxy) -3-methylphenyl] dicyclopentane and the like.

Examples of the monoamino compound represented by the general formula (10) include those obtained by removing one of the above diamino compounds, such as an aminophenoxyphenyl group. For example, if the diamino compound is bis [4- (4-aminophenoxy) phenyl] menthane, the monoamino compound is [4- (4-aminophenoxy) phenyl] menthane.

A thermosetting reaction containing a target bismaleimide compound and a monomaleimide compound by reacting a mixture of the diamino compound of the general formula (9) with the monoamino compound of the general formula (10) and maleic anhydride. A resin composition is obtained.

According to the above operation, only the monomaleimide compound of the general formula (2) is synthesized, and one or more of them are added to the separately synthesized bismaleimide compound of the general formula (1). You may obtain the thermosetting resin composition of this invention. Examples of such monomaleimide compounds include maleimidophenoxyphenylmenthane, maleimidophenoxyphenyldicyclopentane, maleimidophenoxyphenyltricyclopentane, maleimidophenoxyphenylcyclohexane, maleimidophenoxyphenyldecalin and the like.

The mixing ratio of the bismaleimide of the general formula (1) and the monomaleimide of the general formula (2) is 95: 5, respectively.
It is preferably in the range of 70:30. When the content of monomaleimide is less than this range, the effect of reducing the viscosity is small, and when it is more than this range, the decrease of Tg becomes remarkable. The mixing ratio is gel permeation chromatography (hereinafter G
Abbreviated as PC. ) And high performance liquid chromatography (hereinafter L
Abbreviated as C. ) Is used to determine the peak area ratio when measured with a UV detector at 254 nm.

As the curing accelerator, known curing accelerators (catalysts) can be used. Examples of such catalysts include triphenylphosphine, tri-4-methylphenylphosphine, tri-4-methoxyphenylphosphine, tributylphosphine, trioctylphosphine, tri-2-cyanoethylphosphine, tetraphenylphosphonium tetraphenylborate, and the like. Tertiary amines such as organic phosphine compounds, tributylamine, triethylamine, 1,8-diazabicyclo (5,4,0) undecene-7, triamylamine, benzyltrimethylammonium chloride, benzyltrimethylammonium hydroxide, triethylammonium tetraphenylborate Such as quaternary ammonium salts, imidazoles, boron trifluoride complex, transition metal acetylacetonate, benzoyl peroxide, di-t-butyl peroxide, Radical initiators such as cumyl peroxide, lauroyl peroxide, acetyl peroxide, methyl ethyl ketone peroxide, cyclohexanone peroxide, t-butyl hydroperoxide, and azobisisobutyronitrile are exemplified, but are not limited thereto. is not.
Among these, organic phosphine compounds, 1,8-diazabicyclo (5,4,0) undecene-7 and triethylammonium tetraphenylborate are particularly preferable from the viewpoint of moisture resistance and curability.

It is also possible to use a known polymerization inhibitor together in order to adjust the curing speed. For example,
2,6-di-t-butyl-4-methylphenol, 2,2'-methylenebis (4-ethyl-6-t-butylphenol),
Phenols such as 4,4′-methylenebis (2,6-di-t-butylphenol), 4,4′-thiobis (3-methyl-6-t-butylphenol), hydroquinone monomethyl ether, hydroquinone, catechol, p- t-butylcatechol, 2,5-di-t-butylhydroquinone,
There are polyhydric phenols such as methylhydroquinone, t-butylhydroquinone and pyrogallol, phenothiazine compounds such as phenothiazine, benzophenothiazine and acetamidophenothiazine, and N-nitrosamine compounds such as N-nitrosodiphenylamine and N-nitrosodimethylamine.

As the epoxy resin used in the present invention, known epoxy resins can be used. Specific examples thereof include phenols such as phenol and o-cresol, and naphthols such as hydroxynaphthalene and dihydroxynaphthalene. Epoxy resins derived from novolac resins, which are reaction products of aldehydes such as formaldehyde, phenols such as phenol and o-cresol, naphthols such as hydroxynaphthalene and dihydroxynaphthalene, and xylylenedichlorides. Aralkyl-based epoxy resins derived from aralkylphenol resin, which is a reaction product with, etc., phloroglysin, tris- (4-hydroxyphenyl) -methane, 1,1,2,2, -tetrakis (4-hydroxyphenyl) ) Trivalent or higher such as ethane Glycidyl ether compounds derived from phenol such,

Bisphenol A, bisphenol F, hydroquinone, resorcin, dihydroxynaphthalene,
Bis (4-hydroxyphenyl) menthane, bis (4-hydroxyphenyl) dicyclopentane, 4,4'-dihydroxybenzophenone, bis (4-hydroxyphenyl)
Ether, bis (4-hydroxy-3-methylphenyl)
Ether, bis (3,5-dimethyl-4-hydroxyphenyl) ether, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxy-3-methylphenyl) sulfide, bis (3,5-dimethyl-4-hydroxy) (Phenyl) sulfide, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxy-3-methylphenyl) sulfone, bis (3,5-dimethyl-4-hydroxyphenyl)
Sulfone, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxy-3-methylphenyl) cyclohexane, 1,1-bis (3,5-dimethyl-4)
-Hydroxyphenyl) cyclohexane,

4,4'-dihydroxybiphenyl, 4,4'-dihydroxy-3,3 ', 5,5'-tetramethylbiphenyl, bis (hydroxynaphthyl) methane, 1,1'-binaphthol, 1,1' -Glycidyl ether compounds derived from dihydric phenols such as bis (3-t-butyl-6-methyl-4-hydroxyphenyl) butane or diglycidyl ethers derived from halogenated bisphenols such as tetrabromobisphenol A Compounds, glycidyl ether compounds of polyhydric phenols obtained by condensation reaction of phenols and aromatic carbonyl compounds, p-aminophenol, m-aminophenol, 4-aminometacresol, 6-aminometacresol, 4,4 ' -Diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 4,4'-
Diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 1,4-bis (4-aminophenoxy) benzene, 1,4-bis (3-aminophenoxy) benzene, 1,3
-Bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 2,2-bis (4-aminophenoxyphenyl) propane, p-phenylenediamine, m-phenylenediamine, 2,4 -Amine derived from toluenediamine, 2,6-toluenediamine, p-xylylenediamine, m-xylylenediamine, 1,4-bis (methylamino) cyclohexane, 1,3-bis (methylamino) cyclohexane Epoxy resin,

Glycidyl ester compounds derived from aromatic carboxylic acids such as p-oxybenzoic acid, m-oxybenzoic acid, terephthalic acid and isophthalic acid, and hydantoin epoxy compounds derived from 5,5-dimethylhydantoin and the like. 2,2-bis (3,4-epoxycyclohexyl) propane, 2,2-bis [4- (2,3-epoxypropyl) cyclohexyl] propane, vinylcyclohexenedioxide, 3,4-epoxycyclohexylmethyl-
There are alicyclic epoxy resins such as 3,4-epoxycyclohexanecarboxylate, aliphatic epoxy resins obtained by oxidizing double bonds in unsaturated hydrocarbon compounds such as polybutadiene, and N, N-diglycidylaniline. One or more of these epoxy resins are used. Among them, dihydroxynaphthalene, bis (4-hydroxyphenyl) ether, bis (3,5-dimethyl-4-hydroxyphenyl) sulfide, 1,1-bis (4-hydroxy-3-methylphenyl) cyclohexane, 4,4 ′ -Dihydroxybiphenyl, 4,4'-dihydroxy-3,3 ', 5,5'-
Diglycidyl ether compounds of tetramethylbiphenyl, bis (4-hydroxyphenyl) menthane and bis (4-hydroxyphenyl) dicyclopentane are preferable from the viewpoint of viscosity, adhesiveness and low hygroscopicity.

Also, known epoxy curing agents can be used in the present invention. Examples of these are phenols such as phenol, o-cresol and catechol, hydroxynaphthalenes, polyphenols and polynaphthol novolac resins which are reaction products of naphthols such as dihydroxynaphthalene and aldehydes such as formaldehyde, and phenols. , O-cresol, catechol, and other phenols, hydroxynaphthalene, dihydroxynaphthalene, and other naphthols, and polyaralkylphenol resins and polyaralkylnaphthol resins, which are reaction products of xylylenedichloride, phenol, o-cresol Fat which is the reaction product of phenols such as catechol, naphthols such as hydroxynaphthalene and dihydroxynaphthalene, and unsaturated alicyclic hydrocarbons such as dicyclopentadiene and limonene Wherein the hydrocarbon-containing polyphenol resins and poly naphthol resins,

Trihydric or higher phenols such as phloroglysin, tris- (4-hydroxyphenyl) -methane, 1,1,2,2, -tetrakis (4-hydroxyphenyl) ethane, bisphenol A, bisphenol F, hydroquinone , Resorcin, dihydroxynaphthalene, bis (4
-Hydroxyphenyl) ethane, bis (4-hydroxyphenyl) propane, bis (4-hydroxyphenyl)
Butane, bis (4-hydroxyphenyl) pentane, bis (4-hydroxyphenyl) hexane, 1,3,3-trimethyl-1-m-hydroxyphenylindane-5 or 7
-Ol, bis (4-hydroxyphenyl) menthane,
Bis (4-hydroxyphenyl) dicyclopentane, 4,
4'-dihydroxybenzophenone, bis (4-hydroxyphenyl) ether, bis (4-hydroxy-3-methylphenyl) ether, bis (3,5-dimethyl-4-hydroxyphenyl) ether, bis (4-hydroxyphenyl) Sulfide, bis (4-hydroxy-3-methylphenyl) sulfide, bis (3,5-dimethyl-4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxy-3-methylphenyl) Sulfone, bis (3,5-dimethyl-4-hydroxyphenyl) sulfone, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxy-3-)
Methylphenyl) cyclohexane, 1,1-bis (3,5-dimethyl-4-hydroxyphenyl) cyclohexane, 4,
4'-dihydroxybiphenyl, 4,4'-dihydroxy-3,
3 ', 5,5'-tetramethylbiphenyl, bis (hydroxynaphthyl) methane, 1,1'-binaphthol, 1,1'-bis (3-t-butyl-6-methyl-4-hydroxyphenyl)
Dihydric phenols such as butane or halogenated bisphenols such as tetrabromobisphenol A,

Polyhydric phenols obtained by condensation reaction of phenols with aromatic carbonyl compounds, polycarboxylic acids such as maleic acid, phthalic acid, nadic acid, methyl-tetrahydrophthalic acid, methyl nadic acid and their anhydrides, diaminodiphenylmethane. , Diaminodiphenyl sulfone, diaminodiphenyl ether, phenylenediamine, diaminodicyclohexylmethane, xylylenediamine, toluenediamine, diaminocyclohexane,
Examples thereof include polyamine compounds such as dichloro-diaminodiphenylmethane (each including isomers), ethylenediamine, hexamethylenediamine, etc., and active hydrogen-containing compounds capable of reacting with an epoxy group such as dicyandiamide, tetramethylguanidine and the like. Among them, phenolic novolac resins, naphthol novolac resins, phenolic aralkyl resins, naphthol aralkyl resins,
An alicyclic hydrocarbon-containing polyphenol resin and an alicyclic hydrocarbon-containing polynaphthol resin are preferably used in terms of curability and moisture resistance.

A thermosetting resin composition comprising (A) a bismaleimide compound and a monomaleimide compound of the present invention, (B) a curing accelerator, (C) an epoxy resin and (D) an epoxy curing agent, The quantitative ratio of each component (A), (B), (C), (D) of the resin can be appropriately selected according to the application, desired heat resistance and the like. However, in general, the content ratio of the bismaleimide compound and the monomaleimide compound {(A) / [(A) + (C) + (D)]} is 90% to
It is preferable to select 10%. More preferably, it is 70 to 30%. If the blending ratio of the bismaleimide compound and the monomaleimide compound deviates from the above range, the moisture resistance and heat resistance decrease, which is not preferable.

The epoxy resin as the component (C) and the epoxy curing agent as the component (D) are preferably mixed in the same equivalent amount. If the blending ratio of the component (C) and the component (D) deviates from the same equivalent amount, the moisture resistance, curability and the like will deteriorate, which is not preferable.

Examples of the filler used in the present invention include fused silica, crystalline silica, alumina, talc, calcium carbonate, titanium white, clay, asbestos, mica, red iron oxide, and glass fiber. Among them, fused silica and crystals are particularly preferable. Silica and alumina are preferably used.

Further, the blending ratio of the filler can be appropriately determined according to the purpose, but when it is used for encapsulating a semiconductor, it is preferably 30 to 90% by weight in the total amount of the resin composition, and more preferably. Is 60 to 85% by weight. If the amount of the filler is less than 30% by weight, the moisture resistance is inferior, and if it exceeds 90% by weight, there is a problem in moldability.

In the present invention, if necessary, a natural wax, a synthetic wax, a higher fatty acid and its metal salt, a releasing agent such as paraffin or a coloring agent such as carbon black, and a surface treatment such as a silane coupling agent. Agents and the like may be added. Further, a flame retardant such as antimony trioxide, a phosphorus compound and a brominated epoxy resin may be added. A brominated epoxy resin is particularly preferable for producing a flame retardant effect.

Further, in order to reduce the stress, for example, various elastomers may be added or reacted in advance and used. Specific examples thereof include addition type or reaction type elastomers such as polybutadiene, butadiene-acrylonitrile copolymer, silicone rubber and silicone oil.

The thermosetting resin composition thus obtained can be compounded by mixing with a general kneader such as a roll or a co-kneader.

In order to seal electronic parts such as semiconductors using the thermosetting resin composition according to the present invention, curing molding may be carried out by a conventionally known molding method such as transfer molding, compression molding or injection molding.

[0047]

EXAMPLES Examples of the present invention will be shown below, but the present invention is not limited thereto. The evaluation method of the kneaded product and the cured molded product is as follows. Gel time: The kneaded products obtained in Examples and Comparative Examples
0.5g was taken in the concave portion of the hot plate at 180 ° C, and the time until gelation was measured.・ Glass transition temperature: Thermomechanical analyzer (SHIMADZU DT
-30).・ Barcol hardness: 17 according to ASTM D-648 with 935 type
It was measured under the condition of 5 ° C / 3 minutes. Bending strength and flexural modulus: Measured with an Instron universal material testing machine (SHIMADZU IS-10T) according to JIS K-6911.・ Moisture absorption rate: Constant temperature and humidity chamber (Advantech Toyo Corp.)
AGX-225) was used to measure the weight change under the conditions of 85 ° C / 85% RH.・ Spiral flow: 17 according to EMMI-1-66
It was performed under the conditions of 5 ° C./70 kg / cm ² . -Adhesive strength (aluminum peel): A molded product was transfer-molded on a commercially available aluminum foil, and the peel strength was evaluated.

・ Solder cracking: Simulated IC (52 pin QFP
Package: Package thickness 2.05mm) 85 ℃ / 85% RH / 72
The number of individual ICs in which cracks have occurred after being soaked in a solder bath at 240 ° C for 30 seconds immediately after absorbing moisture under the conditions of time.
8 test individuals.

Synthesis Example 1 Phenol 188 g, toluene 1 in a 1-liter four-necked flask equipped with a thermometer, a stirrer, and a dropping funnel.
Charge 88 g and 13 g of boron trifluoride ether complex and dissolve under a nitrogen stream. 136 g of dipentene in toluene 1
The liquid dissolved in 36 g was added dropwise at a temperature of 0 to 5 ° C over 2 hours. The reaction was further continued at a temperature of 0 to 5 ° C for 2 hours and at room temperature for 2 hours, and then the temperature was raised to 60 ° C to complete the reaction. When 250 g of a 5% aqueous sodium hydroxide solution was added and stirring was continued at room temperature for a long time, the brown solution turned pale yellow. After liquid separation, the organic layer is purified water
Washed 3 times with 250 g. The reaction solution was refluxed under reduced pressure using a Dean-Stark azeotropic dehydrator to separate and remove water. 309 g of a light brown solid was obtained by concentrating the solvent under reduced pressure.
(Yield 95.4%) was obtained. From GPC (UV detector, detected at 254 nm) measurement, it was found that the adduct of one molecule of dipentene and two molecules of phenol was contained in 88%, and the adduct of one molecule of dipentene and one molecule of phenol was contained in 12%. This mixture is designated as phenol A.

Synthesis Example 2 Phenol A 25 obtained in Synthesis Example 1 was placed in a 2-liter four-necked flask equipped with a thermometer, a stirrer and a condenser.
0.0 g, 246.5 g of p-chloronitrobenzene and 844 g of dimethylacetamide (hereinafter abbreviated as DMAc) were charged and dissolved at 50 ° C. under a nitrogen stream. Sodium hydroxide
79 g was added, the temperature was raised to 80 ° C, the reaction was continued at 80 to 90 ° C for 3 hours, and the reaction was continued for 2 hours after raising the internal temperature to 100 ° C. Product name Kyoward 10 after neutralization with carbon dioxide
00 (filter aid, manufactured by Kyowa Chemical Industry Co., Ltd.) was added to 30 g of the reaction mixture to remove salts generated by filtration. It was washed with 200 g of dimethylacetamide and combined with the filtrate. A part of this solution was concentrated under reduced pressure, washed with water and then with methanol, and pale yellow crystals were collected by filtration. The crystals were dried under reduced pressure. 1340 and 1512 cm from infrared absorption spectrum
Absorption by the nitro group was observed at ^-1 . This compound is named Nitro A.

Synthesis Example 3 The nitro obtained in Synthesis Example 2 was placed in a 1-liter eggplant-shaped flask.
350 g of A DMAc solution (concentration adjusted to 33.3% by weight)
5.8 g of 5% palladium / activated carbon catalyst was charged. Decompress
Then, the pressure was restored with nitrogen to remove oxygen in the system. Then again
Repeat the operation of depressurizing and then re-pressurizing with hydrogen three times.
The inside of the reaction vessel was replaced with hydrogen. Internal temperature of 80 under hydrogen atmosphere
Raise the temperature to ± 5 ° C, continue the reaction at the same temperature for 12 hours, and
The response was completed. After reducing the pressure, restore the internal pressure with nitrogen,
Hydrogen was removed. Separately, the product name on the filter paper of the filter device
Coat with Olite (a type of filter aid made by Mizusawa Chemical Co., Ltd.)
The reaction solution was filtered at 80 ° C. and washed with 20 g of DMAc.
It was Put the filtrate in a 1 liter flask and use DMA under reduced pressure.
c was recovered. Add chlorobenzene and add reaction mixture.
After dissolution, azeotropic dehydration is performed under reduced pressure, and Dean-Stark dehydrator is used.
Was used to separate and remove water in the system. Subsequent filtration
The soluble component was removed. Concentrate a portion of the solution under reduced pressure to obtain a standard
I got the goods. This product is a light brown glass and has infrared absorption.
Collection spectrum at 1228 cm^-1To ether bond, 3210, 336
0, 3440 cm ^-1Absorption due to amino bond was observed. This
Is referred to as amine A.

Synthetic Example 4 Imide compound; N, N'-bis (4-aminophenoxyphenyl) menthane Synthesis of resin composed of bismaleimide and maleimidophenoxyphenylmenthane. A 500 ml four-necked flask was charged with 47.6 g of maleic anhydride, 67.8 g of chlorobenzene and 3.6 g of DMAc, and dissolved by stirring under a nitrogen stream. Amine A chlorobenzene solution obtained by the operation of Synthesis Example 3 (concentration adjusted to 33.3% by weight)
Using a dropping funnel, 150.0 g was added dropwise to the flask at 25 ± 5 ° C. over 2 hours. The reaction was continued at 35 ° C. for 2 hours to complete the amide oxidation reaction. Subsequently, 1.9 g of p-toluenesulfonic acid monohydrate was added, and 100% was carried out under reduced pressure while performing azeotropic dehydration.
The dehydration ring closure reaction was carried out at 131 ° C. for 4 hours at 110 ° C. for 1 hour at 110 ° C., and then gradually returning to normal pressure. The produced water was separated from the system using a Dean-Stark azeotropic dehydrator to proceed the reaction.

Then, under reduced pressure, chlorobenzene and then D
A total of 90% of MAc was recovered. Subsequently, 220 g of methyl isobutyl ketone (hereinafter abbreviated as MIBK) was added and dissolved. The solution was cooled to 60 ° C., and sodium bicarbonate and 300 g of water, which were weighed so that the pH of the aqueous layer was 5 to 7, were added to neutralize the solution, followed by washing and liquid separation. 2 at 300 ° C with 15% saline at 60 ° C
After washing twice and separating, azeotropic dehydration was performed under reduced pressure, and salts were removed by filtration. The filtrate is concentrated under reduced pressure, finally 15
After reaching the condition of 0 ° C / 5 Torr, the product was taken out from the flask in a molten state, and a light brown solid was obtained in an amount of 129 g (yield: 97.6
%) (Denoted as imide A). Ether bond 1238 cm ^-1 by infrared absorption spectrum, absorption by imide bond at 1712 cm ^-1. Also, from GPC, N,
The content of N'-bis (4-aminophenoxyphenyl) menthane bismaleimide was 86%, that of maleimidophenoxyphenylmenthane was 11%, and that of the high molecular weight component was 3%.

Example 1 Imide A obtained in the above Synthesis Example 4, glycidyl ether of o-cresol novolac as an epoxy resin (trade name: Sumiepoxy ESCN-195, manufactured by Sumitomo Chemical Co., Ltd., epoxy equivalent 201 g / equivalent) , Hydrolyzable chlorine (330 ppm), phenol novolac as an epoxy curing agent (manufactured by Arakawa Chemical Co., Ltd., trade name Tamanol 759, OH equivalent = 106 g /
eq), triphenylphosphine as a curing accelerator and
Tetraphenylphosphonium tetraphenylborate,
Fractured fused silica (brand name FS-891, manufactured by Denki Kagaku), spherical fused silica (brand name FB-74, manufactured by Denki Kagaku), as filler, carnauba wax as coupling agent, coupling agent (Product name SH-6040, Toray Dow Corning Silicone product and product name KBM-573, Shin-Etsu Chemical Co., Ltd.) were blended in the amounts (g) shown in Table 1, heated and kneaded with a roll, and transfer molding was performed. went. Further, post-curing was performed at 200 ° C. for 5 hours to obtain a cured molded product. Further, when the melt viscosity at 175 ° C. of the imide A obtained in Synthesis Example 4 was examined, it was 4.6 poise. At this time, no evaporative component was recognized and there was no irritating odor.

Comparative Example 1 N, N′-bis (4-aminophenoxyphenyl) menthane bismaleimide as an imide compound (Sumitomo Chemical Co., Ltd., trade name Bestlex MPD, melt viscosity 7.3 poise / 150 ° C.) A cured molded product was obtained in the same manner as in Example 1 except that was used. The formulation is shown in Table 1. The results of the physical properties of the resin compositions obtained in Example 1 and Comparative Example 1 and the physical properties of the cured moldings thereof are shown in Table 1.

[0056]

[Table 1]

[0057]

INDUSTRIAL APPLICABILITY The thermosetting resin composition of the present invention has a low viscosity, is excellent in workability and heat resistance, and particularly excellent in adhesiveness, and is useful as a composition for a sealing material. The resin composition of the present invention is mainly used for sealing electronic parts such as semiconductors.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Internal reference number FI Technical indication location C08K 5/3415 KBG (72) Inventor Hiroshi Shiomi 6 Kitahara, Tsukuba, Ibaraki Sumitomo Chemical Co., Ltd. ( 72) Inventor Noriaki Saito 6 Kitahara, Tsukuba, Ibaraki Sumitomo Chemical Co., Ltd.

Claims (6)

[Claims] (A) General formula (1): (In the formula, Q represents a hydrocarbon group having an alicyclic structure and having 4 to 20 carbon atoms. R ₁ , R ₂ , R ₃ , R ₄ , R _i and R _j are each a halogen atom and 1 to 6 carbon atoms. Represents a hydrocarbon group or a halogen-containing hydrocarbon group having 1 to 6 carbon atoms, and a, b, c, d, e and f are each an integer of 0 or more and 4 or less, a + b ≦ 4, c + d ≦ 4, e + f ≦ 4 And a bismaleimide compound represented by the general formula (2): (In the formula, Q ₁ represents a hydrocarbon group having an alicyclic structure and having 4 to 20 carbon atoms. R ₁ , R ₂ , R _i , and R _j are each a halogen atom,
It represents a hydrocarbon group having 1 to 6 carbon atoms or a halogen-containing hydrocarbon group having 1 to 6 carbon atoms, and a, b, c, and d each are an integer of 0 or more and 4 or less, and satisfy a + b ≦ 4 and c + d ≦ 4. And a monomaleimide compound represented by the formula (1) as an essential component. 2. The thermosetting resin composition according to claim ₁ , wherein Q and Q ₁ in the general formulas (1) and (2) are dipentene residues or dicyclopentadiene residues. 3. A thermosetting resin composition comprising each component of the thermosetting resin composition according to claim 1 or 2 and a curing accelerator as essential components. 4. A thermosetting resin composition comprising each component of the thermosetting resin composition according to claim 1, 2 or 3; an epoxy resin; and an epoxy resin curing agent as essential components. 5. A thermosetting resin composition comprising each component of the thermosetting resin composition of claim 4 and a filler as essential components. 6. An electronic component molded and encapsulated with the thermosetting resin composition according to claim 5.