JPH089653B2 - Curable resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial field of application] The present invention provides a novel addition reaction type unsaturated bisimide compound capable of providing a cured product having excellent heat resistance, flexibility and adhesiveness. A composition comprising:

[Conventional technology]

In the fields of electric equipment and electronic parts, achieving small size, light weight, high performance, and high reliability is a very important key technology in terms of the performance of the applied material. Among these materials, organic materials are required to balance a wide range of characteristics such as heat resistance, flexibility, adhesiveness, and moisture resistance, and are being studied intensively. Heretofore, N, N′-substituted bismaleimide-based materials, which are advantageous in terms of imparting heat resistance, have mainly been the subject of research and application.

[Problems to be solved by the invention]

However, conventional N, N′-substituted bismaleimide-based materials are mainly aromatic ring-based compounds, and have many problems in terms of moldability, adhesion, and flexibility. For the purpose of compensating for these drawbacks, the compounds have been dealt with by combining them with amine compounds, epoxy compounds, unsaturated polyesters and the like. However, by this means, it is unavoidable that the original heat resistance of the N, N′-substituted bismaleimide is deteriorated, and the balance of the required properties is becoming a major issue. In order to deal with these problems, recently, a bismaleimide compound having a novel skeleton in the main chain (JP-A-60-185784) has been proposed. But,
With respect to the compound as well, sufficient processability was taken, such as low moldability, particularly low solubility in common solvents (ketones and petroleum-based solvents), poor compatibility with other concomitant materials, and the like. It is not a thing.

An object of the present invention is to provide a novel addition reaction type unsaturated bisimide compound compounding composition capable of achieving both heat resistance and flexibility, improving adhesiveness, and improving moldability.

[Means for solving problems]

Briefly describing the present invention, the present invention is an invention relating to a curable resin composition, the following general formula I: [In the formula, D ₁ and D ₂ are the same or different, and are represented by the formula -CH = CH-, The groups represented by R ₁ and R ₂ are the same or different, and have the formula CH ₂
n, (Wherein q is the same or different, H, CH ₃ , C
_{2 H 5, Cl, Br,} F, -OCH 3, -OC 2 H 5 or -OH group, x
CH ₂ n, -O -, - COO -, - CO -, - NH -, - S-, SO 2 -, -
CH = CH-, -CH = N-, -N = N-, Group, n represents a group represented by 1 to 10)], and an unsaturated bisimide compound of 2,4,8,10-tetraoxaspiro [5.5] undecane represented by And a compound having.

In the present invention, the unsaturated bisimide compound of 2,4,810-tetraoxaspiro [5.5] undecane represented by the general formula I is, for example, and so on.

The unsaturated bisimide compound of 2,4,8,10-tetraoxaspiro [5.5] undecane represented by the general formula I is, for example, the following general formula II: (In the formula, R ₁ and R ₂ have the same meaning as those in the formula I)
A terminal diamine compound of 2,4,8,10-tetraoxaspiro [5.5] undecane and the following general formula III: (In the formula, D ₁ and D ₂ have the same meanings as those in the formula I), and subjected to an addition reaction with a corresponding unsaturated dicarboxylic acid anhydride,
Then, it can be produced by dehydration cyclization.

The reaction method for obtaining the general formula I of the present invention from the general formula II and the general formula III is not particularly limited, but in order to produce the unsaturated bisimide compound of the general formula I, In one step, Formula IV: An ether unsaturated carboxylic acid amic acid represented by the formula: wherein D ₁ , D ₂ and R ₁ , R ₂ have the same meanings as in the above formula I is produced.

For this purpose, a known method can be applied. For example, there is a method in which a diamine compound having a spiro ring represented by the general formula II and an ethylenically unsaturated dicarboxylic acid anhydride represented by the general formula III are homogeneously contacted in an organic liquid which is a common solvent for both.

Usually, as a commonly used solvent, dimethylformamide, dimethylacetamide, dimethylsulfoxide, N-methyl-2-pyrrolidone, N-methylcaprolactam, tetrahydrofuran, dioxane, acetone,
For example, diethyl ketone. Next, as the second step, the unsaturated carboxamic acid is cyclized and dehydrated to generate an imide ring. As this method, U.S. Patent 3,018,290,
Known methods described in the respective specifications of No. 3,018,292 and No. 3,127,414 may be used. That is, dehydration from the amic acid of formula VI yields acetic anhydride as the anhydride,
The tertiary amine, for example triethylamine, is used in an amount of 1.05 to 1.5 moles per mole and is added in an amount of 0.15 to 0.15 moles per 1 mole of amic acid groups.
It is advisable to add 0.5 mol, and further to carry out the reaction in acetone in the presence of 0.5 to 0.05 mol of potassium acetate, nickel acetate or the like as a catalyst with respect to 1 mol of an amic acid group.

As a specific example, for example, the following synthetic reaction process, Or Then, the unsaturated bisimide compound targeted by the present invention can be obtained.

The 3,9-bis (3-amino) 2,4,8,10-tetraoxaspiro [5.5] undecane compound represented by the general formula II of the present invention is, for example, and so on. The compounds may be used alone or in combination. Further, in the present invention, the above general formula II
The ethylenically unsaturated dicarboxylic acid anhydride represented by I is, for example, a compound represented by the following formula, which is a Diels-Alder adduct of maleic anhydride or a corresponding compound and dicyclopentadiene: The unsaturated bisimide compound represented by the general formula I of the present invention is modified by adding at least one monomer containing a polymerizable CH ₂ ═C group, which may be of vinyl, allyl or acrylic type. it can. Here, as the monomer, for example, styrene, vinyltoluene, α-methylstyrene, divinylbenzene, diallyl phthalate,
Diallyl phthalate prepolymer, chlorostyrene, dichlorostyrene, bromostyrene, dibromostyrene,
There are diallyl benzene phosphonate, diallyl aryl phosphinic acid ester, acrylic acid, methacrylic acid ester, triallyl cyanurate, triallyl cyanurate prepolymer, tribromophenol allyl ether, etc., and one or more of them may be used in combination. Can be used.

Further, the unsaturated bisimide compound represented by the general formula I of the present invention can be modified before curing by adding a known unsaturated polyester. Here, the unsaturated polyester means an unsaturated dibasic acid, a saturated dibasic acid and an anhydride thereof or a lower alkyl ester derivative thereof and a diol or an alkylene monoxide and a derivative thereof in the presence or absence of a catalyst. Polyester resin matrix containing unsaturated groups synthesized by condensation or addition polymerization utilizing reactions such as esterification and transesterification, and ethylene (eg vinyl group, allyl group, etc.) polymerizability It is composed of a compound and a mixture with a peroxide catalyst. In addition to these, vinyl ester resins obtained by reacting bisphenol A type and novolak type epoxy compounds with methacrylic acid or acrylic acid are also useful. Here, as the representative of the unsaturated dibasic acid and the saturated dibasic acid, maleic acid, maleic anhydride, fumaric acid, chloromaleic acid, dichloromaleic acid, citraconic acid, citraconic anhydride, mesaconic acid, and itacone Acid, succinic acid, adipic acid, sebacic acid, azelaic acid, phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, methylglutaric acid anhydride, pimelic acid, hexahydrophthalic acid and its anhydride, tetrahydrophthalic acid, carbic anhydride Acids, hettic acid and its anhydrides, tetrachlorophthalic acid and its anhydrides, tetrabromophthalic acid and its anhydrides, lower alkyl esters thereof and the like are used, and as the diol component, ethylene glycol, diethylene glycol, triethylene glycol, Polyethylene glycol, propylene glycol Alcohol, dipropylene glycol, trimethylene glycol, tetramethylene glycol, hexamethylene glycol, 2,2-diethylpropanediol, 1,3-neopentyl glycol, dibromoneopentyl glycol, bisphenol ethyl ether of bisphenol, hydrogenation Bisphenol A, 2,2-
Di (4-hydroxypropoxyphenyl) propane, ethylene oxide, propylene oxide, 3,3,3-trichloropropylene oxide, 2-methyl-3,3,3-trichloropropylene oxide, phenyl glycidyl ether, allyl glycidyl ether, etc. used. Also,
If necessary, a trifunctional or higher-functional polybasic acid and / or polyhydric alcohol may be used in combination as long as the object of the present invention is not impaired. Examples of the cross-linking agent include styrene, vinyltoluene, α-methylstyrene, divinylbenzene, diallyl phthalate, diallyl phthalate prepolymer, glorostyrene, dichlorostyrene, promostyrene, dipromostyrene, diallylbenzene sulfonate, diallyl arylphosphinic acid ester, and acrylic. Acid ester,
Methacrylic acid ester, triallyl cyanurate, triallyl cyanurate prepolymer, tripromophenol allyl ether and the like are used. In the present invention,
The acid component, alcohol component, and crosslinking agent are not limited to one type, and two or more types can be used in combination. Further, it is possible to add various modifying agents and modifying agents. Further, the unsaturated polyester is not limited to one kind, and two or more kinds may be mixed.

Further, the unsaturated bisimide compound represented by the general formula I of the present invention becomes a heat resistant material having excellent flexibility by reacting with polyamine, especially diamine. Here, examples of the amine compound include m-phenylenediamine, p-phenylenediamine, benzidine, and 3,3′-dimethyl-4,4 ′.
-Diaminobiphenyl, 3,3'-dichlorobenzidine,
3,3'-dimethoxybenzidine, 4,4'-diaminodiphenylmethane, 1,1-bis (4-aminophenyl) ethane, 2,2-bis (4-aminophenyl) propane, 2,2-
Bis (4-aminophenyl) hexafluoropropane,
2,2-bis (4-aminophenyl) -1,3-dichloro-1,
1,3,3-tetrafluoropropane, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide, 4,4'-diamino Diphenyl sulfoxide, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 3,3'-diaminobenzophenone, 4,4'-diaminobenzophenone, 3,4'-diamino Benzophenone, N, N
-Bis (4-aminophenyl) aniline, N, N-bis (4-aminophenyl) methylamine, N, N-bis (4
-Aminophenyl) -n-butylamine, N, N-bis (4-aminophenyl) amine, m-aminobenzoyl-p-aminoanilide, 4-aminophenyl-3-aminobenzoate, 4,4'-diaminoazobenzene, 3,3 ′
-Diaminoazobenzene, bis (3-aminophenyl)
Diethylsilane, bis (4-aminophenyl) phenylphosphine oxide, bis (4-aminophenyl) ethylphosphine oxide, 1,5-diaminonaphthalene, 2,6
-Diaminopyridine, 2,5-diamino-1,3,4-oxadiazole, m-xylylenediamine, p-xylylenediamine, 2,4 (p-β-amino-tertiary butylphenyl) ether, p -Bis-2- (2-methyl-4-aminopentyl) benzene, p-bis (1,1-dimethyl-5)
-Aminopentyl) benzene, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, 2,
11-diaminododecane, 1,12-diaminooctadecane,
2,2-dimethylpropylenediamine, 2,5-dimethylhexamethylenediamine, 3-methylheptamethylenediamine, 2,5-dimethylheptamethylenediamine, 4,4-dimethylheptamethylenediamine, 5-methylnonamethylenediamine, 1 , 4-diaminocyclohexane, bis (p-
Aminocyclohexyl) methane, 3-methoxyhexamethylenediamine, 1,2-bis (3-aminopropoxy)
Ethane, bis (3-aminopropyl) sulfide, N, N
-Bis (3-aminopropyl) methylamine and the like.

Further, examples of the N-aryl-substituted aromatic triamine include 2,4-diaminodiphenylamine and 2,4-diamino-
5-methyl-diphenylamine, 2,4-diamino-4 '
-Methyl-diphenylamine, 1-anilino-2,4-diaminonaphthalene, 3,3'-diamino-4-anilinobenzophenone and the like.

Further, in the present invention, in particular, the general formula V: (In the formula, R ₅ and R ₆ are hydrogen, a methyl group, an ethyl group, a trifluoromethyl group or a trichloromethyl group, which may be the same or different from each other.) And have an ether bond. The use of diamine is also effective in improving the solubility of the composition in a solvent and achieving a balance between heat resistance and flexibility. Examples of such a compound include 2,2-bis [4- (4-aminophenoxy) phenyl] propane and 2,2'-bis [3-methyl-
4- (4-aminophenoxy) phenyl] propane, 2,
2-bis [3-chloro-4- (4-aminophenoxy)
Phenyl] propane, 2,2-bis [3-bromo-4-
(4-Aminophenoxy) phenyl] propane, 2,2-
Bis [3-methyl-4- (4-aminophenoxy) phenyl] furopan, 22-bis [3-propyl-4- (4-
Aminophenoxy) phenyl] propane, 2,2'-bis [3-isopropyl-4- (4-aminophenoxy) phenyl] propane, 2,2-bis [3-n-butyl-4-
(4-Aminophenoxy) phenyl] propane, 2,2 ′
-Bis [3-sec-butyl-4- (4-aminophenoxy) phenyl] propane, 2,2-bis [3-methoxy-
4- (4-aminophenoxy) phenyl] propane, 1,
1-bis [4- (4-aminophenoxy) phenyl] ethane, 1,1-bis [3-methyl-4- (4-aminophenoxy) phenyl] ethane, 1,1-bis [3-chloro-
4- (4-aminophenoxy) phenyl] ethane, 1,1
-Bis [3-promo-4- (4-aminophenoxy) phenyl] ethane, bis [4- (4-aminophenoxy)
Phenyl] methane, bis [3-methyl-4- (4-aminophenoxy) phenyl] methane, bis [3-chloro-
4- (4-aminophenoxy) phenyl] methane, bis [3-bromo-4- (4-aminophenoxy) phenyl] methane, 1,1,1,3,3,3-hexafluoro-2,2-bis [4 -(4-aminophenoxy) phenyl] propane,
1,1,1,3,3,3-hexachloro-2,2-bis- [4- (4-
Aminophenoxy) phenyl] propane, 3,3-bis [4- (4-aminophenoxy) phenyl] pentane,
1,1-bis [4- (4-aminophenoxy) phenylpropane, 1,1,1,3,3,3-hexafluoro-2,2-bis [3,
5-Dimethyl-4- (4-aminophenoxy) phenyl] propane, 1,1,1,3,3,3-hexafluoro-2,2-bis [3,5-dibromo-4 (4-aminophenoxy) phenyl] Propane, 1,1,1,3,3,3-hexafluoro-2,2-
Bis [3-methyl-4- (4-aminophenoxy) phenyl] propane and the like.

Further, by further reacting the terminal amine compound of 2,4,8,10-tetraoxaspiro [5.5] undecane represented by the general formula II with the unsaturated bisimide represented by the general formula I, heat resistance It is also possible to provide a cured product in which flexibility and low shrinkage are balanced.

Furthermore, the general formula (In the formula, R ₇ is an alkylidene group containing a methylene group, n is an average number of 0.1 or more), and the like polyamines can be used.

In addition, you may use these amine compounds in mixture.

In addition, the unsaturated bisimide compound represented by the general formula I of the present invention can be used for a wide range of applications by combining it with an epoxy compound. Examples of such epoxy compounds include diglycidyl ether of bisphenol A, butadiene diepoxide, 3,4-epoxycyclohexylmethyl- (3,4-epoxy) cyclohexanecarboxylate, vinylcyclohexanedioxide, 4,4 '. -Di (1,2-epoxyethyl) diphenyl ether, 4,4 '-(1,2-epoxyethyl) biphenyl, 2,
2-bis (3,4-epoxycyclohexyl) propane, resorcin diglycidyl ether, phloroglucin diglycidyl ether, methyl phloroglucin diglycidyl ether, bis- (2,3-epoxycyclopentyl) ether, 2- (3 , 4-Epoxy) cyclohexane-5,5-spiro (3,4-epoxy) -cyclohexane-m
-Difunctional epoxy compounds such as dioxane, bis- (3,4-epoxy-6-methylcyclohexyl) adipate, N, N'-m-phenylenebis (4,5-epoxy-1,2-cyclohexane) dicarboximide Triglycidyl ether of para-aminophenol, polyallyl glycidyl ether, 1,3,5-tri (1,2-epoxyethyl) benzene, 2,2 ', 4,4'-tetraglycidoxybenzophenone, tetraglyci Trifunctional or higher functional epoxy compounds such as doxytetraphenylethane, phenol formaldehyde novolac polyglycidyl ether, glycerin triglycidyl ether, and trimethylolpropane triglycidyl ether are used.

Further, an epoxy compound having at least one terminal vinyl group or terminal allyl group and at least one terminal epoxy group (ethylene oxide group) in one molecule is also useful. For example, the general formula (In the formula, R ₈ is H or CH ₃ ) and is a monomer having a structure of glycidyl acrylate, glycidyl methacrylate, β-methylglycidyl acrylate, β-methylglycidyl methacrylate, and the like. Also, the general formula (In the formula, R ₉ and R ₁₀ are H or CH ₃ ), which is a monomer having a structure of (methyl) glycidyl (meth) acryl ether.

Also, the general formula (In the formula, R ₉ and R ₁₀ represent H or CH ₃ , and R ₁₁ 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 ₁₃ is H, or a lower alkyl group having 1 to 4 carbon atoms, or CH ₂ or Cl, x ₃ is an integer of 1 to 9, and y is an integer of 0 to 10.) Compounds of, for example, (2
-Allyloxy) ethylene glycidyl ether, 4-butenyl glycidyl ether, and the like.

Also, Or general formula (In the formula, one of R _{14 to} R ₁₉ represents a hydrogen atom, a methyl or allyl group, and the other R represents a hydrogen atom).

Also, vinyl cyclohexene monoxide, glycidyl ether of furfuryl alcohol or and so on. At least one of these is used.

In the present invention, the compounding ratio of the unsaturated bisimide compound represented by the general formula I and the compound having at least one less vinyl group or terminal allyl group and at least one terminal epoxy group in one molecule is as follows. 100
It can be said that the latter is generally in the range of 10 to 1000 parts by weight with respect to parts by weight. When the ratio of the latter decreases, the heat resistance increases, but the fluidity decreases, and as the ratio increases, the opposite tendency is exhibited.

Further, in the method for curing the resin composition of the present invention, a conventionally known curing agent can be used in combination.

Hiroshi Kakiuchi: Epoxy resin (9
Moon, published by Shokoido, pp. 109-149, Lee, Neville
ville): Epoxy Resins, Matsuguro Wu-Hill Book Company, New York City
Incorporated (Mc Graw-Hill Book Company I
nc) (issued in 1957) pages 63-141, PE Brunis (PEB)
runis): Epoxy R Technology
esins Technology) New York City, Interscience Publishers (196)
Issued for 8 years) Compounds described on pages 45 to 111, such as aliphatic polyamines, aromatic polyamines, second and third compounds.
Amines including primary amines, carboxylic acids, esters such as trimellitic acid triglyceride, carboxylic acid anhydrides, aliphatic and aromatic polyamide oligomers and polymers, boron trifluoride-amine complexes, phenolic resins, melamine Resin, urea resin, synthetic resin initial condensate such as urethane resin, dicyandiamide, carboxylic acid hydrazide, polyaminomaleimides, etc.

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

In particular, a phenol novolac 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, various catalysts can be added for the purpose of accelerating the curing reaction of the resin composition of the present invention, and as the catalyst, triethanolamine, tetramethylbutanediamine, tetramethylpentanediamine, tetramethylhexanediamine, A tertiary amine such as triethylenediamine or dimethylaniline, an oxyalkylamine such as dimethylaminoethanol or dimethylaminopentanol, or an amine such as tris (dimethylaminomethyl) phenol or N-methylmorpholine can be used.

Further, for the same purpose, as a catalyst, for example, cetyltrimethylammonium bromide, cetyltrimethylammonium chloride, dodecyltrimethylammonium iodide, trimethyldodecylammonium chloride, benzyldimethyltetradecylammonium chloride, benzyldimethylpalmitylammonium chloride, (allyldodecyl) trimethyl. There are quaternary ammonium salts such as ammonium bromide, benzyl dimethyl stearyl ammonium bromide, stearyl trimethyl ammonium chloride and benzyl dimethyl tetradecyl ammonium acetate.

Also, 2-methylimidazole, 2-ethylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-methyl-4-ethylimidazole,
1-butylimidazole, 1-propyl-2-methylimidazole, 1-benzyl-2-methylimidazole,
Imidazoles such as 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-azine-2-methylimidazole, 1-azine-2-undecylimidazole , Triphenylphosphine tetraphenylborate, tetraphenylphosphonium tetraphenylborate, triethylamine tetraphenylborate, N-methylmorpholine tetraphenylborate, pyridinetetraphenylborate, 2-ethyl-4-methylimidazole tetraflate Enilborate, 2
Tetraphenylboron salts such as -ethyl-1,4-dimethylimidazole tetraphenylborate are useful.

The above-mentioned catalysts may be used in combination of two or more thereof, and the amount thereof may be used within a range of 0.01 to 20 in a weight ratio with respect to 100 of the polyfunctional epoxy compound.

In addition, the unsaturated bisimide-based compound represented by the general formula I of the present invention has the following formula [Wherein X ₂ represents an alkylene group, an arylene group or a substituted divalent organic group thereof] can be used in combination, and 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'-4,4'-diphenylcyclohexane bismaleimide and the like can be mentioned, and two or more of these can be used in combination. You can also Furthermore, a mixture of mono-substituted maleimide, tri-substituted maleimide, tetra-substituted maleimide and the above-mentioned substituted bismaleimide can be appropriately used.

Also, the following formula (In the formula, R ₃ and R ₄ are hydrogen, a methyl group, an ethyl group, a trifluoromethyl group or a trichloromethyl group, and D ₁ and D ₂ have the same meanings as those in the formula I), Particularly, it is useful for obtaining a heat-resistant and flexible cured product. Examples of the ether imide compound include 2,
2-bis [4- (4-maleimidophenoxy) phenyl] propane, 2,2-bis [3-methyl-4- (4-maleimidophenoxy) phenyl] propane, 2,2-bis [3- Chloro-4- (4-maleimidophenoxy) phenyl] propane, 2,2-bis [3-bromo-4- (4-
Maleimidophenoxy) phenyl] propane, 2,2-bis [3-ethyl-4- (maleimidophenoxy) phenyl] propane, 2,2-bis [3-propyl-4- (4-
Maleimidophenoxy) 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-maleimidophenyloxy) phenyl] ethane, bis [4- (4-maleimidophenoxy) phenyl] methane, bis [3-methyl-4- (4-maleimidophenoxy) phenyl] methane, bis [3-chloro-4- (4-
Maleimidophenoxy) phenyl] methane, bis [3-
Bromo-4- (4-maleimidophenoxy) phenyl]
Ethane, 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- There are (4-maleimidophenoxy) phenyl] propane and the like, and one or more of them can be used in combination.

In addition, the following 2,2-bis [4- (4-substituted phenoxy)
A compound with a phenyl] propane-based compound can provide a cured product having excellent solubility in a solvent and excellent flexibility. Examples of this compound include: and so on. These may be used alone or in combination.

Further, the unsaturated bisimide compound represented by the general formula I of the present invention has the following formula: [In the formula, R ₃ and R ₄ are the same as the above], by mixing with an orthoallyl bisphenol compound, a low-viscosity insulating varnish or prepreg for heat-resistant use excellent in impregnability Useful for making. For example, and so on. Also, It is also possible to add monoallylphenols such as and the derivatives of the compounds.

It is desirable to add a polymerization initiator to the resin composition of the present invention for the purpose of completing the curing by heating for a short time. Examples of such a polymerization initiator include benzoyl baroxide, p-chlorobenzoyl baroxide, 2,
4-dichlorobenzoyl peroxide, caprylyl peroxide, lauroyl peroxide, acetyl peroxide, methyl ethyl ketone peroxide, cyclohexanone peroxide, bis (1-hydroxycyclohexyl peroxide), hydroxyheptyl peroxide,
Tertiary butyl hydroperoxide, p-mentha hydroperoxide, tertiary butyl perbenzoate, tertiary
Organic peroxides such as tert-butyl peracetate, tert-butyl peroctoate, tert-butyl peroxyisobutyrate, and di-tert-butyl diperphthalate are useful, and one or more of them may be used. Can be used.

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. Further, 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-butylcatechol and 2,5-di- Known polymerization inhibitors such as phenols such as tertiary butyl hydroquinone 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, for use as a molding material, zircon oxide, silica, alumina, aluminum hydroxide, titania, zinc white, calcium carbonate,
Inorganic fillers such as magnesite, clay, kaolin, talc, poppy sand, glass, fused silica glass, asbestos, mica, various whiskers, carbon black, graphite and molybdenum disulfide, higher fatty acids and waxes, etc. A releasing agent, a coupling agent such as an epoxy silane, a vinyl silane, a borane, an alkoxy titanate compound, or the like is added. If necessary, a flame retardant-imparting agent such as a halogen-containing compound, antimony oxide and a phosphorus compound can be used.

In addition, various polymers such as polystyrene, polyethylene, polybutadiene, polymethylmethacrylate,
Known resin modifiers such as polyacrylic acid ester, acrylic acid ester-methacrylic acid ester copolymer, phenol resin, epoxy resin, melamine resin or urea resin can be used.

It can also be used as a solution such as varnish. The solvent used at that time is N-methyl-
2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, N, N-diethylformamide, N
-Methylformamide, dimethyl sulfoxide, N, N-
There are diethylacetamide, N, N-dimethylmethoxyacetamide, hexamethylphosformamide, pyridine, dimethylsulfone, tetramethylsulfone, dimethyltetramethylenesulfone, and the like.As the phenolic solvent group, there are phenol, cresol, xylenol, and the like. is there.

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

〔Example〕

Hereinafter, the present invention will be described more specifically by way of examples, but the present invention is not limited to these examples.

Example 1 3,9-bis (3-aminopropyl) -2,4,8,10-tetraoxaspiro [5.5] undecane (12.3 parts by weight) was dissolved in 200 cc of acetone, and 10 parts by weight of maleic anhydride (5 parts by weight) was added thereto.
After stirring reaction at ℃ or less, with 10 parts by weight of acetic anhydride,
0.05 parts by weight of potassium acetate was added and the reaction was carried out for about 1 hour.
Then, the mixture was filtered, washed and dried to obtain a spiroimide compound (a).

As a result of measuring the IR spectrum, characteristic absorption derived from an imide bond was observed at 1715 cm ^-1 and 1780 cm ^-1 .

Example 2 16.5 parts by weight of 3,9-bis (3-aminophenyl) -2,4,8,10-tetraoxaspiro [5.5] undecane was dissolved in 500 cc of acetone, and 20 parts by weight of maleic anhydride was added to 5 parts thereof.
After reacting with stirring in a N ₂ stream for 2 hours at a temperature below ℃, add 30 parts by weight of acetic anhydride and 0.05 parts by weight of lithium acetate, and add about 1 part.
Allowed to react for hours. After that, overwash, wash and dry,
A spiroimide compound (b) was obtained. The IR spectrum of this spiroimide compound (b) shows 1723 cm ^-1 and 1781 cm ^-1.
The characteristic absorption derived from the imide bond was observed.

Application Examples 1 to 4 Spiroimide compounds (a) and (b) obtained in Example 1 and Example 2, unsaturated polyester (manufactured by Hitachi Chemical Co., Ltd .; PS-518), 2,2-bis [4-] (4-Aminophenoxy) phenyl] propane and an epoxy compound (novolak type; epoxy equivalent 225) were separately blended in the proportions (parts by weight) shown in Table 1 to prepare four types of blends. To these, 75% by weight of quartz glass powder as a filler, 2 parts by weight of stearic acid as a release agent, and 1 part by weight of carbon black as a colorant were further added, and then uniformly mixed by a kneader, and , At 150-170 ℃
By heat molding for 5 minutes, various cured products (test pieces) were prepared. Table 1 shows the characteristics of various cured products.

Example 3 24.6 parts by weight of 3,9-bis (3-aminopropyl) -2,4,8,10-tetraoxaspiro [5.5] undecane was dissolved in 500 cc of acetone, and maleic anhydride dissolved in acetone was dissolved therein. Add 10 parts by weight and 17.8 parts by weight of 4-methylendomethylene tetrahydrophthalic anhydride, and add 1 at 5 ° C or below.
After stirring for ₂ hours in a N ₂ stream, acetic anhydride 150
Add 1 part by weight of sodium acetate and 1 part by weight, and at room temperature or higher,
The reaction was performed for about 1 hour. Then, excess, washing and drying were performed to obtain a spiroimide compound (c).

The IR spectrum of this spiroimide compound (c) is
Characteristic absorption derived from an imide bond was observed at 1713 cm ^-1 and 1782 cm ^-1 .

Example 4 12 parts by weight of 3,9-bis (3-aminopropyl) -2,4,8,10-tetraoxaspiro [5.5] undecane was added to acetone 2
15 parts by weight of endomethylene tetrahydrophthalic anhydride dissolved in 00 cc and dissolved in acetone at 5 ° C or lower,
After reacting for about 2 hours in N ₂ gas atmosphere, acetic anhydride 10
0 part by weight and 0.5 part by weight of potassium acetate were added, and the mixture was reacted at room temperature or higher for about 1 hour. Then, water was added, and the mixture was washed, dried, and a spiroimide compound (d) was obtained.

The IR spectrum of this spiroimide compound (d) is
Characteristic absorption derived from the imide bond was observed at 1711 cm ^-1 and 1780 cm ^-1 .

Application Examples 5 to 9 The spiroimide compounds (c) and (d) obtained in Examples 3 and 4 and the unsaturated polyester, triallyl cyanurate, orthodiallyl bisphenol F and epoxy compound are shown in Table 2 respectively. Separately mixed in the proportions (parts by weight) shown in to prepare 5 kinds of formulations.

After further adding the same additives as those in Application Examples 1 to 4 to each of these, molding was performed under the same conditions as in Application Examples 1 to 4 to prepare various test pieces, and the characteristics thereof were measured. Table 2 shows the results.

The unsaturated polyester and epoxy compound in Table 2 are the same as those in Table 1 above.

Examples 10 to 19 Ten kinds of compounded compositions shown in Table 3 were prepared. The numerical values in the table are parts by weight.

Each compounded composition was kneaded at 50 to 70 ° C. for 10 minutes and then cooled to obtain a desired heat resistant resin composition.

Each composition was transfer-molded under the conditions of 170 ° C., 70 kg / cm ² , and 5 minutes to prepare various test pieces for measuring characteristics. Table 3 shows the glass transition point, the bending strength at 180 ° C., the bending elastic modulus, the heat deterioration property after standing for 30 days at 200 ° C., and the storage stability of the material.

All of the cured products have a glass transition point of 190 ° C or higher, bending strength of 180 ° C, 450 kg / cm ² or more, 200 ° C, strength retention after standing for 30 days of 90% or more, bending elastic modulus of 1.30 × 10 ³ kg. It has excellent heat resistance and flexibility of less than / mm ² .

Example 20 As a bisphenol A type epoxy resin, 60 parts by weight of Ep1001 (made by Ciel) and 40 parts by weight of Ep828 (made by Ciel) were taken. And 30 parts by weight of 2,2-bis [4- (4-maleimidophenoxy) phenyl] propane were added in an amount of 80 parts by weight,
A varnish solution having a concentration of 45% by weight was prepared by dissolving in a mixed solution of methyl ethyl ketone and dimethylformamide in an equal amount.

This varnish solution was applied to a glass fiber cloth (epoxysilane KBM 303 with a thickness of 0.1 mm) using a coating-drying device (coating machine).
Treatment) and 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 and the thickness is 35 μm on the outside.
Place the electrolytic copper foil of No.2, sandwich the two steel plates, heat and press at 180 ° C, 50kg / cm ² for 2 hours + 200 ° C for 2 hours with a hot plate breath, and double-sided steel with a thickness of 1.0mm A stretched laminate was obtained.

 Table 4 shows the performance of this copper-clad laminate.

Table 4 Bending strength (180 ℃) 65kg / mm ² Volume resistivity (160 ℃) 2.0 10 ¹⁵ Ω ・ cm Thermal expansion coefficient 1.6 × 10 ^-5 ℃ ^-1 Peel strength (100 ℃, 90 ° direction) 2.4kg / cm Solder heat resistance (280 ° C, 60 seconds immersion) No blistering Example 21 And 10 parts by weight of 2,2-bis-[-4- (4-aminophenoxy) phenyl] propane were dissolved in dimethylformamide to prepare a 2% by weight solution. Next, using a spinner, 3500 was put on a polyethylene terephthalate film having a sufficiently washed transparent conductive film.
After uniformly applying at rpm, it was heated at 120 ° C. for 15 minutes to evaporate dimethylformamide and form an orientation control film with a film thickness of 630 Å. 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 oppose each other, and these films were adhered with a sealing material made of a polyester adhesive to prepare 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 device.
When the orientation of the liquid crystal was examined between the orthogonal polarizing plates, it showed good orientation.

Example 22 Method for producing heat-resistant prepreg 30 parts by weight, Was dissolved in 30 parts by weight, 40 parts by weight of ortho-diallylbisphenol F and 5 parts by weight of dicyandiamide in dimethylacetamide to prepare 1000 ml of an 8% by weight varnish solution. Then, a glass fiber cloth (WF-230 manufactured by Nitto Boseki Co., Ltd.) was immersed in the varnish solution. 100 of the impregnated prepreg sheet
A prepreg was obtained by heating and drying at about 110 ° C. for about 2 hours. The resin content of the prepreg was 46% by weight.

Next, stack 6 pieces of the obtained prepregs at 150-160 ℃, 50
It was compression molded under the conditions of kg · f / cm ² for 2 hours. The tensile strength of the molded product is 18.2 kg / cm ² (140 ° C) (ASTM D-638), the bending strength is 17.7 kg / cm ² (140 ° C) (ASTM D-790), and the Izod impact strength (with notch) is 6.9kg ・ cm / cm ² (25 ℃) (AST
MD-256).

Example 23 1,4-bis [2- (4'-maleimidobenzoyl) as a bis- (benzoylethenyl) benzene compound
20 parts by weight of ethenyl] benzene and 3,9-bis (3-maleimidopropyl) -2,4,8,10-tetraoxaspiro [5.
5] Undecane 20 parts by weight, benzoin methyl ether 0.5
A part by weight of the composition was taken, and a 20% by weight solution was prepared by mixing an equal amount of acetone and N, N-dimethylacetamide. The solution was applied onto a glass plate using a spinner (rotation speed 3500 to 4000 rpm), and under reduced pressure of 1 to 2 mmHg.
It was dried at 50 ° C. for 5 hours. As a result, a thin film having a thickness of 3.0 to 4.5 μm was obtained.

The thin film was irradiated with an illuminance of 7.2 mW / cm ² (350 mμ) using an ultra-high pressure mercury lamp (Jetlite ² KW), and the light irradiation amount (J / cm ² ) until curing was measured, which was 3.8 J / cm. ^{It was 2} .

Regarding the above thin film, a negative type test chart manufactured by Toppan Printing Co., Ltd. (Toppan test chart N, minimum line width 0.98 ±
0.25 μm) was used to form a relief pattern, and the resolution of the pattern was evaluated. As a result, good results were shown.

Example 24 Manufacturing method of sliding member Cu90-Sn10 alloy powder (32 mesh passes) is sprinkled on the surface of a strip steel with a thickness of 1 mm, and a porous layer is formed by sintering at 810-830 ° C for 40 minutes in a reducing atmosphere. It was formed to a thickness of about 350 μm.

After sintering, after cooling to room temperature, 35 parts by weight of graphite, 15 parts by weight of PTFE on the porous layer, 20 parts by weight and 15 parts by weight of N, N'-4,4'-bis (diphenylmethane) maleimide were sprayed from a hopper, and as a preforming step, the first pressure roller, 100 kg /
cm ² , second pressure roller, 200 kg / cm ² at 160 ° C. for 1 hour, and in the main molding step at a furnace temperature of 230 ° C., a third pressure roller, 300 kg / cm ² fourth pressure roller, It was pressed at 400 kg / cm ² and cured to form a film having a thickness of about 450 μm.

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 0.04 to 0.03 is shown, and the load resistance is also excellent. I found out that

-Test conditions- Example 25 As a spiroimide compound, the following formula The compound represented by 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 as a cross-sectional view in FIGS. 2 and 3.

The structure of the element is such that after forming an insulating layer of SiO ₂ and a polysilicon layer (7), and a first layer of aluminum wiring (4-I) on a Si element substrate (8), the above resin coating material is applied. After coating (using a spinner) and baking (250 ° C., 60 minutes) (3-I), a positive resist was coated to pattern through holes. Then, 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) FIG. 3 shows the case (5) in which a polyimide resin (PIQ manufactured by Hitachi Chemical) was used as the coating resin for the second layer.

A memory LSI product (shown as a cross-sectional view in FIG. 1) in which the semiconductor device of the present invention is resin-packaged using an epoxy resin molding material using a phenol novolak resin as a curing agent (1M bit D-RAM memory). Is an LS that has excellent moisture resistance reliability, with no occurrence of disconnection failure due to corrosion of Al wiring even after 2000 hours of bias application at 85 ° C and 85% relative humidity.
Got I.

In addition, the manufacturing method of the used epoxy resin composition for sealing is shown below.

Epoxy resin composition for encapsulation Novolak type epoxy resin 100 parts by weight phenol formaldehyde resin 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 Above The compounded composition was kneaded with a two-roll roller heated to 70 to 80 ° C. for 10 minutes and then coarsely pulverized to prepare a sealing resin composition.

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

〔The invention's effect〕

As described above, according to the present invention, it is possible to provide a remarkable effect that a semiconductor device having particularly high humidity resistance reliability is provided under high temperature and high humidity, with good adhesiveness.

[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

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI technical display location C07D 519/00

Claims (2)

[Claims] 1. The following general formula I: [In the formula, D ₁ and D ₂ are the same or different, and are represented by the formula -CH = CH-, The groups represented by R ₁ and R ₂ are the same or different, and have the formula CH ₂
n, (Wherein q is the same or different, H, CH ₃ , C
_{2 H 5, Cl, Br,} F, -OCH 3, -OC 2 H 5 or -OH group, x
CH ₂ n, -O -, - COO -, - CO -, - NH -, - S-, SO 2 -, -
CH = CH-, -CH = N-, -N = N-, Or Group, n represents a group represented by 1 to 10)], and an unsaturated bisimide compound of 2,4,8,10-tetraoxaspiro [5.5] undecane represented by Curable resin composition containing the compound which has. 2. The compound having a reactive functional group is an unsaturated polyester resin, an amine compound, an epoxy compound, an N, N'-substituted bismaleimide compound, a general formula (In the formula, R ₃ and R ₄ are the same or different, and H, CH ₃ , C ₂ H ₅ , CCl
₃ or CF ₃ ), a compound of the general formula H ₂ N—X ₁ —C≡CH (wherein X ₁ is an alkylene group, The compound according to claim 1, which is at least one compound selected from the group consisting of 3,9-divinylspirobis (m-dioxane), dicyandiamide, and dicyandiamide derivative. Resin composition.