JP2574847B2 - Ether citraconic imide compound and composition containing this compound - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to an unsaturated imide compound useful as an intermediate of a polymer, and a resin composition containing the unsaturated imide compound.

[Conventional technology]

A typical conventional unsaturated bisimide is disclosed in
-109219, as described in JP-A-56-103162, Or, There is. However, the former is almost insoluble in inexpensive general solvents such as ketone solvents and petroleum solvents, metals,
There are drawbacks such as poor adhesion to inorganic substances and difficulty in achieving both heat resistance and flexibility of the cured product. For this reason, an extremely large number of formulations need to be considered depending on the application and purpose, resulting in a remarkable limitation in the area of application development. On the other hand, the latter has recently been spotlighted as a material that almost overcomes these problems. However, this material also has a lower molding condition,
It is required to provide quick-curing properties, and further, there is a strong demand for heat-resistant materials having excellent curability.

[Problems to be Solved by the Invention] Conventionally, the raw material of the heat-resistant polymer is maleic anhydride,
N, N'-substituted bismaleimides obtained from diamine compounds and reaction products of maleic anhydride and aniline resins are known. However, these arrayamide compounds have good heat resistance, but have difficulty in imparting flexibility and poor solubility in solvents such as acetone and toluene.

An object of the present invention is to provide an unsaturated imide compound useful as a raw material for a polymer having excellent heat resistance, flexibility, adhesiveness, and molding curability.

[Means for solving the problem]

(1) General formula [I] [Where X is none, (R ₁ and R ₂ are either a lower alkyl group or a perfluoroalkyl group, and may be the same or different from each other.) Is one of Y ₁ and Y ₂ are —O—, —S—, And may be the same or different from each other. ] The ether citraconic imide type compound represented by these.

(2) When the general formula [I] is The ether citraconic imide compound according to claim 1, wherein

(3) When the general formula [I] is The ether citraconic imide compound according to claim 1, wherein

(4) When the general formula [I] is The ether citraconic imide compound according to claim 1, wherein

(5) When the general formula [I] is The ether citraconic imide compound according to claim 1, wherein

(6) When the general formula [I] is [Where X is none, (R ₁ and R ₂ are either a lower alkyl group or a perfluoroalkyl group, and may be the same or different from each other.) Is one of Y ₁ and Y ₂ are —O—,
-S-, And may be the same or different from each other. ] A composition characterized by comprising an ether citraconic imide compound represented by the formula: and a compound capable of undergoing a polymerization reaction with the ether citraconic imide compound.

(7) The composition according to claim 6, comprising an ether citraconic imide compound represented by the general formula [I] and a polyfunctional epoxy compound.

(8) The composition according to claim 6, comprising an ether citraconic imide compound represented by the general formula [I] and a compound containing at least one N-substituted maleimide group.

In the present invention, the general formula [I] [Where X is none, (R ₁ and R ₂ are either a lower alkyl group or a perfluoroalkyl group, and may be the same or different from each other.) Is one of Y ₁ and Y ₂ are —O—, —S—, And may be the same or different from each other. Examples of the ether citraconic imide compound represented by the formula

The method for producing the ether citraconimide compound represented by the general formula [I] of the present invention is not particularly limited, but preferred methods include the following.

That is, the general formula [II] [Where X is none, (R ₁ and R ₂ are either a lower alkyl group or a perfluoroalkyl group, and may be the same or different from each other.) Is one of Y ₁ and Y ₂ are —O—, —S—, And may be the same or different from each other. And citraconic anhydride in an organic solvent.

The ether diamine-based compound and citraconic anhydride are stoichiometrically at a 1: 2 equivalent ratio, and industrially from 1: 1.95 to
A 2.10 equivalent ratio is appropriate. By this reaction, once the general formula (III) [Where X is none, (R ₁ and R ₂ are either a lower alkyl group or a perfluoroalkyl group, and may be the same or different from each other.) Is one of Y ₁ and Y ₂ are —O—,
-S-, And may be the same or different from each other. Is formed.

Normally, generally used organic solvents include ditimelformamide, dimethylacetamide, dimethylsulfoxide, N-methyl-2-pyrrolidone, N-methylcaprolactam, tetrahydrofuran, dioxane, acetone, methylethylketone, diethylketone, and the like. .

Next, as a second step, the ether citraconic amide compound is dehydrated and ring-closed to form an imide ring.

For this method, a known method described in U.S. Pat. Nos. 3,018,290, 3,018,292, and 3,127,414 may be used. That is, the dehydration reaction from the ether trachamidic acid compound of the general formula (III) is, for example, as an example,
Acetic anhydride is used as an anhydride in an amount of 1.0 mol per mol of amic acid groups.
Using a tertiary amine, for example triethylamine, in an amount of 0.15
To 0.5 mol, and furthermore, amic acid groups (0.5 to 0.05 mol per mol of sodium acetate,
It is preferable to carry out the reaction with an organic solvent φ in the presence F of potassium acetate, nickel acetate or the like.

In the present invention, the general formula (II) [Where X is none, (R ₁ and R ₂ are either a lower alkyl group or a perfluoroalkyl group, and may be the same or different from each other.) Is one of Y ₁ and Y ₂ are —O—, —S—, And may be the same or different from each other. Examples of the ether diamine compound represented by the following formula are as follows.

The ether citraconic imide compound represented by the general formula [I] of the present invention is at least one polymerizable compound which may be of vinyl, allyl and acrylic type. Can be modified by adding a monomer having the formula: Here, the monomer is, for example, styrene, vinyl toluene, α
-Methyl styrene, divinyl benzene, diallyl phthalate, diallyl phthalate prepolymer, chlorostyrene, dichlorostyrene, bromostyrene, dibromostyrene, diallyl benzene phosphonate, diallyl aryl phosphate, acrylic acid, methacrylic ester, triaryl There are Lucianurate, Triallyl cyanurate blepolymer, Tribromophenol allyl ether and the like, and one or more of these can be used in combination.

Further, the ether citraconic imide 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 refers to 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 monooxide and a derivative thereof. A polyester resin matrix containing an unsaturated group synthesized by condensation or addition polymerization utilizing a reaction such as esterification or transesterification in the presence or absence of a catalyst; , An allyl group, etc.) and a mixture with a peroxide catalyst. In addition, vinyl ester resins obtained by reacting bisphenol A type or novolak type epoxy compounds with methacrylic acid or acrylic acid are also useful. Here, typical examples of unsaturated dibasic acids and saturated dibasic acids include maleic acid, maleic anhydride, fumaric acid, chloromaleic acid, dichloromaleic acid, citraconic acid, citraconic anhydride, mesaconic acid, and itaconic acid. Acid, succinic acid, adibic acid, sebacic acid, azelaic acid, phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, methyl glutaric anhydride, pimelic acid, hexahydrophthalic acid and its anhydride, tetrahydrophthalic acid,
Carboxylic anhydride, heptanoic acid and its anhydride, tetrachlorophthalic acid and its anhydride, tetrabromophthalic acid and its anhydride, lower alkyl esters thereof and the like are used, and the diol component is ethylene glycol, diethylene glycol, triethylene glycol. Glycol,
Polyethylene glycol, propylene glycol, dipropylene glycol, trimethylene glycol, tetramethylene glycol, hetisamethylene glycol, 2,2
-Diethylpropanediol, 1,3-neopentyl glycol, dibromoneopentyl glycol, bisphenoldioxydiethylether, bisphenol A hydride, 2,2-di (4-hydroxypropoxyphenyl) propane, ethylene oxide , Propylene oxide,
For example, 3,3,3-trichloropropylene oxide, 2-methyl-3,3,3-trichloropropylene oxide, phenyl glycidyl ether, allyl glycidyl ether and the like are used. If necessary, a trifunctional or higher polybasic acid and / or a polyhydric alcohol may be used in combination as long as the object of the present invention is not impaired. The crosslinking agent is, for example,
Styrene, vinyl toluene, α-methyl styrene, divinyl benzene, diallyl phthalate, diallyl phthalate prepolymer, chlorostyrene, dichlorostyrene,
Bromostyrene, dibromostyrene, diallylbenzenephosphonate, diallylarylphosphyl ester, acrylate, methacrylate, triallyl cyanurate, triallyl cyanurate blepolymer, tribromophenol allyl ether, and the like are used. In the present invention, the acid component, the alcohol component, and the crosslinking agent are not limited to one kind, and two or more kinds can be used in combination. Further, various types of denaturation and addition of denaturing agents are also possible. The unsaturated polyester is not limited to one type, and two or more types can be mixed.

The ether citraconic imide compound represented by the general formula [I] of the present invention reacts with a polyamine, particularly a diamine, to become a flexible and heat-resistant material. Here, the amine compound is, for example, m-phenylenediamine, p
Phenylenediamine, benzidine, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dichlorobenzidine, 3,3'-dimethoxybenzidine, 4,4'-diaminodiphenylmethane, 1 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'-diaminodiphenylsulfoxide, 4,
4'-diamicidiphenylsulfone, 3,3'-diaminodiphenylsulfone, 3,3'-diaminodibenzophenone, 4,4'-diaminobenzophenone, 3,4'-diaminobenzophenone, 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-1,1,4-oxadiazole, m-xylylenediamine, p-xylylenediamine, 2,4 (p-β-
Amino-t-butylphenyl) ether, p-bis-2
-(2 (methyl-4-aminobentyl) benzene, p-
Bis (1,1-dimethyl-5-aminobentyl) benzene, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine,
Decamethylenediamine, 2,11-diaminododecane, 1,12
-Diaminooctadecane, 2,2-dimethylpropylenediamine, 2,5-dimethylenehexamethylenediamine, 3
-Methylheptamethylenediamine, 2,5-dimethylheptamethylenediamine, 4,4-dimethylheptamethylenediamine, 5-methinonamethylenediamine, 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 can be mentioned. Also, 2,4-
Diaminodiphenylamine, 2,4-diamino-5-methyldiphenylamine, 2,4-diamino-4'methyldiphenylamine, 1-anilino-2,4-diaminonaphthalene, 3,3'-diamino-4 -N-aryl substituted aromatic triamines such as anilinobenzophenone. In addition, the general formula (Wherein, X represents an alkylidene group containing a methylene group, and m represents a number of 0.1 or more on average). In particular, 2,2 'is effective for imparting flexibility.
There are diamine compounds having an ether bond, such as -bis [4- (4-aminophenoxy) phenyl] propane and 2,2'-bis [3-methyl-4- (4-aminophenoxy) phenyl] propane.

Further, by adding the epoxy compound, a cured product having excellent heat resistance and moldability can be obtained.

The epoxy compound of the present invention includes, for example, glycidyl ether of bisphenol A, butadiene diepoxide,
3,4-epoxycyclohexylmethyl- (3,4-epoxy) cyclohexanecarboxylate, vinylcyclohexanedioxide, 4,4′-di (1,2-epoxyethyl) diphenyl ether, 2,2-bis (3, 4-epoxycyclohexyl) propane, glycidyl ether of resorcinol, diglycidyl ether of phloroglysin, diglycidyl ether of methylphloroglysin, 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'-m-phenylenebis (bifunctional epoxy compound such as 4,5-epoxy-1,2-cyclohexanedicarboximide, triglycidyl ether of paraaminophenol, polyallylglycidyl ether, 1,3,5-tri (1 , 2
-Epoxyethyl) benzene, 2,2 ', 4,4'-tetraglycidoxybenzophenone, polyglycidyl ether of phenol formaldehyde novolak resin, triglycidyl ether of glycerin, triglycidyl ether of trimethylolpropane, etc. Functional or higher epoxy compounds, halogenated epoxy compounds such as brominated epoxy, or hydantoin epoxy compounds are used.

In particular, in the present invention, [Wherein, Z is none, -CH _2- , Is one of ], For example, benzophenone tetraglycidyl ether (BPTGE) and resorcin sulfide tetraglycidyl ether (RSTGE) are useful.

In the present invention, a known curing agent and catalyst for an epoxy compound can be added to the composition containing the ether citraconimide compound represented by the general formula [I]. Such materials include Hiroshi Kakiuchi; Epoxy resin (September 1970)
Published monthly) 109-149 pages, by Lee and Neville; Epoxy Resins
(Mc Graw-Hill Book Company Inc. New York, 1957), pp. 63-141, by PEBrunis; Epoxy Resins Techno
logy (Intersci-ence Publishers, New York, 1986), pp. 45-111, for example, aliphatic polyamines, aromatic polyamines, amines including secondary and tertiary amines, carboxylic acids, Synthetic resin precondensates such as carboxylic anhydrides, aliphatic and aromatic polyamide oligomers and polymers, boron trifluoride-amine complexes, phenolic resins, melamine resins, urea resins, urethane resins, and others, dicyandiamide Carboxylic acid hydrazide, polyaminomaleimides and the like.

One or more of these curing agents can be used depending on the use and purpose.

In particular, phenolic resin is suitable as a hardener component of the semiconductor encapsulating material in terms of adhesion of the hardened resin to the metal insert, workability during molding, and the like.

Furthermore, various catalysts can be added for the purpose of accelerating the curing reaction of the epoxy resin composition. Examples of the catalyst include triethanolamine, tetramethylbutanediamine, tetramethylpentanediamine, tetramethylhexanediamine, and trimethylamine. Tertiary amines such as ethylenediamine and dimethylaniline, oxyalkylamines such as dimethylaminoethanol and dimethylaminopentanol, and amines such as tris (dimethylaminomethyl) phenol and methylmorpholine can be applied.

For the same purpose, examples of the catalyst include 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, and further, 2-undecylimidazole, 2-methylimidazole, Ethyl imidazole, 2-heptadecyl imidazole, 2-methyl 4-ethylimidazole, 1-
Butyl imidazole, 1-propyl-2-methylimidazole, 1-benzyl-2-methylimidazole, 1-
Imidazoles such as cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-azine-2-methylimidazole, 1-azine-2-undecylimidazole, Triphenyl phosphine tetraphenyl borate, tetraphenyl phosphonium tetraphenyl borate, triethylamine tetraphenyl borate, N-methylmorpholine tetraphenyl borate, 2-ethyl-4-methylimidazole tetraphenyl borate, 2-ethyl-1 And tetraphenylborate such as 4-dimethylimidazole tetraphenylborate.

Also, 1,5-diaza-bicyclo (4,2,0) octene-
5,1,8-diaza-bicyclo (7,2,0) undecene-8,
1,4-diaza-bicyclo (3,3,0) octene-4,3-methyl-1,4-diazabicyclo (3,3,0) octene-4,3,
6,7,7-tetramethyl-1,4-diaza-dicyclo (3,3,
0) octene-4,1,5-diaza-bicyclo (3,4,0) nonene-5,1,8-diaza-bicyclo (7,3,0) dodecene-
8,1,7-diazabicyclo (4,3,0) nonene-6,1,5-
Diazabicyclo (4,4,0) decene-5,1,8-diazabicyclo (7,4,0) tridecene-8,1,8-diazabicyclo (5,3,0) decene-7,9-methyl-1, 8-diazabicyclo (5,3,0) decene-7,1,8-diazabicyclo (5,4,
0) Undecene-7,1,6-diazabicyclo (5,5,0) dodecene-6,1,7-diazabicyclo (6,5,0) tridecene-7,1,8-diazabicyclo (7,5,0) Tetradecene
8,1,10-diazabicyclo (7,3,0) dodecene-9,1,1
Diazabicyclo-alkenes such as 0-diazabicyclo (7,4,0) tridecene-9, 1,14-diazabicyclo (11,3,0) hexadecene-13 and 1,14-diazabicyclo (11,4,0) heptadecene-13 And the like are also useful. One or more of these compounds may be used in combination depending on the purpose and application. Among the above compounds, in particular, 1,8-diazabicyclo (5,4,0) undecene-7 (DBU) and carboxylate salts of this compound are effective in exhibiting the effects of the present invention.

Further, it is also possible to use N, N'-substituted bismaleimide in combination with the ether citraconimide compound represented by the general formula [I] of the present invention. The N, N'-substituted bismaleimide compound is represented by the following formula: [Wherein R represents an alkylene group, an arylene group or a substituted divalent organic group thereof], for example, N, N'-ethylenebismaleimide, 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-dicyclohexylmethane bismaleimide,
N, N'-4,4'-metaxylene bismaleimide, N, N'-
4,4'-diphenylcyclohexanebismaleimide and the like can be mentioned, and a mixture of two or more of these can be used. Further, a mixture of a mono-substituted maleimide, a tri-substituted maleimide, a tetra-substituted maleimide and the above-mentioned substituted bismaleimide can be used as appropriate.

Among the N, N'-substituted bismaleimide-based compounds, in particular, the general formula (IV) (Wherein, 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 may be hydrogen, a methyl group, An ethyl group, a trifluoromethyl group or a trichloromethyl group,
D represents a divalent organic group having 2 to 24 carbon atoms. The use of the etherimide compound represented by ()) makes it possible to improve the solubility in general-purpose solvents, improve the adhesion to inorganic substances, metals, etc., and provide both heat resistance and flexibility, and the development area is large. Spread over the width.

The etherimide compound represented by the general formula [IV] of the present invention includes, for example, 2,2-bis [4- (4-maleimidophenoxy) phenyl] propane and 2,2-bis [3
-Methyl-4- (4-maleimidophenoxy) phenyl] propane, 2,2-bis [3-chloro-4- (4-maleimidophenoxy) phenyl] propane, 2,2-bis [3-promo -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-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-promo-4- (4-maleimidophenoxy) 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-promo-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 (maleimidophenoxy) phenyl] propane,
1,1,1,3,3,3-hexafluoro-2,2-bis [3-methyl-4 (4-maleimidophenoxy) phenyl] propane and the like.

 It is also advantageous to use the following compounds in combination.

In addition, the ether citraconic imide compound represented by the general formula [I] of the present invention includes the following formula A (OCN) m wherein m is 2 to 5. A is an m-valent organic group having at least one aromatic nucleus, wherein the cyanate group is bonded to the aromatic nucleus of the organic group. ] Can be used in combination.

Polyfunctional cyanate-based compounds include, for example, 1,3-
Dicyanatobenzene, 1,4-dicyanatobenzene, 1,
3,5-tricyanatobenzene, 1,3-dicyanatonaphthalene, 1,4-dicyanatonaphthalene, 1,6-dicyanatonaphthalene, 1,8-dicyanatonaphthalene, 2,6-dicyanatonaphthalene, 2, 7-dicyanatonaphthalene, 1,3,6-tricyanatonaphthalene, 4,4′-dicyanatobiphenyl,
4,4'-dicyanato-diphenyl methane, 4,4'-dicyanato-diphenyl ether, 4,4'-dicyanato-diphenyl sulfone, 4,4'-dicyanato-diphenyl sulfide, 2,2 -Bis (4-cyanatophenyl) propane, 2,2-bis [4- (4-cyanatophenyl) phenyl] propane, 2,2-bis (4-cyanatophenyl) hexafluoropropane, 2,2-bis [4- (4-
Cyanatophenoxy) phenyl] hexafluoropropane, 2,2-bis (3,5-dichloro-4-cyanatophenyl) propane, 2,2-bis (3,5-dibromo-4-cyanatophenyl) propane, tris ( 4-cyanatophenyl) phosphite, tris (4-cyanatophenyl) phosphate and the like.

When the aforementioned N, N′-substituted maleimide-based compound or a compound having a polymerizable functional group such as an unsaturated polyester is used in combination with the compound represented by the general formula (I) of the present invention, the resin composition includes: It is desirable to add a polymerization initiator for the purpose of completing the curing by heating for a short time. Such polymerization initiators include benzoyl peroxide, p-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, cabrilyl peroxide, lauroyl peroxide, acetyl peroxide,
Methyl ethyl ketone peroxide, cyclohexanone peroxide, bis (1-hydroxycyclohexyl peroxide), hydroxyheptyl peroxide, tertiary butyl hydroperoxide, p-menthane hydroperoxide, tertiary butyl perbenzoate, tertiary petit Luper acetate, tertiary butyl peroctoate,
Organic peroxides such as tertiary butyl peroxyisobutyrate and di-tert-butyl diperphthalate are useful, and one or more of them can be used.

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

In the present invention, a known coupling agent can be added to the resin composition containing the general formula [I]. Such materials include, for example, metal alkoxides such as titanium, aluminum, and zirconium, or metal chelate compounds, silane compounds, fluorine-containing compounds, and borane-based compounds. The combined use of these may have a great effect on improving adhesiveness, improving moisture resistance, improving mechanical strength, improving electrical characteristics, improving heat resistance, and improving crank resistance. Among these, it is particularly useful to add a silane coupling agent. Such include, for example, γ-glycidoxypropylmethyldiethoxysilane, Epoxysilane-based compounds such as N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N ₂ N · C ₂ H ₄ —NHC ₃ H ₆ —SiOCH ₃ ) ₃ KBM603 N-β (aminoethyl) γ- Aminopropylmethyldimethoxysilane γ-aminopropyltriethoxysilane H ₂ N · C ₃ H ₆ -SiOC ₂ H ₅ ) ₃ KBE903 N-phenyl-γ-aminopropyltrimethoxy silane C ₆ H ₅ NHC ₃ H ₆ Si (OCH ₃ ) ₃ KBM573 Aminosilane-based compound, or γ-methcaptopropyltrimethoxysilane, HS-C ₃ H ₆ -Si (OCH ₃ ) ₃ KBM803 vinyltris (β-methoxyethoxy) silane CH ₂ CHCHSi (OC ₂ H ₄ OCH ₃ ) ₃ KBC1003 vinyltriethoxysilane CH ₂ CHCHSi (OC ₂ H ₅ ) ₃ KBE1003 vinyltrimethoxysilane CH ₂ CHCHSi (OCH ₃ ) ₃ vinylsilane compounds such as KBM1003, γ-methacryloxypropyltrimethoxysilane Acrylic silane compounds such as β- (3,4 epoxycyclohexyl) ethyltrimethoxysilane γ-glycidoxypropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, ClC ₃ H ₆ —SiOCH ₃ ) ₃ KBM703 N, O- (bistrimethylsilyl) acetamide N, N'-bis (trimethylsilyl) urea [(H ₃ C) ₃ SiNH] ₂ CO BTSu tetramethoxysilane, methyltrimethoxysilane,
Examples include dimethyldimethoxysilane, phenyltrimethoxysilane, tetraethoxysilane, dimethyldiethoxysilane, diphenyldiethoxysilane, and the like.

In order to cure the resin composition of the present invention, a curing method using ionizing radiation or light (ultraviolet light) can be used in addition to the above-described heating method.

As the ionizing radiation, electron beams from various accelerators, gamma rays from isotopes such as cobalt-60, and the like can be used.

As a light source for photo-curing, a solar ray, a tungsten lamp, an arc lamp, a Canon lamp, a halogen lamp, a low-pressure or high-pressure mercury lamp is used.

In the case of photocuring, the use of a photosensitizer is not limited. Such are, for example, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzathrone, β-methylanthraquinone, benzophenone, 9,10-phenanthrenequinone, anthraquinone, benzophenone, 5-nitroacenaphthene, Examples include 1-nitronaphthalene, Michler's ketone, eosin, erythrosine, and acridine, and one or more of these can be used in combination.

The curable resin composition of the present invention may contain various natural, semi-synthetic, or synthetic resins for the purpose of improving the properties of the resin in the final coating film, adhesive layer, resin molded product, and the like. Can be blended. Such resins include drying oils,
Oleoresin, rosin, sierrac, koval, oil-modified rosin, phenolic resin, alkyd resin,
One kind of urea resin, melamine resin, polyester resin, vinyl butyral resin, vinyl acetate resin, vinyl chloride resin, acrylic resin, and silicone resin, or a combination of two or more kinds thereof, may be used. The ether citraconic imide can be blended in an amount that does not impair the essential properties of the ether citraconic imide, for example, an amount of 30% by weight or less based on the total resin amount.

The resin composition of the present invention can further contain a reinforcing material or a filler in the form of fibrous or powder. Powdered reinforcing agents or fillers include inorganic powders such as carbon black, fine powdered silica, calcined clay, basic magnesium silicate, diatomaceous powder, alumina, calcium carbonate, magnesium carbonate, magnesia, kaolin, and sericite. Can be used. Examples of the fibrous reinforcing material include inorganic fibers such as ceramic fiber asbestos, rock wool, glass fiber, slag / wool, and carbon fiber, and various synthetic fibers such as paper, valp, wood flour, cotton, linter, and polyimide fiber. This fibrous reinforcing material can be used in the form of fibrils, stables, tows, webs, woven fabrics, non-woven fabrics, or paper products. These reinforcing materials or fillers differ depending on the application, but can be used in an amount of up to about four times the weight of the resin solid content for the application of the laminated material or the molding material. In addition, the resin composition of the present invention may contain, for the purpose of coloring this composition, white pigments such as titanium dioxide, graphite, carbon black, iron black, molybdenum red, konjiyo, gunjiyou, gadmium yellow, and cadmium red. Or various organic dyes and pigments. Further, when the resin composition of the present invention is used for paints, in addition to the coloring pigment, rust-preventive pigments such as zinc chromate, leadtan, red iron oxide, zinc white, strontium chromate, and aluminum stearate. A well-known compounding agent for paints such as anti-dripping agent, dispersant, thickener, coating film modifier, extender, flame retardant and the like can be contained.

The resin composition of the present invention is applied to a substrate as a coating film or an adhesive layer, or molded or laminated in a state of being impregnated in a powder, a pellet, or a substrate, and then cured by heating. The temperature required for curing the resin composition of the present invention varies depending on whether or not a catalyst or a curing agent is used and the type of resin, but is generally 0 to 300 ° C., particularly preferably 100 ° C. The temperature is preferably in the range of ~ 250 ° C. The required heating time varies considerably depending on whether the resin composition containing the ether citraconimide is a thin coating film or a relatively thick molded product or a laminate, but generally, the heating time is generally different. A time sufficient for the resin component to be completely cured may be selected from the range of 30 seconds to 10 hours.

In the present invention, a semiconductor device obtained by coating and / or encapsulating at least a part of a semiconductor element with a composition containing an ether citraconic imide compound represented by the general formula [I] has heat resistance, It has excellent moisture resistance. In this case, the composition containing the ether citraconimide compound represented by the general formula [I] is preferably obtained in a state of being soluble in an organic solvent.

This composition is desirably applied as a solution to the surface of a semiconductor device or the like, and the solvent is, for example, benzene,
Aromatic hydrocarbons such as toluene and xylene, ethanol,
Alcohols such as 2-propanol, ketones such as acetone and methyl ethyl ketone, chlorinated hydrocarbons, and polarities such as N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide and dimethylmalfoxide Solvents.

Solutions of these compositions are applied to surfaces such as semiconductor elements and lead wires. Coating may be performed by dipping the element or lead wire into the solution, dropping the solution onto the element or lead wire, or by spraying or spinner coating.

The semiconductor element or lead wire to which the composition solution has been applied by this method is then heated and baked at a light energy and / or greenhouse or higher, particularly preferably at 100 to 250 ° C. By this treatment, the composition of the present invention is polymerized and crosslinked to form a protective coating layer on the device. The thickness of the coating layer is appropriately adjusted depending on the purpose. That is, LSI
The α-ray shielding film for soft error countermeasures requires a thickness of 10 to 70 μm, preferably 30 to 60 μm, and the interlayer insulating film for multilayer wiring is formed to 10 μm or less, particularly 1 μm or less. preferable. It is achieved by appropriately adjusting the concentration of the solution to around 10% by weight in the former case and around 1% by weight in the latter case.

In this manner, as shown in FIG. 1, for example, a device composed of the element 2 having the protective coating layer 3 and the lead wire 1 is encapsulated with the following epoxy resin composition 6 for encapsulation molding. Thus, a resin-sealed semiconductor device is obtained.

The composition solution of the present invention may contain a silane-based coupling agent such as epoxysilane, aminosilane, mercaptosilane, or vinylsilane, or a metal alcoholate,
Metal chelate type coupling agents, alkoxy titanate type coupling agents, polybutadiene and butadicon copolymers, siloxane compounds, phenoxy resins,
By blending various known fluorine-based compounds and the like, it is possible to improve the adhesiveness and adhesiveness to the surface of the semiconductor element and also to improve the film properties (flexibility and crack resistance).

<Example 1> Citraconic anhydride was placed in a three-necked flask having a capacity of 1000 ml.
20.0 weight (0.2 mol), 200 ml of acetone and 300 ml of N-methyl-2-pyrrolidone were taken and dissolved by stirring in a nitrogen atmosphere. Then, 41.0 parts by weight of 2,2-bis [4 (4-aminophenoxy) phenyl] propane was added to 200 ml of acetone.
Was added dropwise to the citraconic anhydride solution from a dropping funnel with stirring. After the dropwise addition, the mixture was stirred at room temperature for about 3 hours, and then stirred at 60 to 80 ° C for 2 hours.

Next, 200 ml of acetic anhydride, 0.5 part by weight of potassium acetate and 5 ml of triethylamine were added to the solution, and 60 to 90
The mixture was further heated and stirred at ℃ for 3 hours. Thereafter, the reaction solution was poured into 3000 ml of cooling water (5 ° C. or lower). The deposited precipitate was filtered, washed, and dried under reduced pressure to obtain a citraconic imide compound (A) having an ether bond, which is the object of the present invention. The infrared absorption (IR) spectrum of the compound (A), the absorption derived from the ether bond in 1160 cm ^-1, the absorption derived from the imide bond to 1790 cm ^-1 and 1718 cm ^-1 were observed.

<Example 2> In a three-necked flask having a capacity of 1000 ml, citraconic anhydride was added.
20.0 weight (0.2 mol), 200 ml of acetone and 300 ml of N-methyl-2-pyrrolidone were taken and dissolved by stirring in a nitrogen atmosphere. Next, 51.2 parts by weight of 2,2-bis [4 (4-aminophenoxy) phenyl] hexafluoropropane was added.
A solution dissolved in 300 ml of acetone was dropped into the citraconic anhydride solution from a dropping funnel with stirring. After dripping,
After stirring at room temperature for about 3 hours, stirring was performed at 60 to 80 ° C for 2 hours.

Next, 200 ml of acetic anhydride, 0.5 part by weight of potassium acetate and 5 ml of triethylamine were added to the solution, and 60 to 90
The mixture was further heated and stirred at ℃ for 3 hours. Thereafter, the reaction solution was poured into 3000 ml of cooling water (5 ° C. or lower). The resulting precipitate was filtered, washed, and dried under reduced pressure to obtain a citraconic imide compound (B) having an ether bond, which was the object of the present invention. The IR spectrum of the compound (B) shows an absorption derived from an ether bond at 1158 cm ^-1 and an absorption at 1780 cm ^-1.
And 1720 cm ^-1 , absorptions due to imine bonds were observed.

<Example 3> Citraconic anhydride was placed in a three-necked flask having a capacity of 1000 ml.
20.0 weight (0.2 mol), 200 ml of acetone and 300 ml of N-methyl-2-pyrrolidone were taken and dissolved by stirring in a nitrogen atmosphere. Next, a solution prepared by dissolving 44.2 parts by weight of 2,2-bis [4 (4-aminobenzthioether) phenyl] propane in 300 ml of acetone was dropped from a dropping funnel into a ratraconic anhydride solution with stirring. After the dropwise addition, the mixture was stirred at room temperature for about 3 hours, and then stirred at 60 to 80 ° C for 2 hours.

Then, in the solution, 200 ml of acetic anhydride and potassium acetate,
0.5 parts by weight, 5 ml of triethylamine are added, and 60 to 90 ° C
Then, heating and stirring were further performed for 3 hours. Thereafter, the reaction solution was poured into 3000 ml of cooling water (5 ° C. or lower). The precipitated precipitate was filtered, washed, and dried under reduced pressure to obtain a citraconic imide compound (C) having a thioether bond, which is the object of the present invention.

<Example 4> Citraconic anhydride was placed in a three-necked flask having a capacity of 1000 ml.
20.0 parts by weight (0.2 mol), 200 ml of acetone and 300 ml of N-methyl-2-pyrrolidone were taken and dissolved by stirring in a nitrogen atmosphere. Then, 2,2-bis [4 (4-aminobenzthioether) phenyl] hexafluoropropane 55.0
A solution prepared by dissolving parts by weight in 300 ml of acetone was dropped from a dropping funnel into a citraconic anhydride solution with stirring. After the dropwise addition, the mixture was stirred at room temperature for about 3 hours, and then stirred at 60 to 80 ° C for 2 hours.

Next, 200 ml of acetic anhydride, 0.5 part by weight of potassium acetate and 5 ml of triethylamine were added to the solution, and 60 to 90
The mixture was further heated and stirred at ℃ for 3 hours. Thereafter, the reaction solution was poured into 3000 ml of cooling water (5 ° C. or lower). The precipitated precipitate was filtered, washed, and dried under reduced pressure to obtain a citraconic imide compound (D) having a thioether bond, which is the object of the present invention.

<Example 5 (Comparative Example)> Citraconic anhydride was placed in a 1000 ml four-necked flask in which a stirrer, a separating funnel, and a thermometer nitrogen gas inlet tube were set.
20 parts by weight and 200 ml of N-methyl-2-pyrrolidone (NMP)
And kept at 5 ° C. or lower.

Then, N, N'-diaminodiphenylmethane- [bicyclo- (2.2.2) octyne- (7) -2,3,5,6-tetracarboxylic acid-2: 3,5: 6-diimide] 56.6 wt. Section, NMP400m
The solution dissolved in l was dropped into the maleic anhydride solution maintained at 5 ° C. or lower while stirring. Then 40-50 ° C
After reacting for 2 hours, 200 ml of acetic anhydride, 1.5 parts by weight of potassium acetate and 0.8 ml of triethylamine are added, and
The reaction was performed at about 3 hours.

Next, the reaction solution is poured into 3000 ml of cooling water to precipitate a reaction product, which is filtered, washed, and dried under reduced pressure all day and night to obtain a comparative reaction product (E) with respect to the target reaction product of the present invention. Obtained.

Citraconimide compound (A) obtained in Examples 1 to 5
Using (E), various composition compositions shown in Table 1, Table 2 and Table 3 were prepared, and various properties of cured products thereof were measured. The results are shown.

That is, Table 1 shows bisphenol A type diglycidyl ether DER332 (manufactured by Dow Chemical Company) and 4,4'-bis (diphenylmethane) maleimide as epoxy compounds, and dicyandiamide as a curing accelerator. A predetermined amount of benzoguanamine, a predetermined amount of an epoxy silane KBM403 (manufactured by Shin-Etsu Chemical Co., Ltd.) as a coupling agent, and a predetermined amount of a spherical solvent silica powder having an average particle size of 5 to 10 μ as a filler.

These acid compounds were sufficiently kneaded with two rolls heated to 75 to 85 ° C., then cooled and roughly pulverized to obtain a molding composition. Next, transfer molding was performed under the conditions of 180 ° C., 70 kg / cm ² , and two minutes to prepare various characteristic specimens.

Table 2 shows that, as an epoxy compound, ortho-cresol novolak dust epoxy EOCN102S (manufactured by Nippon Kayaku Co., Ltd.)
And 2,2-bis [4 (4-maleimidophenoxy) phenyl] propane as a bismaleimide-based compound and 2,2-bis [4- (4-aminophenoxy) phenyl] propane as an amine-based compound , 2,2-bis [4
-(4-aminobenzthioether) phenyl] propane as a catalyst, triphenylphosphine;
DBu (made by Sam Abbot) as a coupling agent with KBM
403, prescribed amounts of fused silica glass powder as a filler, carbon black (manufactured by Cabot Corporation) as a colorant, and Hoechstwax E (manufactured by Hoechst) as a dissociating agent. Next, kneading was performed under the same conditions as above to obtain a composition for encapsulating a semiconductor. Then, using the composition,
A 1M bit D-RAM LSI was sealed and molded by transfer molding at 180 ° C., 70 kg · / cm ² , for 2 minutes. Obtained
Table 2 shows the results of the moisture resistance reliability test of the resin-sealed LSI.

In the moisture resistance reliability test, the resin-encapsulated LSI was left in supersaturated steam at 121 ° C. and 2 atm for a predetermined period of time, taken out, and checked for abnormal electric power operation (whether or not there was a disconnection).

Table 3 shows unsaturated polyesters (Hitachi Chemical Co.,
S-518, containing 40% of styrene), diallyl phthalate, triallyl isocyanurate, ortho diallyl bisphenol F, novolak type phenol resin HP607N (manufactured by Hitachi Chemical Co., Ltd.), poly-P-hydroxystyrene, each component of methyl methacrylate, and Dicyandiamide as catalyst,
Dicumyl peroxide, aluminum chelate ALCH-TR (manufactured by Kawaken Fine Chemicals Co.), methacrylsilane (manufactured by Shin-Etsu Chemical Co., Ltd.) as a coupling agent, fused silica powder as a filler, Kistwax E as a release agent,
Each was blended in a predetermined amount, and kneaded under the same conditions as above to prepare a molding composition.

<Examples 6 to 12> As the citraconimide-based compound of the present invention, the following two types, Further, 2,2-di- (4,4'-cyanatophenyl) propane, orthodiallylbisphenol F and 4,4'-diphenylmethanebismaleimide are shown in Table 4. A predetermined amount was blended.

These blended compositions were then dissolved in an equal volume mixture of N-methyl-2-pyrrolidone and methyl ethyl ketone to form a varnish containing 48-50% by weight solids.

This varnish solution was applied to a glass cloth (WE-116P-
104, BY-54), coated with a resin and dried at 160 ° C. for 20 minutes to prepare a coated cloth having a resin content of 45 to 48% by weight.

After this, use 8 pieces of each coated cloth, 35μm above and below
Thick TAI-treated copper foil (made by Furukawa Electric)
At 80 ° C, 40kg ・ / cm ² for 80 min.
Seven types of double-sided copper-clad laminates of mm were prepared.

The seven types of copper-clad laminates were further post-cured at 200 ° C. for 240 minutes. Table 4 shows the properties of the seven types of copper-clad laminates.

-Measurement method- Copper foil peeling strength: A test piece was cut out to a size of 25 mm x 100 mm from the copper-clad laminate, the copper foil was left at the center at a width of 10 mm, and the other copper foil was removed by etching. Next, center the copper foil vertically
The film was peeled off at a speed of 5 mm / min, and the strength was measured.

Solder heat resistance:-A 25 mm square piece cut from the copper-clad laminate was used as a test piece. The test piece was floated in a 300 ° C. solder bath, and the time during which an abnormality such as blistering occurred was measured.

Anti-inflammatory; measured according to the UL-94 vertical method. Test pieces were cut from various copper-clad laminates to a width of 12 mm and a length of 125 mm, and the copper foil was etched and removed. The test was performed for each 10 samples, and the results were expressed as the average extinction time and the variation.

The average quenching time is 5 seconds or less, the maximum quenching time is 10 seconds or less, UL-94V-O, the average quenching time is 25 seconds or less,
Within seconds, it is UL-94U-1.

(Effect of the present invention)

The ether citraconic imide compound of the present invention is useful as a heat resistance-imparting material having addition reactivity. Also,
A wide variety of compositions with many materials having polymerization reactivity can be developed. These can provide a cured product having excellent heat resistance, flexibility, and crack resistance, and also excellent moisture resistance.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code Agency reference number FI Technical indication location // C09K 3/10 C09K 3/10 Z (72) Inventor Toshikazu Narahara 4026 Kuji-cho, Hitachi City, Ibaraki Prefecture Address Hitachi Research Laboratory, Ltd. Hitachi Research Laboratory (56) References JP-A-1-186865 (JP, A)

Claims (8)

(57) [Claims] 1. A compound of the formula [I] [Where X is none, (R ₁ and R ₂ are either a lower alkyl group or a perfluoroalkyl group, and may be the same or different from each other.) Is one of Y ₁ and Y ₂ are —O—, —S—, And may be the same or different from each other. ] The ether citraconic imide type compound represented by these. 2. A compound represented by the general formula [I]: The ether citraconic imide compound according to claim 1, wherein 3. A compound represented by the general formula [I]: The ether citraconic imide compound according to claim 1, wherein 4. A compound represented by the general formula [I]: The ether citraconic imide compound according to claim 1, wherein 5. A compound of the general formula [I] The ether citraconic imide compound according to claim 1, wherein 6. A compound represented by the general formula [I]: [Where X is none, (R ₁ and R ₂ are either a lower alkyl group or a perfluoroalkyl group, and may be the same or different from each other.) Is one of Y ₁ and Y ₂ are —O—,
-S-, And may be the same or different from each other. ] A composition characterized by comprising an ether citraconic imide compound represented by the formula: and a compound capable of undergoing a polymerization reaction with the ether citraconic imide compound. 7. The composition according to claim 6, comprising an ether citraconic imide compound represented by the general formula [I] and a polyfunctional epoxy compound. 8. The composition according to claim 6, comprising an ether citraconimide compound represented by the general formula [I] and a compound containing at least one N-substituted maleimide group.