JPH0749401B2 - Cinnamanilide compounds, production method and applications - Google Patents

Description

TECHNICAL FIELD The present invention relates to an intermediate useful as a photosensitive material and / or a heat-resistant material, and in particular, a photoresist, a laminated material, a molding material, a paint, an adhesive. The present invention relates to a compound capable of being easily cured by light and / or heat energy in use and imparting excellent heat resistance and adhesiveness, a process for producing the same, and use thereof.

[Conventional technology]

Conventionally, N has been used as an addition reaction type material capable of imparting heat resistance.
Compounds having a -substituted maleimide group, such as N, N'-substituted bismaleimide diphenylmethane or various adducts of the compounds, or imide compounds having an ethynyl group as a terminal group are known. In order to provide a polymer having excellent heat resistance by applying thermal energy, the compound is being actively studied for application to a laminate material, a molding material, an adhesive, and the like.

[Problems to be solved by the invention]

However, the conventional addition reaction-type material is hardly soluble in acetone, toluene, and other generally inexpensive solvents, and moreover, it gives a large amount of heat energy during curing, that is, the curing temperature is high and the curing time is long. However, due to its long length, it is not always an excellent material system in terms of moldability. Furthermore, when considering application to fields such as electric equipment and electronic parts, it is difficult to deal with the improvement of adhesiveness as a problem, although improvement of adhesiveness to metals and inorganic substances is an essential condition. Has been done.

An object of the present invention is to provide a novel addition reaction-type polymer intermediate capable of providing a cured product (polymer) having excellent heat resistance and adhesiveness, which easily undergoes a crosslinking reaction by application of light and / or heat energy. To provide the body.

[Means for solving problems]

Briefly describing the present invention, the first invention of the present invention relates to cinnamanilide compounds, and is represented by the following general formula I: [In the formula, X ₁ and X ₂ are the same or different, and -NH ₂ , -NH-C≡
N, -OH, -O-C≡N, -C≡N, -C≡CH or (D is a group containing at least one ethylenically unsaturated double bond), and X ₁ and X ₂ are not —NH ₂ at the same time ”.

A second invention of the present invention relates to a method for producing a cinnamanilide compound, which is the method of producing the cinnamanilide compound represented by the general formula I of the first invention, wherein the following general formula: An acetanilide compound represented by the formula (wherein X ₂ has the same meaning as the above formula I), and the following general formula: It is characterized in that a dehydration condensation reaction is carried out with a corresponding benzaldehyde compound represented by the formula (X ₁ has the same meaning as in formula I).

A third invention of the present invention relates to a resin composition, which is characterized by containing a cinnamanilide compound represented by the general formula I of the first invention.

And a fourth invention of the present invention relates to a cured polymer, wherein the cinnamanilide compound represented by the general formula I of the first invention, or a resin composition containing the compound is treated with at least thermal energy. And / or is cross-linked and cured by light energy.

In the present invention, the cinnamanilide compound represented by the general formula I is, for example, and so on.

In the present invention, when the compound of the general formula I is used as a composition and a cured product, the following general formula II: [In the formula, Y ₁ and Y ₂ are —NH ₂ , —NH.C≡N, —OH, —
O-C≡N, -C≡N, -C≡CH, (Wherein D is a group containing at least an ethylenically unsaturated double bond), and they may be the same or different from each other]
It may be extremely effective to use it in combination with a (benzoylethenyl) benzene compound. As such a compound, for example, and so on.

The compound represented by the above general formula II can be obtained, for example, by the reaction shown in the following reaction equation.

Further, a compound of the following formula can be obtained by reacting the above diol with cyanogen halide.

Further, a compound having ethynyl groups at both ends is obtained by the following reaction.

Further, a compound having cyano groups at both ends can be obtained by the following reaction.

The substituents X ₁ and X ₂ in the compound of general formula I can also be formed by the same reaction as above.

Furthermore, the above-mentioned reaction and the formation of an ethylene bond by the reaction between the acetyl group and the benzaldehyde group in the second invention of the present invention are themselves well-known reactions.

The cinnamanilide compound represented by the general formula I of the present invention is further compounded with an N, N′-substituted bismaleimide compound to further enhance its effect and expand the application range requiring heat resistance. It is effective in doing.

The N, N′-substituted bismaleimide compound has the following formula III: [Wherein R ₃ represents an alkylene group, an arylene group or a substituted divalent organic group thereof], for example, N, N′-ethylene bismaleimide, N, N′-hexamethylenebis Maleimide, 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, in particular the general formula IV: (In the formula, R _{4 to} R ₇ represent hydrogen, a lower alkyl group, a lower alkoxy group, chlorine or bromine, and may be the same or different from each other. R ₈ and R ₉ are hydrogen, a methyl group, Ethyl group, trifluoromethyl group or trichloromethyl group, D ₁
And D ₂ each represent a group having at least one ethylenically unsaturated double bond and having 2 to 24 carbons, which may be the same as or different from each other) It is effective in balancing the flexibility and heat resistance.

Examples of the etherimide compound represented by the general formula [IV] of the present invention include 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-
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-maleimidophenoxy) phenyl] ethane, bis [4- (4-maleimidophenoxy) phenyl] methane, bis [3-methyl-4-
(4-maleimidophenyloxy) phenyl] methane, bis [3-chloro-4- (4-maleimidophenoxy) phenyl] methane, bis [3-bromo-4- (4-maleimidophenoxy) phenyl] Methane, 1,1,1,3,3,3-hexafluoro-2,2-bis [4- (4-maleimidophenoxy) phenyl] propane, 1,1,1,3,3,3-hexachloro -2,2-bis [4- (4-maleimidophenoxy) phenyl] propane, 3,3-bis [4- (4-maleimidophenoxy) phenyl] pentane, 1,1-bis [4-
(4-maleimidophenoxy) phenyl] propane, 1,
1,1,3,3,3-hexafluoro-2,2-bis [3,5-dibromo-4- (4-maleimidophenoxy) phenyl] propane, 1,1,1,3,3,3 -Hexafluoro-2,2-bis [3-
Methyl-4- (4-maleimidophenoxy) phenyl]
There is propane etc. Also the general formula V: [In the formula, R _{10 to} R ₁₂ represent CH ₃ or CF _3, and may be the same as or different from each other. Further, D ₁ and D ₂ have the same meanings as those in the general formula IV], and 2,4-bis [4
-(4-unsaturated imidophenoxy) phenyl] -2-
(Fluoro) -methylpentane is effective in imparting flexibility to the cured product, and is preferably used together when it is applied to an adhesive, a paint or the like.

Examples of the compound represented by the general formula V include: and so on.

In addition, the general formula VI: [In the formula, D ₁ and D ₂ have the same meanings as those in the general formula IV, R ₁₃ and R ₁₄ represent CH _{2 n} (n is 1 to 10), (Q is _{H, CH 3, C 2 H} 5, Cl, Br, F, -OCH 3, -OC 2 H 5,
One of -OH. Also, x is CH _{2 n} , -O -, - COO -, - CO -, - NH -, - S -, - SO 2 -,
-CH = CH-, -CH = N-, -N = N-, Is one of the ), Which may be the same or different from each other] 2,4,
When the unsaturated bisimide compound of 8,10-tetraoxaspiro [5.5] undecane is used in combination with the compound represented by the general formula I of the present invention, the curing shrinkage rate of the cured product is reduced, and the thermal cycle resistance ( It is effective in improving the crack resistance). Examples of such compounds include, for example: and so on.

When the following compound is used in the general formula I of the present invention, it is effective for a laminated material, a molding material, a coating material, an adhesive agent and the like. For example, Etc., and one or more kinds can be used in combination.

As the compound having an N-substituted maleimide group, a mono-substituted maleimide, a tri-substituted maleimide, or a tetra-substituted maleimide can be appropriately used in combination.

Further, if necessary, a sensitizer and a photopolymerization initiator, and a photopolymerizable compound having an ethylenically unsaturated group may be added to the cinnamanilide compound represented by the above general formula I. it can.

Examples of the sensitizer and photopolymerization initiator include Michler's ketone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether,
2-tert-butylanthraquinone, 1,2-benzo-9,10
-Anthraquinone, 4,4'-bis (diethylamino) benzophenone, acetophenone, benzophenone, thioxanthone, 1,5-acenaphthene, N-acetyl-4-
Examples thereof include nitro-1-naphthylamine. The addition amount is preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of the cinnamanilide compound.

Further, in the present invention, the cinnamanilide compound represented by the general formula I is modified by adding a monomer containing at least one polymerizable CH ₂ ═C group which may be vinylallyl and acrylic type. it can. here,
Examples of the monomer include styrene, vinyltoluene, α
-Methylstyrene, divinylbenzene, diallylphthalate, diallylphthalate blepolymer, chlorostyrene, dichlorostyrene, bromostyrene, dibromostyrene, diallylbenzenephosphonate, diallylarylphosphinic acid ester, acrylic acid, methacrylic acid ester, triallyl cyanurate, There are triallyl cyanurate prepolymers, tribromophenol allyl ether and the like, and one or more of these can be used in combination.

Further, the cinnamanilide 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-based (eg vinyl, allyl, etc.) polymerizability It is composed of a compound and a mixture with a peroxide catalyst.

In addition, 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 saturated dibasic acid and the saturated dibasic acid, maleic acid, maleic anhydride, fumaric acid, chloromaleic acid, dichloromaleic acid, citraconic acid, citraconic anhydride, mesaconic acid, itaconic 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, Hettic acid and its anhydride, tetrachlorophthalic acid and its anhydride, tetrabromophthalic acid and its anhydride, and their lower alkyl esters are used, and the diol component is ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol. , Propylene glycol , Dipropyl propylene glycol, trimethylene glycol, tetramethylene glycol, hexamethylene glycol, 2,2-diethyl-propanediol, 1,3
-Neopentyl glycol, dibromoneopentyl glycol, bishydroxyethyl ether of bisphenol, hydrogenated 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 and the like are used. Moreover, you may use together trifunctional or more than trifunctional polybasic acid and / or polyhydric alcohol as needed in the range which does not impair the objective of this invention. Examples of the crosslinking agent include styrene, vinyltoluene, α-methylstyrene, divinylbenzene, diallylphthalate, diallylphthalate prepolymer, chlorostyrene, dichlorostyrene, bromostyrene, dibromostyrene, diallylbenzenephosphonate, diallylarylphosphinic acid ester, and acrylic. Acid ester, methacrylic acid ester, triallyl cyanurate, triallyl cyanurate prepolymer, tribromophenol 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.

It is desirable to use a catalyst to complete the cross-linking between the cinnamanilide compound of general formula I of the present invention and the cross-linking agent. Examples of such a catalyst include benzoyl peroxide, parachlorobenzoyl peroxide, 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-menthane hydroperoxide, cumene hydroperoxide, di-tertiary butyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-di (tertiary butyl peroxide) hexane, 2,5 -Dimethylhexyl-2,5
-Di (peroxybenzoate), tertiary butyl perbenzoate, tertiary butyl peracetate, tertiary butyl peroctoate, tertiary butyl peroxyisobutyrate, di-tertiary butyl diperphthalate, etc. These organic peroxides are useful, and one or more of them can be used in combination.

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

By the way, a relief pattern can be formed as follows by preparing a photosensitive solution containing a cinnamanilide compound represented by the general formula I.

The above-mentioned photosensitive solution is applied to a substrate and dried at 150 ° C or lower, preferably 100 ° C or lower to remove the organic solvent. After drying, a negative-type photomask chart is placed on the coating film and irradiated with active rays such as ultraviolet rays, visible rays, electron rays, and X-rays. Then, the unexposed portion is washed away with a developing solution to obtain a relief pattern formed of a cinnamanilide polymer.

As the developer, N, N-dimethylformamide,
N, N-dimethylacetamide, dimethyl sulfoxide,
N-methyl-2-pyrrolidone, hexamethylphosphoamide, acetone, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, isobutyl cellosolve, benzene, toluene, methanol, ethanol, isopropyl alcohol, etc. may be used alone or in combination.

Further, the cinnamanilide compound represented by the general formula I of the present invention can improve the coating property and the adhesive property by combining with the epoxy resin.

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

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 may be used in combination. (In the formula, R ₁₅ is H or CH ₃ ) and there are monomers having a structure, and glycidyl acrylate, glycidyl methacrylate, β-methylglycidyl acrylate, and β-methylglycidyl methacrylate are typical examples.

Also, the general formula (In the formula, R ₁₆ and R ₁₇ represent H or CH ₃ , and R ₁₈ 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 ₁₉ is H, a lower alkyl group having 1 to 4 carbon atoms, or CH ₂ Cl, and x is an integer of 1 to 9,
y is an integer of 0 to 10), for example, (2-allyloxy) ethylene glycidyl ether, 4-butenyl glycidyl ether and the like.

Also, Or general formula (In the formula, one of R _{20 to} R ₂₅ represents hydrogen, a methyl or allyl group, and the other R represents hydrogen).

When the cinnamanilide compound represented by the general formula I of the present invention is used in combination with the epoxy compound, it is desirable to use a conventionally known curing agent for the epoxy compound.
Hiroshi Kakiuchi: Epoxy resin (September 45, published by Shokoido) pages 109-149, Lee, Nevill
e) Written by: Epoxy Resins Mc Graw−Hill Book Company In
c) (published in 1957) pages 63-141, PE Brunis (PEBr
unis: Epoxy Resins Technology (Epoxy
Resins Technology) New York City, Interscience Publishers
(Published in 1968) pages 45 to 111 and the like, for example, aliphatic polyamine, aromatic polyamine, second
And amines, including tertiary amines, carboxylic acids, esters such as trimellitic acid triglyceride, carboxylic acid anhydrides, aliphatic and aromatic polyamide oligomers and polymers, boron trifluoride-amine complexes, phenols Resins, melamine resins, urea resins, urethane resins, and other synthetic resin initial condensates, as well as dicyandiamide, carboxylic acid hydrazides, polyaminomaleimides, and the like.

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.

Furthermore, various catalysts can be added for the purpose of accelerating the curing reaction of the epoxy resin composition.
For example, tertiary ethanol such as triethanolamine, tetramethylbutanediamine, tetramethylpentanediamine, tetramethylhexanediamine, triethylenediamine, and dimethylaniline; oxyalkylamines such as dimethylaminoethanol and dimethylaminopentanol; and tris (dimethyl). Aminomethyl) phenol,
There are amines such as N-methylmorpholine.

Further, as a catalyst for the same purpose, for example, cetyl trimethyl ammonium bromide, cetyl trimethyl ammonium chloride, dodecyl trimethyl ammonium iodide, trimethyl dodecyl ammonium chloride,
Benzyl dimethyl tetradecyl ammonium chloride, benzyl dimethyl palmityl ammonium chloride, (allyl dodecyl) trimethyl ammonium bromide, benzyl dimethyl stearyl ammonium bromide, stearyl trimethyl ammonium chloride,
There are quaternary ammonium salts such as benzyl dimethyl tetradecyl ammonium acetate.

In addition, 2-methylimidazole, 2-ethylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-methyl-4-ethylimidazole, 1
-Butylimidazole, 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 , Triphenylphosphine tetraphenylborate, triethylamine tetraphenylborate, N-methylmorpholine tetraphenylborate, pyridine tetraphenylphenylborate, 2-
There are tetraphenylboron salts such as ethyl-4-methylimidazole tetraphenylborate and 2-ethyl-1,4-dimethylimidazole tetraphenylborate.

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

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, magnesite, clay, kaolin, talc, silica sand, glass, fused silica glass, asbestos, Inorganic fillers such as mica, various whiskers, carbon black, graphite and molybdenum disulfide, release agents such as higher fatty acids and waxes, and coupling such as epoxysilane, vinylsilane, borane and alkoxy titanate compounds. The agent is blended. If necessary, a flame retardant-imparting agent such as a halogen-containing compound, antimony oxide and a phosphorus compound can be used.

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

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

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

〔Example〕

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

Example 1 In a 1000 ml three-necked flask, 500 ml of N-methyl-2-pyrrolidone (NMP) and 19.6 parts by weight of maleic anhydride were collected,
Dissolved. Then, a solution prepared by dissolving 23.9 parts by weight of 4,4′-diaminocinnamanilide in 300 ml of NMP was added dropwise at −5 ° C. or lower with stirring. After carrying out a stirring reaction for about 4 hours, 200 ml of acetic anhydride was added in a N ₂ reflux atmosphere, and 60 to 1 parts was added in the presence of 1.0 part by weight of a potassium acetate ring closure accelerator.
The mixture was heated to 00 ° C, reacted for 4 hours, and then cooled. The reaction solution was added dropwise to about 3000 ml of water cooled to 5 ° C or lower to deposit a precipitate.

After separating the precipitate, it was washed with water and dried to obtain the desired 4,4'-bismaleimidocinnamanilide. As a result of measuring the IR of the reaction product, characteristic absorption derived from the carbonyl atom group of the imide ring was confirmed at 1712 cm ^-1 and 1780 cm ^-1 .

Examples 2-5 4,4'-bismaleimidocinnamanilide obtained in Example 1 and unsaturated polyester (Hitachi Chemical Co., Ltd .: PS-5
18), 4,4′-diaminocinnamanilide, 1,4 of the following formula
-Bis [2- (maleimidobenzoyl) ethenyl] benzene, Ratio (parts by weight) of epoxy compound (Novolak type: epoxy equivalent 205) and dicumyl peroxide shown in Table 1
Were separately blended with each other to prepare 4 kinds of blends.

Furthermore, 78% by weight of quartz glass powder (spherical) as a filler, 2.0 parts by weight of stearic acid as a release agent, 1.5 parts by weight of carbon black as a colorant, and epoxysilane KBM303 (a product of Shin-Etsu Chemical Co., Ltd.) as a coupling agent. ) After adding 2.0 parts by weight, the mixture was uniformly mixed with a kneader and heat-molded at 175 ° C. for 5 minutes to prepare cured product specimens for measuring various characteristics.

Example 6 As a cinnamanilide type compound, 23.9 parts by weight of 4,4′-diaminocinnamanilide was dissolved in 500 ml of NMP, and a solution of 21.2 parts by weight of Br · C≡N in 200 ml of acetone was added thereto, 80-100 in the presence of triethylamine catalyst
The mixture was heated to ℃, reacted in a stirring state, and then cooled. Then, the mixture was dropped into about 3000 ml of + 5 ° C. cooling water to deposit a precipitate. After separating the precipitate, wash with water and dry to obtain the desired 4,4 '
-Dicyanamide Cinnamanilide Got The IR spectrum of the reaction product was measured and found to be 2230.
A characteristic absorption derived from a cyanamide group was observed at cm ^-1 .

Example 7 The same procedure as in Example 1 was repeated except that the amount of maleic anhydride was changed to 9.8 parts by weight. Got The IR spectrum of the reaction product was measured and found to be 3200.
cm ^-1 to an amino group, characteristic absorption derived from Mareimino group 1710 and 1780 cm ^-1 were observed.

Examples 8 to 12 Cinnamanilide compounds obtained in Examples 6 and 7, an unsaturated polyester, triallyl cyanurate, and the following formula The bis [2- (maleimidobenzoyl) ethenyl] benzene represented by and the epoxy compound were separately mixed in the proportions (parts by weight) shown in Table 2 to prepare 5 kinds of blends. After adding the same additives as those of Examples 2 to 5 to these, respectively, under the same conditions, for identifying various characteristics,
A test piece was created. The results are shown in Table 2.

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

Example 13 60 parts by weight of Ep1001 (manufactured by Ciel) and 40 parts by weight of Ep828 (manufactured by Ciel) were used as a bisphenol A type epoxy resin, and 4,4'-as a cinnamanilide compound.
A system in which 100 parts by weight of bismaleimidocinnamanilide was added was dissolved in a mixed solution of methyl ethyl ketone and dimethylformamide in an equal amount to prepare a varnish solution having a concentration of 45% by weight.

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

10 pieces of this brib leg are piled up, 35 μm thick electrolytic copper foil is placed on the outside, sandwiched between two steel plates, and 180 ° C by a heat plate bracelet, 50 kg / cm ² for 2 hours at + 200 ° C. It was heated and pressed for 2 hours to obtain a double-sided copper clad laminate having a thickness of 1.0 mm.

Table 3 shows the performance of this copper-clad laminate.

Table 6 Bending strength (180 ℃) 62kg / mm ² Volume resistivity (160 ℃) 1.5 × 10 ¹⁵ Ω ・ cm Thermal expansion coefficient 1.2 × 10 ^-5 ℃ ^-1 Peel strength (100 ℃, 90 ° direction) 2.2kg / cm Solder heat resistance (280 ℃, 60 seconds immersion) No blister.

Example 14 Method for producing heat-resistant prepreg 2,2-bis [4- (4-maleimidophenoxy) phenyl] propane, 40 parts by weight, and 4,4'-bismaleimidocinnamanilide 35 parts by weight were added as dimethyl. After dissolving in acetamide, 1000 ml of 8% by weight varnish solution was prepared. Then, a glass fiber cloth (WF-23 manufactured by Nitto Boseki Co., Ltd. was added to the varnish solution.
0) was soaked. The impregnated prepreg sheet at 100 to 110 ° C
It was heated and dried for about 2 hours to obtain a prepreg. The resin content of the prepreg was 46% by weight.

Next, stack 6 pieces of the obtained prepreg, 150-160 ℃, 50kg
-Compression molding was performed under the condition of f / cm ² for 2 hours. Tensile strength of the molded product is 18.3kg / cm ² (140 ℃) (ASTM.D-638), bending strength is 18.5kg / cm ² (140 ℃) (ASTM.D-790), Izod impact strength (with notch) ) Is 6.7 kg ・ cm / cm ² (25 ℃) (ASTM.
D-256).

Example 15 Method for manufacturing sliding member Cu90-Sn10 alloy powder (32 mesh passes) is sprinkled on the surface of a steel strip having a thickness of 1 mm, and the porous layer is formed by sintering for 40 minutes at 810-830 ° C 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 polytetrafluoroethylene on the porous layer,
4,4'-Bismaleimidocinnamanilide 20 parts by weight, 4,
A powder mixture consisting of 30 parts by weight of 4 '-(diphenylmethane) bismaleimide was sprayed from a hopper, and as a preforming step, a first pressure roller, 100 kg / cm ² , a second pressure roller, 200
Press at 160 ° C for 1 hour at kg / cm ^{2 and then} at the furnace temperature of 230 ° C as the main molding process, press to the 3rd pressure roller, 300kg / cm ² 4th pressure roller, 400kg / cm ² to cure. Let the thickness be about 4
A 50 μm coating was formed.

As a result of performing a thrust load resistance test on the plate-like sliding member thus obtained under the test conditions shown in Table 4 below, a low coefficient of friction of 0.05 to 0.03 was exhibited under high speed conditions and excellent load resistance. I found out that

Table 4-Test conditions-Slip velocity V = 278m / min Load P = 10kg / cm ² cumulative load every 10 minutes, 45
Completion of 0 kg / cm ² Counterpart material S45C lubrication, complete lubrication Example 16 20 parts by weight of 1,4-bis [2- (maleimidobenzoyl) ethenyl] benzene as a bis- (benzoylethenyl) benzene compound, 20 parts by weight of 4'-dicyanamide cinnamanilide and 5 parts by weight of benzophenone were taken, and a 20% by weight solution was prepared with an equal mixture of acetone and N, N-dimethylacetamide. The solution was applied onto a glass plate using a spinner (rotation number: 3500 to 4000).
rpm) and a reduced pressure of 1-2 mmHg, and 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 (jet light 2 kW), and the light irradiation amount (J / cm ² ) until curing was measured, and the result was 3.8 J / It was cm 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 17 A glycidyl group-terminated Schiff compound having the following formula 50 parts by weight of cinnamanilide compound as 4,4 '
20 parts by weight of bismaleimidocinnamanilide and 4-amino-4'-maleimidocinnamanilide 20 parts by weight, acetophenone 2.5 parts by weight, dicumyl peroxide 2.0 parts by weight, 2-ethyl-4-methylimidazole 1.0 parts by weight, 20 parts by weight in a mixed solution of acetone and N, N-dimethylacetamide in an equal amount. % Solution was prepared. The solution is applied onto a glass plate using a spinner (rotation speed 3500 to 4000 rpm), and 50 to 60 under reduced pressure of 1 to 2 mmHg.
C., dried for 5 hours. As a result, a thin film having a thickness of 3.5 to 4.5 μm was obtained.

The thin film was irradiated with an ultra-high pressure mercury lamp (jet light 2kW) at an illuminance of 7.2 mW / cm ² (350 mμ), and the light irradiation amount (J / cm ² ) until curing was measured, and the result was 3.6 J / cm ^2. It was cm 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 18 A cinnamanilide compound having the following formula 4,4'-dinitrile cinnamanilide 20 represented by
By weight, 0.5 parts by weight of benzophenone and 5 parts by weight of N-phenylmaleimide were dissolved in dimethylformamide to prepare a 2% by weight solution. Next, a polyethylene terephthalate film having a sufficiently washed transparent conductive film was applied uniformly at 3500 rpm with a spinner, and then heated at 120 ° C for 15 minutes to evaporate dimethylformamide to a film thickness of 630Å The orientation control film of was formed. This film was rubbed with a felt in a certain direction to prepare a substrate film having an orientation control film.

The alignment control films of the two films thus formed were arranged so as to face each other, and these films were adhered with 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, and the orientation of the liquid crystal was examined between the two orthogonal polarizing plates. showed that.

Example 19 250 ml of NMP was placed in a 500 ml Erlenmeyer flask, and 5 parts by weight of phenoxy resin PKHB (manufactured by Union Carbide Co.) was added and dissolved by heating and stirring to prepare a phenoxy resin solution.

Then, 15 parts by weight of 4,4'-bismaleimidocinnamanilide and 0.25 parts by weight of aluminum chelate coupling agent ALCH-TR (manufactured by Kawaken Fine Chemicals Co., Ltd.) were added to and dissolved in the solution to coat the solution. Obtain the composition.

Then, the solution of the coating composition was dropped onto the element and the lead wire (including wire bonding) of the 1M bit D-RAM memory LSI (18-pin). Then, after heating for 2 hours at 100 ℃, while maintaining the state of 100 ~ 200 ℃, using an ultra-high pressure mercury lamp (jet light 2kW), illuminance 7.2mW
Irradiation was performed at / cm ² (350 mμ). Thus 25 on the element
A coating film with a thickness of -50 μm was obtained.

Then, at least, the memory LSI element coated with a composition containing a phenoxy resin and a maleimide compound,
The epoxy resin composition described below is heat-molded and sealed at 180 ° C. for 1.5 minutes to obtain the resin-sealed semiconductor device shown in FIG. That is, FIG. 1 is a sectional view of a semiconductor device according to an embodiment of the present invention. Reference numeral 1 is a lead wire, 2 is a semiconductor element, 3 is a protective coating resin, and 6 is a molding resin.

The resin-encapsulated semiconductor device has excellent α-ray resistance characteristics (soft error rate of 50 Fit or less), and does not cause corrosion breakage failure of the wiring Al on the element even after standing in 121 ° C., 2 atmosphere supersaturated steam for 2500 hours. It has excellent moisture resistance and reliability.

Example 20 A cinnamanilide compound having the following formula 5 parts by weight of 4,4′-bisnorbornanedieneimidocinnamanilide represented by the formula, and 2,2-bis [4- (4-
5 parts by weight of maleimidophenoxy) phenyl] propane,
As a coupling agent, 0.2 part by weight of aluminum chelate ALCH (manufactured by Kawaken Fine Chemical Co., Ltd.) was dissolved in toluene to prepare a 1% by weight resin solution. The element structure when the solution is used as a multilayer (two-layer) wiring insulating film is shown in FIGS. 2 and 3. That is, FIGS. 2 and 3 are partial cross-sectional views of the element portion of the semiconductor device according to the present invention, in which reference numeral 3-I is the first layer protective coating resin, 3-II is the second layer protective coating resin, 4 -I is the first layer wiring, 4-II is the second layer wiring, 5 is the polyimide resin, 7 is the thermal oxide film, and 8 is the Si element substrate.

As for the constitution of the element, after the SiO ₂ insulating layer and the polysilicon layer (7) and the first layer aluminum wiring (4-I) are formed on the Si element substrate (8), the resin solution is applied ( Spinner used), baked (250 ° C, 60 minutes) (3-
After I layer), a positive resist was applied to pattern the through holes. After that, plasma etching was performed using CF ₄ —O ₂ as a reaction gas. Then, the positive resist was removed by plasma etching using O ₂ as a reaction gas.

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

An LSI product for memory (1M bit D-RAM memory) in which the semiconductor device of the present invention is resin-packaged by using an epoxy resin forming material using a phenol novolac resin as a curing agent.
The LSI has excellent moisture-proof reliability without the occurrence of disconnection failure due to corrosion of Al wiring even after 2000 hours with a bias applying device at 85 ° C and 85% relative humidity.

The epoxy resin composition used above is shown below.

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

〔The invention's effect〕

As described above, according to the present invention, it is possible to provide a semiconductor device having particularly high moisture resistance reliability under high humidity and high humidity due to excellent α-ray resistance and good adhesiveness. Played.

[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 C07C 253/30 255/56 255/60 261/02 C08G 73/06 NTM

Claims (5)

[Claims] 1. The following general formula I: [In the formula, X ₁ and X ₂ are the same or different, and -NH ₂ , -NH-C≡
N, -OH, -O-C≡N, -C≡N, -C≡CH or (D is a group containing at least one ethylenically unsaturated double bond), and X ₁ and X ₂ are not —NH ₂ at the same time. ”, Cinnamanilide Compounds. 2. The following general formula I: [In the formula, X ₁ and X ₂ are the same or different, and -NH ₂ , -NH-C≡
N, -OH, -O-C≡N, -C≡N, -C≡CH or (D is a group containing at least one ethylenically unsaturated double bond), but X ₁ and X ₂ are not —NH ₂ at the same time, ”and a cinnamanilide compound is produced. In the method, the following general formula: An acetanilide compound represented by the formula (wherein X ₂ has the same meaning as the above formula I), and the following general formula: A method for producing a cinnamanilide compound represented by the above formula I, which comprises subjecting a corresponding benzaldehyde compound represented by the formula (wherein X ₁ has the same meaning as the above formula I) to a dehydration condensation reaction. 3. The following general formula I: [In the formula, X ₁ and X ₂ are the same or different, and -NH ₂ , -NH-C≡
N, -OH, -O-C≡N, -C≡N, -C≡CH or (D is a group containing at least one ethylenically unsaturated double bond), but X ₁ and X ₂ are not —NH _{2 ”} , and a cinnamanilide compound is contained. A resin composition comprising: 4. The resin composition according to claim 3, wherein the composition also contains a compound having an N-substituted unsaturated imide group and / or a polyfunctional epoxy compound. 5. The following general formula I: [In the formula, X ₁ and X ₂ are the same or different, and -NH ₂ , -NH-C≡
N, -OH, -O-C≡N, -C≡N, -C≡CH or (D is a group containing at least one ethylenically unsaturated double bond), but X ₁ and X ₂ are not both —NH ₂ ], or a cinnamanilide compound represented by A cured polymer obtained by crosslinking and curing a resin composition containing a compound with at least heat energy and / or light energy.