JPH01306405A - Ortho diallylbiscyanate compounds and compositions containing these compounds - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed Description of the Invention] (Industrial Application Field) The present invention relates to a novel polymerizable monomer, and in particular, by heating, it is possible to provide a cured product with excellent heat resistance, flexibility, and adhesiveness. monomer, and compositions containing this monomer,
and regarding the uses of this monomer.

[Conventional technology]

Conventionally, as one of the means for imparting heat resistance to solvent-free panels for coil insulation, combinations of ortho-diallyl bisphenol-based compounds and N-substituted maleimide-based compounds (Japanese Unexamined Patent Publication No. 184024/1982), Applications such as combinations with epoxy compounds have been studied. However, these compositions require a long curing time, the resulting cured product has poor flexibility, and often results in product defects due to cracking. Furthermore, it has poor adhesion to inorganic substances, and is not an effective means for improving the mechanical strength of structures.

[Problem to be solved by the invention]

The above conventional technology uses an ortho-diallyl bisphenol compound to reduce the viscosity of the composition (liquid state near room temperature).
Because the main focus was placed on achieving this, it was difficult to improve curability, and crosslinking efficiency was not necessarily high, resulting in poor mechanical strength, even though the glass transition point was not very low, and often There have been problems with cracks occurring in the cured product (molded product), or poor adhesion and adhesion to metals (Cu, AQ, etc.) and inorganic materials (coils, glass fibers, etc.). This is due to the fact that the allyl group and the hydroxyl group of the ortho-diallyl bisphenol compound as the material imparting heat resistance have different reaction forms.

The object of the present invention is to provide a composition that can reduce the viscosity of the composition and provide a cured product with excellent curability, heat resistance, flexibility, and adhesion, and a laminate using the composition. Our goal is to provide the following.

[Means to solve the problem]

The above purpose was achieved as a result of various studies in order to eliminate the above-mentioned problems of conventional ortho-diallyl bisphenol compounds.
achieved. The summary is as follows.

(1) General 2 [) [In the formula, ), -0-.

-Co+, -coo+, -s+, -8Oz-9. ] An ortho diallyl biscyanate compound.

(2) A polyfunctional epoxy compound and the general formula (1)z [wherein, ), -0-.

-〇〇-, -CO〇-, -s-, -5ob-.

It is. A resin composition comprising an ortho diallylbiscyanate compound represented by the formula:

(3) General formula [1].

The resin composition according to (2), which is an ortho diallylbiscyanate compound represented by:

(4) N-substituted unsaturated imide compound and the general formula [wherein, X is none, -CHz, C-(RtZ and R2 are lower alkyl group, perfluoroalkyl group,
Any one of hydrogen, which may be the same or different from each other. ), -〇-1-Co+, -coo+,
-s+, -8O2-.

It is. A composition characterized by containing an ortho diallylbiscyanate compound represented by:

(5) The N-substituted unsaturated imide compound is an N,N'-substituted bismaleimide compound (4)
) composition.

(6) The N-substituted unsaturated imide compound has the following formula [11]
[In the formula, R1 and R2 are the same as above. Further, D is a divalent organic group having an ethylenically unsaturated double bond.

The composition (4) is an aromatic ether unsaturated bisimide compound represented by the following.

(7) At least general 2N) [In the formula, or without, -CH2-, C(Rt and R2
are any one of a lower alkyl group, a perfluoroalkyl group, and hydrogen, and may be the same or different. ), −〇−.

-〇〇-, -coo-, -s-, -s○2-9. ] and the general formula (III [in the formula, or the same as above. In addition, Yl and Y2 are hydrogen, a lower alkyl group, and glycidyl \ R′″′ is CFa , Cabs, C3F7, which may be the same or different from each other.), which may be the same or different from each other. A composition characterized in that it is an ortho-diallyl bisphenol derivative.

(8) General formula (III) is replaced by the following formula (IV) Ri [wherein, ), -〇-1. The composition according to (7), which is an ortho diallyl bisglycidyl ether compound represented by the following.

(9) (A) polyfunctional epoxy compound, (B)
A compound containing an N-substituted unsaturated imide group, (C) a phenol/aldehyde condensate.

(D) one or more selected from poly-bara-hydroxystyrene; and (E) general formula [
■] [In the formula, Good.), -0-.

-co-, -co○-, -S-, -SO2-.

It is. ] A laminate comprising a composition comprising an ortho-diallyl biscyanate compound represented by:

[Effect]

In the present invention, the general formula ([] (R1 and R2 are any of a lower alkyl group, a perfluoroalkyl group, and hydrogen, and may be the same or different from each other), -0 −.

It is. Examples of the ortho diallylbiscyanate compounds represented by the formula include the following. That is, Ha CH3 CFδ The ortho diallyl biscyanate compound represented by the above general formula [1] is, for example, the general formula (V) I [wherein, X is none, -CH2-, -c -(R1 and R2 is a lower alkyl group, a perfluoroalkyl group, or hydrogen, and may be the same or different.), -0-.

It is. It can be obtained by reacting the or-1-diallylbisphenol compound represented by the formula with a halogenated cyanogen compound, such as chlorocyan or bromcyan, in the presence of a tertiary amine or the like.

Furthermore, in the present invention, the general formula (in) [wherein, X is as defined above] is used. In addition, Yl and Yl are any one of hydrogen, a lower alkyl group, glycidyl ether\R''' CzFs, CaP2, and may be the same or different from each other. They may be the same or different from each other. Examples of the ortho-diallylbisphenol derivatives represented by the above formula include the following.

or and so on.

The ortho diallyl biscyanate compound represented by the general formula (1) of the present invention can be prepared by adding a monomer containing at least one polymerizable CHx=C group which can be of vinyl, allyl or acrylic type. It can be denatured by

Here, the monomer is, for example, styrene, vinyltoluene,
α-methylstyrene, divinylbenzene, diallyl athalate, diallyl phthalate prepolymer, chlorstyrene, dichlorostyrene, bromstyrene, dibromstyrene, diallylbenzene phosphonate, diallyl arylphosphylate, acrylic acid, methacrylate, Examples include triallyl cyanurate, triallyl cyanurate prepolymer, and tribromophenol allyl ether, and one or more of these can be used in combination.

Further, the ortho diallylbiscyanate compound represented by the general formula [1] of the present invention can be modified before curing by adding a known unsaturated polyester. Here, what is unsaturated polyester?9. Esterification or esterification of unsaturated dibasic acids, saturated dibasic acids and their anhydrides, or their lower alkyl ester derivatives, etc., with diols, or alkylene monooxides and their derivatives, etc., in the presence or absence of a catalyst. A polyester resin base containing an unsaturated group synthesized by condensation or addition polymerization using reactions such as exchange, an ethylene-based (e.g. vinyl group, allyl group, etc.) polymerizable compound, and peroxide It consists of a mixture with a chemical catalyst. In addition, vinyl ester resins obtained by reacting bisphenol A type and novolac type epoxy compounds with methacrylic acid or acrylic acid are also useful. Here, typical unsaturated dibasic acids and saturated dibasic acids are maleic acid, maleic anhydride, fumaric acid, gloromaleic 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 anhydride, pimelic acid, hexahydrophthalic acid and its anhydride, tetrahydrophthalic acid, carbic acid anhydride, Hett's acid and its anhydride, tetrahyphthalic acid and its anhydride, tetrahyphthalic acid and its anhydride, These lower alkyl esters are used, and diol components include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, trimethylene glycol, tetramethylene glycol, hexamethylene glycol, and 2,2-diethyl. Propanediol, 1,3-neopentyl glycol, dibromneopentyl glycol, bisphenol dioxyethyl ether, 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, phenylglycidyl ether, allylglycidyl ether, etc. are used. Further, if necessary, a trifunctional or higher functional polybasic acid and/or a polyhydric alcohol may be used in combination within a range that does not impair the object of the present invention. Crosslinking agents include, for example, styrene, vinyltoluene, α-methylstyrene, divinylbenzene, diallyl phthalate, diallyl phthalate prepolymer, chlorstyrene, dichlorostyrene, bromustyrene, dibromostyrene, diallylbenzenephosphonate, diallylaryl phosphyl. Acid esters, acrylic esters, methacrylic esters, triallyl cyanurate, triallyl cyanurate prepolymers, 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.

Furthermore, various modifications and addition of modifiers are also possible. Further, the unsaturated polyester is not limited to one type, and a mixture of two or more types is also possible.

The ortho diallylbiscyanate compound represented by the general formula (1) of the present invention reacts with a polyamine, particularly a doamine, and becomes a heat-resistant material with excellent flexibility. here,
Examples of amine compounds include m-phenylenediamine,
p-phenylenediamine, benzidine, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dichlorobenzidine, 3,3'-dimethoxybenzidine, 4
゜4'-diaminodiphenylmethane, 1,1-bis(4
-7minophenol)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 needle, 4,4'-diaminodiphenyl sulfide, 3°3'-diaminodiphenyl sulfide, 4,
4'-diaminodiphenylsulfoxide, 4,4'diaminodiphenylsulfone, 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 oxyto, bis(4-aminophenyl)ethylphosphine oxyto, 1,5-diaminonaphthalene, 2,6-diamitupyridine, 2.5
-Diamino-1,1,4-oxadiazole, m-xylylenediamine, P-xylylenediamine, 2+4(p
-β-amino-butylphenyl) ether, p-bis-2-(2-methyl-4-aminopentyl)benzene, p-bis(1゜1-dimethyl-5-aminopentyl)
Benzene, hexamethylene diamine, heptamethylene diamine, octamethylene diamine, nonamethylene diamine, decamethylene diamine, 2,11-diaminododecane, 1,12-diaminooctadecane, 2,2-dimethylpropylene diamine, 2,5-dimethylene Hexamethylenediamine, 3-methylhbutamethylenediamine, 2
．． 5-dimethylhbutamethylenediamine, 4,4-dimethylhbutamethylenediamine, 5-methynonamethylenediamine, 1,4-diaminocyclohexane, bis(p-
aminocyclohexyl)methane, 3-methoxyhexamethylenediamine, 1,2-bis(3-aminopropoxy)ethane, bis(3-aminopropyl)sulfide,
Examples include N,N-bis(3-aminoflovir)methylamine. Also, 2゜4-diaminodiphenylamine, 2.4-diamino-5-methyldiphenylamine,
2,4-diamino-4'-methyldiphenylamine, 1
-anilino-2,4-diaminonaphthalene, 3.3'
-Diamino-4-anilinobenzophenone and other N-aryl substituted aromatic triamines. Furthermore, polyamines represented by the general formula (wherein, X is an alkylidene group containing a methylene group, and m is a number on average of 0.1 or more) are also useful. In particular, 2 are effective in imparting flexibility.
,2'-bis(4-(4-aminophenoxy)phenyl)propane, 2,2'-bis[3-methyl-4-(4
There are diamine compounds with ether bonds such as -aminophenoxy)phenyl]propane.

In addition, by adding epoxy compounds, heat resistance,
It also becomes a cured product with excellent moldability.

In addition, examples of epoxy compounds include glycidyl ether of bisphenol A, butadiene dieboxide, 3,4-epoxycyclohexylmethyl-(3,4-
epoxy)cyclohexane carboxylate, vinylcyclohexane dioxide, 4,4'-di(1,2-epoxyethyl)diphenyl ether, 2,2-bis(3
, 4-dipoxycyclohexyl)propane, glycidyl ether of resorcinol, diglycidyl ether of phloroglucine, diglycidyl ether of methylphloroglucine, 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-phinidine bis(4゜5-epoxy-1,2-cyclohexanedicarboximide, etc.) epoxy compounds, triglycidyl ether of para-aminophenol, polyallyl glycidyl ether, 1,3.5-tri(1,2-
epoxyethyl)benzene, 2.2'.

4. Tri- or higher-functional epoxy compounds such as 4'-tetraglycidoxybenzophenone, polyglycidyl ether of phenol formaldehyde novolak resin, triglycidyl ether of glycerin, triglycidyl ether of trimethylolpropane, and halogens such as brominated epoxy A modified epoxy compound or a hydantoin epoxy compound is used.

In particular, in the present invention, the following formula CHa ■ [In the formula, Z is a direct bond, CH2, -C-.

It is any one of Ha CFa 0 -C, O-y C, S-, 502t CFa CH3 -8i-. ] Tetrafunctional epoxy compounds represented by CH3 such as benzophenone tetraglycidyl ether (BPTGE) and resorcin sulfide tetraglycidyl ether (R5TGE) are useful.

Known curing agents and catalysts for epoxy compounds can be added to the ortho-diallyl biscyanate composition. As for such products, there is a book written by Hiroshi Kakiuchi; Epoxy Resin (Showa 45
Published in September 2016) pages 109-149, Lee, Nev
Tomi Epoxy Resins (Me Gra
w-Hill Book Cornoany Inc.
New York, 1957) 63-141
Page, P. E. Brunis; Epoxy
Re5ins Technology (Inters
sciencePublishers, New York
K, published in 1968), pages 45 to 111, for example.

aliphatic polyamines, aromatic polyamines, amines including secondary and tertiary amines, carboxylic acids, carboxylic acid anhydrides, aliphatic and aromatic polyamide oligomers, and polymers, boron trifluoride-amine complexes, Synthetic resin initial condensates such as phenol resin, melamine resin, urea resin, urethane resin, etc., and dicyandiamide.

Examples include carboxylic acid hydrazide and polyamides.

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

In particular, phenol borac resin is highly effective in terms of adhesion of the cured resin to metal inserts and workability during molding.
It is suitable as a curing agent component for semiconductor encapsulation materials.

Furthermore, various catalysts can be added for the purpose of promoting the curing reaction of the epoxy resin composition, and these catalysts include, for example, triethanolamine, tetramethylbutanediamine, tetramethylpentanediamine, tetramethylhexanediamine, l - Tertiary amines such as lyethylenediamine and dimethylaniline, oxyalkylamines such as dimethylaminoethanol and dimethylaminopentanol, and amines such as tris(dimethylaminomethyl)phenol and methylmorpholine can be applied.

For the same purpose, as a catalyst, for example, cetyltrimethylammonium bromide, cetyltrimethylammonium chloride, dodecyltrimethylammonium iodide, trimethyldodecylammonium chloride, benzyldimethyltetradecylammonium chloride, pendylmethylpalmitylammonium chloride, allyldodecyltrimethyl ammonium bromide,
benzyldimethylstearylammonium bromide,
Quaternary ammonium salts such as stearyltrimethylammonium chloride and benzyldimethyltetradecylammonium acetate can be applied;
-undecylimidazole, 2-methylimidazole,
2-ethylimidazole, 2-heptadecylimidazole, 2-methyl-4-ethylimidazole, 1-butylimidazole, 1-propyl-2-methylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2 -methylimidazole, ]-]cyanoethyl-2-undecylimidazole 1-cyanoethyl-2-
Imidazoles such as phenylimidazole, 1-azine-2-methylimidazole, 1-azine-2-undecylimidazole, triphenylphosphine tetraphenylbore 1-, tetraphenylphosphonium tetraphenylborate, triethylamine tetraphenylbore 1, Examples include tetraphenylborate such as N-methylmorpholinetetraphenylborate, 2-ethyl-4-methylimidazoletetraphenylborate, and 2-ethyl-1,4-dimethylimidazoletetraphenylborate.

Also, 1,5-diaza-bicyclo(4,2,O)octene-5,1,8-diaza-bicyclo(7゜2,o)undecene-8,1,4-diaza-bicyclo(3,3, O)
octene-4,3-methyl-1,4-diazabicyclo(
3,3,O)octene-4,3,6,7,7-tetramethyl-1,4-diazadicyclo(3,3,O)octene-4,1,5-diaza-bicyclo(3,4,O ) Nonene-5,1,8-diaza-bicyclo(7,3,O) Dodecene-8,1,7-diazabicyclo(4,3°O) Nonene-6,1,5-diazabicyclo(4°4.0 ) Decene-5,1,8-diazabicyclo(7,4,O) Tridecene-8,1,8-diazabicyclo(5,3,O)Decene-7,9-methyl-1,8-diazabicyclo(5,
3,O) Decene-7,1,8-diazabicyclo(5,4
,O) undecene-7,1,6-diazabicyclo(5,
5゜0) Dodecene-6,1,7-diazabicyclo(6゜5,O) Tridecene-7,1,8-diazabicyclo(7
,5,O) Tetradecene-8,1,10-diazabicyclo(7,3,O) Dodecene-9,1゜1o-diazabicyclo(7,4,O) Tridecene-9,i,14
-diazabicyclo(11,3,O)hexadecene-13
Also useful are diazabicyclo-alkenes such as , 1,14-diazabicyclo(11,4,O)butadecene-13. One or more of these compounds can be used in combination depending on the purpose and use. Among the above compounds, 1,8-diazabicyclo(5,4,O)undecene-7 (DBU) and carboxylic acid salts of this compound are particularly effective in exerting the effects of the present invention.

In the present invention, the Na-substituted unsaturated imide compound is
For example, N- such as phenylmaleimide, phenylcitraconimide, phenylendomethylenetetraphthalimide, cyclohexanemaleimide, 2-methylphenylmaleimide, 2,6-dimethylphenylmaleimide, 2-chlorophenylmaleimide, 2,6-cyclohexanemaleimide, etc. Substituted monounsaturated imide compounds, and general formula [V] [wherein D is a divalent organic group having an ethylenically unsaturated double bond]. Furthermore, R3 represents one or more alkylene groups, arylene groups, or substituted divalent organic groups thereof. N,N'-substituted bis-unsaturated imide compounds represented by ], for example, N,N'-ethylene bismaleimide,
N,N'-hexamethylene bismaleimide, N,N'
-dodecamethylene bismaleimide, N,N'-m-phenylene bismaleimide, N,N'-p-phenylene bismaleimide, N,N'-4,4'-diphenyl ether bismaleimide, N,N'-4, 4'-diphenylmethane bismaleimide, N, N-4,4'-dicyclohexylmethane bismaleimide, N.

N, N'-4,4-diphenylcyclohexane bismaleimide, or.

Alternatively, unsaturated imide compounds such as citraconimide, itaconimide, tetrahydrophthalimide, and endomethylenetetraphthalimide corresponding to each of the above maleimide compounds, N.

Among N'-substituted bismaleimide compounds, compounds of general formula (VI) (VI) (wherein R4-R7 represent hydrogen, lower alkyl group, lower alkoxy group, chlorine or bromine, and are the same as each other) (R6 and Re are hydrogen, methyl group, ethyl group, triple ormethyl group or trichloromethyl group, and D is a divalent organic group having an ethylenically unsaturated double bond.) By using the etherimide compounds shown above, it is possible to improve solubility in general-purpose solvents, improve adhesion to inorganic materials, metals, etc., and achieve both heat resistance and flexibility. spread to Examples of the etherimide compound represented by the above general formula (VI) of the present invention 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 -Butyl-4-(4-maleimidophenoxy)phenyl]propane, 2,2-bis[3-see-butyl-4-(4-maleimidophenoxy)phenyl]propane, 2,2-bis[3-methoxy-4 -(4-maleimidophenoxy)phenyl]propane, ]-, ]1-bis4-(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)phenylcomethane, bis[3-methyl-4-(4-maleimidophenoxy)phenylcomethane, bis[ 3-chloro-4-(4-maleimidophenoxy)phenylcomethane, bis[3-bromo-4-(4-maleimidophenoxy)phenylcomethane, 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
3.3
．． 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]propane, etc.

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

u, C"He, Oi'0F・
0n・CF3 Hs H3 4He 4H9 0〆5 CHs CHa CHa Oi0 04' Ctla Hs Hs 0 Also, the ortho diallylbiscyanate compound represented by the general formula CI) of the present invention has the secondary formula A ( 0-CEN
).

[In the formula, m is 2 to 5. A is an m-valent organic group having at least one aromatic nucleus. This cyanate group is bonded to the aromatic nucleus of an organic group. It is also possible to use a polyfunctional cyanate ester compound represented by the following formula.

Examples of polyfunctional acetic acid ester compounds include:

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
-Dolicyanatonaphthalene, 4,4'-dicyanatobiphenyl, 4,4'-dicyanatodiphenylmethane, 4
, 4'-dicyanatodiphenyl ether, 4,4'-dicyanatodiphenyl sulfone, 4,4'-dicyanatodiphenyl sulfide, 2,2-bis(4-cyanatophenyl)propane, 2,2-bis( 4-(4-cyanatophenoxy)phenyl]propane, 2,2-bis(4-cyanatophenyl)hexafluoropropane, 2,2-bis(4-(4-cyanatophenoxy)phenyl)hexafluoro Propane, 2,2-bis(3,S-dichloro-
4-cyanatophenyl)propane, 2,2-bis(3,
5-dibromo-4-cyanatophenyl)propane, tris(4-cyanatophenyl)phosphite, tris(4
-cyanatophenyl) phosphate, etc.

N, N'-substituted maleimide compounds, or.

When a compound having a polymerizable functional group such as unsaturated polyester is used in combination with the compound represented by the general formula (1) of the present invention, the resin composition may contain a compound for the purpose of completing curing by short heating. , it is desirable to add a polymerization initiator. Such polymerization initiators include benzoyl peroxide, P-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, cabrylyl peroxide, lauroyl peroxide, and acetyl peroxide.

Methyl ethyl ketone peroxide, cyclohexanone peroxide, bis(1-hydroxycyclohexyl peroxide), hydroxyhebutyl peroxide, tertiary butyl hydroperoxide.

Organic peroxides such as p-menthane hydroperoxide, tertiary butyl perbenzoate, tertiary butyl peracetate, tertiary butyl peroctoate, tertiary butyl peroxyisobutyrate and di-tertiary butyl perphthalate. Oxides are useful, and one or more of them can be used.

In the present invention, known accelerators such as mercaptans, sulfides, β-diketones, metal chelates, and metal soaps can also be used in combination with the above-mentioned polymerization catalyst.

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, and P-
Known polymerization inhibitors such as phenols and nitro compounds and metal salts such as tert-butylcatechol and 2,5-di-tert-butylhydroquinone can be used if desired.

Further, in the present invention, a known coupling agent can be added to the resin composition containing at least general formula CI). Examples of such materials include metal alkoxides such as titanium, aluminum, and zirconium, metal chelate compounds, silane compounds, fluorine-containing compounds, and borane compounds. Use of one or more of these in combination can improve adhesion, improve moisture resistance, improve mechanical strength, improve electrical properties, and improve heat resistance.

It may be highly effective in improving crack resistance.

Among these, it is particularly useful to add a silane coupling agent. Examples of such substances include γ-glycidoxypropylmethyljethoxysilane, CIl2-CIl-CH2-0-Calls Si-
←0C2H5)2\1 Epoxysilane compounds such as Kn[E402, N-β(aminoethyl)γ-aminopropyltrimethoxysilane.

82N -C2H4-NH-Ca1ls Si-←0
CH3)3K, 8M603N-β (aminoethyl)
γ-aminopropylmethyldimethoxysilane H2N-CzH4-Nil-C3t(s Si-←0
CH3)2 to 8M602γ-aminopropyltriethoxysilane HzN -Ca1ls -St-←0Cz
ll+)) 3KBE903N-phenyl-γ-aminopropyltrimethyl-1-xysilane Co11s-NH-CsHa-3i (OCHa)a
Aminosilane compounds such as 8M573, or γ-mercaptopropyltrimethoxysilane l5-CsHe-5i (OCHa)a
8M803 Vinyltris(β-methoxyethoxy)silane CHz=CH3i (OCzHnOCH
a)a KBC1003 Vinyltriethoxysilane CHx-CH5i (OCzt(3)a
KBE1003 Vinyltrimethoxysilane C11z=CH3i ((lcHa)a
Vinylsilane compounds such as KBM1003.

γ-methacryloxypropyltrimethoxysilane Ha CH2=C-C-0-CaHe-5i(OCHa)a
Acrylic silane compounds such as KBM503.

β-(3,4 epoxycyclohexyl)ethyltrimethoxysilane γ-glycidoxypropyltrimethoxysilane γ-chloropropyl I-rimethoxysilane CQ CaHe -S
i (0CHs)a KBM703N
, O-(bistrimethylsilyl)acetamide N, N'
-bis(trimethylsilyl)urea ((H3C)aSi
N)I]2COBTSIJ tetramethoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane,
Phenyltrimethoxysilane, tetraethoxysilane,
Examples include dimethyljethoxysilane and diphenyljethoxysilane.

As titanate compounds, for example, acylate compounds represented by the formula (% formula %), phosphate compounds represented by the formula (RO) a Ti (0-P (OR' ) z) b, formula %) An alcoholade-based compound represented by the formula % or formula %) [In the above formula, R and R' are H9 lower alkyl groups.

Further, a+b=4. ] There are coordinate compounds represented by

Specifically, isopropyl, triisostearoyl titanate, isopropyl tri(laurylmyristyl) titanate, isopropyl isostearoyl dimethacrylic titanate, isopropyl tri(dodecylbenzenesulfonyl) titanate, isopropyl instearoyl diacrylic titanate. , isopropyl tri(diisooctyl phosphate) titanate, isopropyl trimethacrylic titanate, isopropyl di(dodecylbenzenesulfonyl)-4-aminobenzenesulfonyl titanate, diallylphosphite titanate, isopropyl isostearoyl titanate
Di-4-amino-benzoyl titanate, isopropyl tri(dioctylpyrophosphate) titanate,
Isopropyl triacroyl titanate, dioctyl phosphite titanate, isopropyl tri(
N-ethylamino ethanolamino titanate or 2 is a combination of at least one metal selected from aluminum, titanium, tin, zinc, lead and zirconium, and β-diketone and β-keto acid ester. A metal chelate compound consisting of a ligand selected from, for example, tris(2,4-pentanedionato)aluminum, (2,4-pentanedionato)bis(ethylacetoacetate)aluminum, tris(ethylacetoacetate) acetate) aluminum, bis(ethylacetoacetate) titanium, tetrakis(2,4-pentanedionato) titanium, dibutylbis(2,4-pentanedionato)tin, dimethylbis(ethylacetoacetate)tin, bis( 2゜4-pentanedionate) zinc, bis(
Examples include ethyl acetate (ethyl acetate) lead and tetrakis (ethyl acetate) zirconium.

Furthermore, an alcoholate compound of at least one metal selected from aluminum, titanium, tin, zinc, button, and zirconium is used as a component. Such alcoholate compounds include, for example, aluminum methylate, aluminum ethylate, aluminum i-
Probile-1-.

Aluminum n-butyrate, mono-5ee-butoxyaluminum, Jimmy propylate, ethyl aluminum, diethylate, ethyl aluminum, Jimmy propylate, titanium, tetra-1-propylate, tin, tetra-1-propylate, zinc , Jimmy propylate, lead, Jimmy propylate, zirconium, and tetra-1-propylate, and one or more of them can be used, and some or all of them can be polycondensed. In addition to the heating method described above, a curing method using ionizing radiation or light (ultraviolet light) can be used as a means for curing the resin composition of the present invention even when used as a prepolymer.

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

Further, as a light source for photocuring, sunlight, a tungsten lamp, an arc lamp, a canon lamp, a halogen lamp, a low pressure or a high pressure mercury lamp is used.

There is no restriction on the use of photosensitizers during photocuring. These include, for example, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, penzathrone, β-methylanthraquinone, benzophenone, 9,10-phenanthrenequinone, anthraxin, benzophenone,
- Nitroacenaphthene, 1-nitronaphthalene, Michler's ketone, nioxy, erythrosine, acridine, etc., and one or more of them can be used in combination.

The curable resin composition of the present invention also includes a final coating film,
Various natural, semi-synthetic or synthetic resins can be blended for the purpose of improving the properties of the resin in the adhesive layer, resin molded product, etc. Such resins include oleoresins such as drying oils and semi-drying oils, rosins, shellacs, copals,
Examples include one or a combination of two or more of oil-modified rosin, phenolic resin, alkyd resin, urea resin, melamine resin, polyester resin, vinyl butyral resin, vinyl acetate resin, vinyl chloride resin, acrylic resin, and silicone resin, These resins may be blended in an amount within a range that does not impair the original properties of the ortho-diallyl biscyanate compound of the present invention, for example, 30% by weight or less of the total resin amount.

The resin composition of the present invention may further contain reinforcing materials or fillers in the form of fibers or powder. Powdered reinforcing agents or fillers include inorganic powders such as various carbon blacks, finely powdered silica, calcined clay, basic magnesium silicate, diatomaceous earth 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, slab wool, and carbon fiber, and various synthetic fibers such as paper, bulbs, wood flour, cotton, linters, and polyimide fibers. These fibrous reinforcements include small fibers,
It can be used in the form of stable, tow, web, woven fabric, non-woven fabric, or paper product. These reinforcing materials or fillers may be used in amounts of up to four times the weight of the resin solid content for laminated materials and molding materials, although this will vary depending on the application. In addition, the resin composition of the present invention may contain white pigments such as titanium dioxide, yellow lead, carbon black, iron black, molybdenum red, etc. for the purpose of coloring the composition.
It is possible to contain coloring pigments such as cypress, cadmium yellow, cadmium red, or various organic dyes and pigments.

Furthermore, when the resin composition of the present invention is used as a paint, in addition to these coloring pigments, rust preventive pigments such as zinc chromate, red lead, red iron, zinc white, strontium chromate, and aluminum stearate may be added. anti-sagging agents such as
It may contain well-known paint compounding agents such as dispersants, thickeners, film modifiers, extender pigments, and flame retardants.

The resin composition of the present invention is applied to a substrate as a coating film or adhesive layer, or molded or laminated in the form of powder, pellets, or impregnated into a substrate, and then cured by heating. The temperature required for curing the resin composition of the present invention is determined by a catalyst or a temperature required for curing the resin composition of the present invention.

Although it varies depending on whether or not a curing agent is used and the type of resin, the temperature is generally 0 to 300°C, preferably 100 to 2°C.
It is preferable that the temperature is in the range of 50°C. The required heating time depends on whether the resin composition containing the ortho-diallyl biscyanate compound is a thin coating film or a relatively thick molded product.
Or, although it varies considerably depending on whether it is a laminate,
Generally, a time sufficient to completely cure the resin component may be selected from 30 seconds to 10 hours.

In the present invention, a semiconductor device obtained by coating or sealing at least a part of a semiconductor element with a composition containing an ortho diallylbiscyanate compound represented by the general formula [■] has heat resistance, It has excellent moisture resistance. In this case, it is preferable that the composition containing the ortho diallylbiscyanate compound represented by the general formula CI) be obtained in a state soluble in an organic solvent.

This composition is preferably applied as a solution to the surface of a semiconductor element, etc., and examples of solvents include aromatic hydrocarbons such as benzene, toluene, and xylene, alcohols such as ethanol and 2-propanol, and acetone. ,
Examples include ketones such as methyl ethyl ketone, chlorinated hydrocarbons, and polar solvents such as N-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, and dimethylsulfoxide.

Solutions of these compositions are applied to the surfaces of semiconductor elements, lead wires, and the like. The application method includes dipping the element and lead wires into the solution, dropping the solution onto the element and lead wires,
Alternatively, there are methods such as spraying and spinner coating.

The semiconductor elements and lead wires coated with the composition solution by such a method are then subjected to light energy and/or heat baking treatment at least at room temperature or above, particularly preferably at 100 to 250°C. By this treatment, the composition of the present invention is polymerized and cross-linked to form a protective wave RLI layer on the device. The thickness of the coating is adjusted as appropriate depending on the purpose. In other words, the α-ray shielding film to prevent soft errors in LSIs should have a thickness of 10 to 70 μm, preferably 30 to 60 μm.
A thickness of μm is required, and the interlayer insulating film for multilayer wiring is
It is preferably formed to have a thickness of 10 μm or less, particularly 1 μm or less. This is achieved by adjusting the concentration of the solution accordingly, around 10 weight percent in the former case and around 1 weight percent in the latter case.

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

〔Example〕

<Examples 1 to 8. Comparative example> As an ortho-diallyl biscyanate compound.

In addition to the five types of herb containing five types of
4-Maleimidophenoxy)phenyl]hexafluoropropane and triallyl isocyanurate were separately blended in the predetermined amounts (parts by weight) shown in Table 1 to prepare a similar blend. To these were added dicyandiamide, benzoguanamine, and dicumyl peroxide as curing accelerators, and predetermined amounts of epoxysilane KBM403 (manufactured by Shin-Etsu Chemical Co., Ltd.) as a coupling agent.

These blended compositions were then dissolved in an isostatic mixture of N-methyl-2-pyrrolidone and methyl ethyl ketone,
The varnish contained 45 to 48% by weight of solids.

This varnish solution was applied to glass cloth (WE-116 manufactured by Nittobo Co., Ltd.).
9. BY-54) was coated with resin impregnation and heated at 160°C, 1
It was dried for 5 minutes to produce a coated cloth having a resin content of 45 to 48% by weight.

Next, a sheet was applied to the coated cloth, and 35 μm thick TAI-treated copper foil (manufactured by Furukawa Nii CFC Co., Ltd.) was layered on top and bottom of the coated cloth.
0-190℃, 40kg-f/! Lamination and bonding was carried out for 80 minutes under these conditions to create a double-sided copper-clad laminate with a thickness of approximately 1.6 m.

The above copper-clad laminate was further post-cured at 200° C. for 4 hours. Table 1 shows various properties of the types of copper-clad laminates obtained.

-Method for measuring properties- a) Copper foil peel strength After cutting a test piece into a size of 25 nn x 100 nu from a copper-clad laminate, leave a piece of copper foil with a width of 1 ono in the center, and remove the other copper foils. Removed by etching.

Next, the copper foil in the center is vertically spread at a rate of 5 mm/min.
The strength was measured.

b) Solder bath A test piece was cut into a 25 mm square piece from a heat-resistant copper-clad laminate. Float the test piece in a solder bath heated to 300°C,
The time taken for abnormalities such as blistering to occur was measured.

C) Anti-inflammatory UL Measured according to the vertical method. This copper-clad laminate was cut to a width of 12 mm and a length of 125 mm, and the steel foil was removed by etching to prepare a test piece. 10 exams each
Each item was measured and expressed as the average inflammation extinction time. In addition, the average extinguishing time is 5 seconds or less, and the maximum extinguishing time is 10 seconds or less according to UL-94.
V-0, average flame-out time within 25 seconds, and maximum flame-out time within 30 seconds are UL-94 and V-1.

<Examples 9 to 1.6 (Comparative Example)> The three types (B), (C), and (E) above were taken as the ortho-diallylbisthiachi 1-based compound, and the eight types shown in Table 2 were A predetermined amount of was collected. In addition, the epoxy compounds EOCN102S (ortho-cresol novolac type epoxy resin manufactured by Nippon Kayaku Co., Ltd.), N, and N
' -bismaleimide-diphenylmethane, polyP-
Hydroxystyrene (M resin manufactured by Marukubi Sekiyu Co., Ltd.), Or1
-Diallylglycidyl ether and 2,2-bis(4-cyanatophenyl)propane were each blended in predetermined amounts (parts by weight) shown in Table 2. These include, respectively,
As a curing accelerator, 2 parts by weight of imidazole 2E4MZ-CN (manufactured by Shikoku Kasei Co., Ltd.) and triphenylphosphine were added, and as a coupling agent, 13M303 was added to epoxysilane.
(manufactured by Shin-Etsu Chemical Co., Ltd.), 2 parts by weight of carnauba wax as a mold release agent, 80% by weight of spherical silica powder with an average particle size of 10 μm as a filler, and 2 parts by weight of carbon black as a coloring agent were added.

Next, each of the above formulations was roll-kneaded at 75 to 85°C for 7 minutes, cooled, and coarsely ground to obtain a resin composition for LSI sealing.

Using this resin composition, IM bit D-RAM LSI
was transfer molded under the conditions of 180'C, 1.5 minutes, and 70 kg-f/cut to obtain a resin-sealed LSI.

The resin-sealed LSI was left in supersaturated steam at 121° C. and 2 atm (pressure hookah cauldron) for a predetermined period of time, then taken out and checked to see if the AQ wiring on the device had broken due to corrosion. In addition, resin-sealed LS
I was subjected to cooling and heating cycles in liquid nitrogen at -196°C and silicone oil at 200°C, and the number of cycles until the LSI failed due to disconnection was checked.

These evaluation results are shown in Table 2.

〔Effect of the invention〕

According to the present invention, the ortho diallylbiscyanate compound has excellent moldability. Heat-resistant.

Effective as a material that imparts flexibility and adhesion.

In addition, compositions based on ortho-diallyl biscyanate compounds are effective in improving the reliability of applied products as laminates and semiconductor sealing materials.

Claims (1)

[Claims] 1. General formula [I] ▲ Numerical formula, chemical formula, table, etc. ▼ [I] [In the formula, X is none, -CH_2-, ▲ Numerical formula, chemical formula,
There are tables, etc. ▼ (R_1 and R_2 are lower alkyl groups, perfluoroalkyl groups, or hydrogen, and may be the same or different.), -O
-, -CO-, -COO-, -S-, -SO_2-, ▲
There are mathematical formulas, chemical formulas, tables, etc. ▼ (m is 1 to 4). ] An ortho diallyl biscyanate compound. 2. Polyfunctional epoxy compound and general formula [I]▲mathematical formula,
There are chemical formulas, tables, etc. ▼ [I] [In the formula, X is none, -CH_2-, ▲ Numerical formula, chemical formula,
There are tables, etc. ▼ (R_1 and R_2 are lower alkyl groups, perfluoroalkyl groups, or hydrogen, and may be the same or different.), -O
-, -CO-, -COO-, -S-, -SO_2-, ▲
There are mathematical formulas, chemical formulas, tables, etc. ▼ (m is 1 to 4). A resin composition comprising an ortho diallylbiscyanate compound represented by the formula: 3. The resin composition according to claim 2, wherein the general formula [I] is an ortho diallyl biscyanate compound represented by ▲a mathematical formula, a chemical formula, a table, etc.▼. 4. N-substituted unsaturated imide compounds and the general formula [I] ▲Mathematical formula, chemical formula, table, etc.▼[I] [In the formula, X is none, -CH_2-, ▲Mathematical formula, chemical formula,
There are tables, etc. ▼ (R_1 and R_2 are lower alkyl groups, perfluoroalkyl groups, or hydrogen, and may be the same or different.), -O
-, -CO-, -COO-, -S-, -SO_2-, ▲
There are mathematical formulas, chemical formulas, tables, etc. ▼ (m is 1 to 4). A composition characterized by containing an ortho diallylbiscyanate compound represented by: 5. The composition according to claim 4, wherein the N-substituted unsaturated imide compound is an N,N'-substituted bismaleimide compound. 6. The N-substituted unsaturated imide compound has the following formula [II] ▲ Numerical formula, chemical formula, table, etc. ▼ [II] [In the formula, R_1 and R_2 are the same as above. Also,
D is a divalent organic group having an ethylenically unsaturated double bond. ] The composition according to claim 4, which is an aromatic ether unsaturated bisimide compound represented by the following. 7. General formula [ I ] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [ I ] [In the formula, X is none, -CH_2-, ▲ Numerical formula, chemical formula,
There are tables, etc. ▼ (R_1 and R_2 are lower alkyl groups, perfluoroalkyl groups, or hydrogen, and may be the same or different.), -O
-, -CO-, -COO-, -S-, -SO_2-, ▲
There are mathematical formulas, chemical formulas, tables, etc. ▼ (m is 1 to 4). ] and the general formula [III] ▲ There are numerical formulas, chemical formulas, tables, etc. ▼ [III] [In the formula, X is the same as above. Also, Y_1 and Y_
2 is hydrogen, lower alkyl group, glycidyl ether group,
▲There are mathematical formulas, chemical formulas, tables, etc.▼(R', R'', R'
'' is any one of CF_3, C_2F_5, C_3F_7, and may be the same or different from each other.), and may be the same or different from each other. A composition characterized in that it is an ortho-diallyl bisphenol derivative represented by the formula [III]. , X is none, -CH_2-, ▲ mathematical formula, chemical formula,
There are tables, etc. ▼ (R_1 and R_2 are lower alkyl groups, perfluoroalkyl groups, or hydrogen, and may be the same or different.), -O
-, -CO-, -COO-, -S-, -SO_2-, ▲
There are mathematical formulas, chemical formulas, tables, etc. ▼ (m is 1 to 4). 8. The composition according to claim 7, which is an ortho diallyl bisglycidyl ether compound represented by the following formula. 9. A monomer selected from (A) a polyfunctional epoxy compound, (B) a compound containing an N-substituted unsaturated imide group, (C) a phenol-aldehyde condensate, (D) a poly-para-hydroxystyrene. (E) General formula [I] ▲Mathematical formula, chemical formula, table, etc.▼[I] [In the formula, X is none, -CH_2-, ▲Mathematical formula, chemical formula,
There are tables, etc. ▼ (R_1 and R_2 are lower alkyl groups, perfluoroalkyl groups, or hydrogen, and may be the same or different.), -O
-, -CO-, -COO-, -S-, -SO_2-, ▲
There are mathematical formulas, chemical formulas, tables, etc. ▼ (m is 1 to 4). ] A laminate comprising a composition comprising an ortho-diallyl biscyanate compound represented by: