JPS6322853A - Siliconephenolic compound composition and use thereof - Google Patents

Abstract

PURPOSE:To obtain the titled composition outstanding in adhesivity to metallic insert and crack and heat resistances, by blending a specific siliconephenolic compound, epoxy compound, addition type inside compound, isocyanate compound, etc. CONSTITUTION:The objective composition comprising (A) a siliconephenolic compound containing characteristic group of formula III prepared by reaction on heating between i) a novolak type phenolic compound having recurring unit of formula I (R is H or lower alkyl) and ii) a second compound of formula II (R1 is H, OH, methyl or phenyl; Y is functional group reactive with phenolic hydroxyl group; X is 0-1,000), (B) an epoxy compound, (C) an addition type imide compound, (D) an isocyanate compound, and (E) hexamethylenetetramine. This composition is used as a sealing compound for resin-sealed type semiconductor devices.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Application of the Invention] The present invention relates to a novel silicone phenolic compound, a method for producing the same, a thermosetting resin composition containing the compound, and a cured product thereof.

[Prior art]

Conventionally, in the field of semiconductor products and electrical equipment, thermosetting materials have been used as sealing materials and insulating materials, which have excellent adhesion and adhesion to metal inserts, as well as excellent crack resistance and heat resistance. There is a strong demand for low stress resins.

For these purposes, epoxy resins, urethane resins, addition type imide compounds, etc. have been mainly used. However, all of these have problems in terms of the balance of adhesion with the metal insert, crack resistance, heat resistance, etc., and there has been a strong desire to develop a new material system.

[Purpose of the invention]

The present invention was conceived in view of the above-mentioned current situation, and an object of the present invention is to improve the adhesion of metal inserts (preventing water from entering from the interface), and to improve the crack resistance (flexibility) of molded cured products. The object of the present invention is to provide a material useful as a reactive crosslinking agent (curing agent) for various new thermosetting resins, which can provide a material composition with excellent K and heat resistance.

[Summary of the invention]

To summarize the present invention, the first invention of the present invention is an invention of a silicone phenolic compound, which has the following general formula I: [wherein R1 is the same or different, H,0H1aFLRo
n, lower alkyl, lower alkoxy, cyanoal, phenyl, vinyl, allyl, Flol, Br%
HB4, BTl, and R3 are the same or different, lower alkyl, vinyl, allyl, IF, C/.

Br, m% p is 1 to 10000, T
's q represents 1 to 1000, and l represents 0 to 5.

] It is expressed as

Further, a second invention of the present invention is an invention of a method for producing a silicone phenolic compound represented by the general formula I, which comprises a novolac type phenol resin (4) and one or more reactive functional groups at the terminal. The siloxane compound CBI having the following characteristics is heated and reacted with the siloxane compound CBI.

Moreover, the third invention of the present invention is an invention of a thermosetting resin composition, which has the above general formula! It is characterized by containing a silicone phenol compound, an epoxy compound, an addition type imide compound, an isocyanate compound, or hexamethylenetetramine.

Further, a fourth invention of the present invention is an invention of a cured resin product, which comprises a silicone phenol compound represented by the general formula (1) and an epoxy compound, an addition type imide compound, an incyanate compound, or hexamethylene. Tetramine.

A fifth invention of the present invention is an invention of a curing agent for an epoxy resin or an addition type imide resin, which is characterized in that the silicone phenol compound represented by the general formula 1 is used as an active ingredient.

In the present invention, the novolac type phenolic resin particles include phenol, o, m, p cresol, o, to,
What is usually called a phenol novolak resin, which is obtained by reacting p-xylenol, allylphenol, or their derivatives with formaldehyde in the presence of an acidic catalyst such as hydrochloric acid or oxalic acid, can be used.

In addition, examples of the siloxane compound having one or more functional groups at the end include, for example, the general formula (1): R R, -81-R, . . .
has the same meaning as the general formula 1 above. ] Examples include dimethylsilanediol, diethylsilanediol, diphenylsilanediol, diethyldimethoxycin, diethyldimethoxysilane, diphenyldimethoxysilane, dimethylsilane, diethylsilane, and diphenylsilane.

Further, general formula ■: [wherein, Ro has the same meaning as the above general formula I, and k is 0 to 1
Shows 0000. ] is the compound represented by υ, tetramethyldisiloxane, hexamethylenetrisiloxane, 1
-vinyl-5-hydroxytetramethyldisiloxane,
1,5-dihydroxyhexamethyltrisiloxane, 1
．． 5-dihydroxytetramethyldisiloxane, 1,3
-Polymethylhydrosiloxane and its oleic adducts such as dichlorotetramethyldisiloxane, 1,7-cyhydroxyoctylmethyltetrasiloxane, 1,7-cyhydroxyoctaethyltetrasiloxane, 1,7-cyhydroxyoctaptylsiloxane, etc. Examples include polymethylhydromethylcyanopropylsiloxane copolymers, polymethylhydromethyloctylsiloxane copolymers, polymethylhydromethylfluoromethylpropylsiloxane copolymers, and polymethylalkylsiloxanes such as polymethyloctylsiloxane.

The above-mentioned siloxane compounds are commercially available from Chisso, Shin-Etsu Chemical, Toshi Silicone, GK, etc.

The silicone phenolic compound 1 of the present invention can be easily obtained by simply heating (5) and CB).
Methanol, ethanol, methyl ethyl ketone, benzene, toluene, xylene, acetone, cellosolve acetate,
It can also be obtained from K by reacting with cellosolve acetate, N-methylpyrrolidone, dimethylformamide, dimethylacetamide, etc., which may be used alone or in combination. It is preferable that the reaction is carried out in a mixing ratio of 103) = 1/n, o1 to 1.00. Among the obtained silicone phenolic compounds (1), those having a molecular weight of 500 to 50,000 are useful.

The silicone phenol compound obtained by the above method is characterized by having a softening point ranging from a liquid at room temperature to 200°C.

The silicone phenolic compound obtained by the present invention can be easily cured by adding an appropriate amount of a conventionally known curing agent (including accelerator) for phenolic resins, such as hexamethylenetetramine, and has excellent electrical properties, heat resistance, and potency. A cured resin with excellent properties and moisture resistance. Also, epoxy resin,
It is effective as a crosslinking agent (curing agent) for thermosetting resins such as addition-type imide resins, urea resins, urethane resins, and melamine resins.

The blending ratio for the thermosetting resin varies depending on its purpose and use and is not particularly limited, but preferably the reactive functional groups of the thermosetting resin and the hydroxyl groups of the silicone phenolic compound are stoichiometric. It can be used variably over a wide range, centering on the ratio.

These applications include festivals, paints, prepregs, laminates such as printed circuit boards, coils and semiconductor products (:[
It can be used in a wide range of applications, including molding materials such as sealants such as O, I, and 8 parts).

When the silicone phenol compound of the present invention is added with a known epoxy compound, it becomes a cured product with excellent heat resistance and moldability.

Examples of the epoxy compound in the present invention include glycidyl ether of bisphenol A, butadiene dieboxide, 3. -mono-epoxycyclohexylmethyl- (so'
-epoxy)cyclohexane carboxylate, vinylcyclohexene dioxide, 4,4'-di(1,2-epoxyethyl)diphenyl ether, 2,2-bis(5
, A-epoxycyclohexyl)propane, glycidyl ether of resorcin, diglycidyl ether of phloroglucin, diglycidyl ether of methylphloroglucin, bis-(2,5-epoxycyclohexyl) ether, 2-(L'-epoxy) Cyclohexane-5,5-
spiro(5,4-epoxy)cyclohexane7-m-dioxane, bix-(5,j-epoxy-6-methylcyclohexyl)azibe), N,11'-m-phenylenebis(4,5-epoxy-1 , bifunctional epoxy compounds such as 2-cyclohexanedicarboximide, p-aminophenol triglycerides, cidyl derivatives, polyallyl glycidyl ether, 1,5,5-toIJ (1,2-epoxyethyl)benzene, 2° 2', A, J'-
Tetraglycidoxybenzophenone, polyglycidyl ether of phenol formaldehyde novolak resin,
Tri- or higher functional epoxy compounds such as triglycidyl ether of glycerin and triglycidyl ether of trimethylolpropane, halogenated epoxy compounds such as brominated epoxy, or hydantoin epoxy compounds are used.

Moreover, the silicone phenol compound of the present invention can be obtained by the following formula: [wherein, R7 represents H or OH8, and R1 represents a divalent organic group. It can also be used in combination with a known bismaleimide compound represented by the following formula, and a cured product with excellent heat resistance can be obtained. Examples of the bismaleimide compound include N.

W-ethylene dimaleimide, N,N'-ethylenebis[2-methylmaleimide), N,N'-trimethylene dimaleimide, NIN'-tetramethylene dimaleimide, N,N'-hexamethylene dimaleimide, N ,N'
-hexamethylenebis[2-methylmaleimide], Nt
l? '-Dodecamethylene dimaleimide, N, N'-m-
722 dimaleimide, N,N'-p-furin2 dimaleimide, NUN'-(oxy-p-phenylene)
Simaleimide, N, N'-(methylene-p-)unisine) simalimide, MIN'-(methylene-p-
) Bis[2-methylmaleimide],”,N'
-2, A-tolylene dimaleimide, L”-2+6-)
! J rangemaleimide s kJtW -m-xylylene cymaleimide, N, N'-p-xylylene cymaleimide, IJ, N'-oxyglobylene dimaleimide,
Examples include N,N'-ethylenebis(oxypropylenemaleimide) and a,N'-oxydiethylene simalimide, which may be used alone or in combination of two or more.

The silicone phenol compound of the present invention has heat resistance,
It also becomes a cured product with excellent moldability.

In the present invention, polyfunctional incyanate compounds include methane diisocyanate, butane-1,1-diisocyanate, ethane-1,2-diisocyanate, and butane-1,2-diisocyanate.
1,2-diisocyanate, transvinylene diisocyanate, propane-1,3-diisocyanate, butane-1,4-diisocyanate, 2-butene-1,4-
Diisocyanate, pentane-1,5-diisocyanate, hexane-1,6-diincyanate, heptane-
1,7-diisocyanate, octane-1,8-diisocyanate, nonane-1,9-diisocyanate, decane-1,10-diisocyanate, dimethylsilane diisocyanate, diphenylsilane diisocyanate, ω
, /-1,3-dimethylbenzene diisocyanate, ω
, Ql'-1゜4-dimethylbenzene diisocyanate, ω, (/-1,3-dimethylcyclohexane diisocyanate, ω, a/-1.4-dimethylcyclohexane diisocyanate, ω, tJ-1.a-dimethylnaphthalene diisocyanate ,ω,i/-1.5-dimethylnaphthalene diisocyanate, cyclohexane-1,5-
Diisocyanate, cyclohexane-1,4-diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, 1,3-phenylene diisocyanate, 1
．． 4-) Unilene diisocyanate, 1-methylbenzene-2,4-diisocyanate, 1-methylbenzene-
2,5-diisocyanate, 1-methylbenzene-2,
6-Diisocyanate, 1-methylbenzene-5゜5-
Diisocyanate, diphenyl ether-4,4'-diisocyanate, diphenyl ether-2,41-diisocyanate, naphthalene-1,4-diisocyanate, naphthalene-1,5-diisocyanate, biphenyl-4,4'-diincyanate, 3. dimethylbiphenyl-4,4'-diisocyanate, 2,5'-dimethoxybiphenyl-4,J'-diisocyanate, diphenylmethane+4, 41-diisocyanate, 3,
3'-dimethoxydiphenylmethane-4,4'-diisocyanate, 4,4'-dimethoxydiphenylmethane-
5-'-diisocyanate, diphenyl sulfide
4゜4'-diisocyanate, diphenylsulfone-4
, bifunctional incyanate compounds such as 4'-diisocyanate, polymethylene polyphenylisocyanate,
Triphenylmethane triisocyanate, tris(4-
Incyanate phenyl) thiophosphate, 515
Isocyanate compounds having 5 or more functional groups such as 'l'l''-diphenyl meta/tetribucyanate are used.Also, dimers of these isocyanate compounds,
S-mers can also be used.

Various catalysts that are important for improving curability can be added to these resin compositions.

Examples of such catalysts include tertiary amines such as tetramethylbutanediamine, tetramethylhexanediamine, triethylenediamine, and dimethylaniline, oxyalkylamines such as dimethylaminoethanol, triethanolamine, and dimethylaminopentanol, and tris(dimethyl There are amines such as (aminomethyl)phenol and N-methylmorpholine.

Also, cetyltrimethylammonium bromide, cetyltrimethylammonium chloride, dodecyltrimethylammonium iodide, trimethyldodecylammonium chloride, benzyldimethyltetradecylammonium chloride, penzyldimethylpalmitylammonium chloride, allyldodecyltrimethylammonium bromide, benzyldimethylstearylammonium bromide , stearyltrimethylammonium chloride, benzyldimethyltetradecylammonium acetate, and other quaternary ammonium salts. 2
-ethylimidazole, 2-undecylimidazole,
2-heptadecylimidazole, 2-methyl-4-ethylimidazole, 1-butylimidazole, 1-propyl-2-methylimidazole, 1-benzyl-2-butylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl -2-undecylimidazole, 1-cyanoethyl-2-phenylimidazole, 1
-Azi/-2-methylimidazole, 1-azine-2-
Imidazoles such as undecylimidazole, triphenylphosphine tetraphenylborate, tetraphenylphosphonium tetraphenylborate, triethylaminetetraphenylborate, N-methylmorpholinetetraphenylborate, pyridinetetraphenylborate, 2-ethyl-4-methylimidazoletetraphenyl Also useful is the tetraphenylboron salt of the borate, 2-ethyl-1,4-dimethylimidazoletetraphenylphorate.

In addition, various known additives may be added depending on the above-mentioned purpose and use. For example, inorganic fillers include zircon, silica, fused silica glass, alumina, aluminum hydroxide, glass, calcium silicate, gypsum, calcium carbonate, magnesite, clay,
Examples include Merck, mica, asbestos, lead oxide, zinc white, titanium white, and molybdenum disulfide. In addition, release agents such as higher fatty acids and waxes, and coupling agents such as epoxysilane, vinyl silane porane compounds, and alkoxy titanate compounds can be used as necessary. Furthermore, flame retardant materials made of antimony, phosphorus compounds, etc. can be used.

[Embodiments of the invention]

EXAMPLES Hereinafter, the present invention will be illustrated by giving Examples, but the present invention is not limited thereto.

Examples 1 to 5 As a phenolic compound, a condensate of novolac type phenol and formaldehyde (average molecular 1i, 37s
) Too weight part of hydroxyl group-terminated polydiphenylsiloxane compound ('pe-oa
o: Chisso Corporation) 5, 10, 20, 50.40 parts by weight were added separately and heated at 120°C to 180°C for 2 to 3 hours.
5 of [(a) to (e) in Table 1] by heating reaction for a period of time
Five types of silicone phenolic compounds were obtained.

Examples 6 to 10 As a phenolic compound, a condensate of novolac type phenol and formaldehyde (average molecular Jim: 41
0) Add a methylol group-terminated polydimethylsiloxane compound (PS-197) as a siloxane compound to 100 parts by weight.
: Manufactured by Chisso Corporation) 10.20. 50.40.50 parts by weight were added separately and reacted at 120 to 180°C for 1 to 2 hours to obtain five types of silicone phenolic compounds shown in Table 1.

Examples 11-12 As a phenolic compound, a condensate of novolak-type ortho-cresol and formaldehyde (average molecular weight: aso
)10 parts by weight of polymethylhydrosiloxane (PS-120: manufactured by Chitsuso Corporation) as a siloxane compound.
．． Add 20 parts by weight separately to 150-200
℃ for 1 to 2 hours to produce 4(6)-2 listed in Table 1.
Various silicone phenolic compounds were obtained.

Examples 13 to 16 Condensate of novolac type phenol and formaldehyde as phenolic compound (average molecular weight: J50) 1
00 parts by weight, as a siloxane compound, silicone oil KF-96 (manufactured by Shin-Etsu Chemical Co., Ltd.), KIF-54
(manufactured by Shin-Etsu Chemical Co., Ltd.) by adding 5.10 parts by weight,
A heating reaction was carried out at 150 to 200° C. for about 1 to 2 hours to obtain four types of silicone phenol compounds M to (a) listed in Table 1.

Example 17 Silicone phenolic compounds obtained in Examples 1 to 5)
- (E) to 100 parts by weight each, 7 parts by weight of hexamethylenetetramine, 1 part by weight of zinc stearate as a mold release agent, 180 parts by weight of silica powder as a filler,
After blending 90 parts by weight of clay powder, 1 part by weight of epoxysilane IBM-Ass (manufactured by Shin-Etsu Chemical Co., Ltd.) as a coupling agent, and 1 part by weight of carbon black as a coloring agent, the mixture was roll-kneaded at 80 to 95°C for 10 minutes. After cooling, a molding material composition was obtained.

Next, transfer molding was performed at 150 to 160° C. for 2 minutes to prepare specimens for measuring each characteristic.

The bending strength of the above cured product is 1000 to 1200 Yu/
The retention rate of bending strength after 180°C SO was 90 to 100 degrees.

In addition, the water absorption rate of the cured product after immersion in water for 24 hours was 15 to 0.
It was 6chi.

Example 18 Silicone phenolic compounds obtained in Examples 6 to 16 (
) to 70 parts by weight, respectively, and novolac type epoxy DInN-4513 (as the epoxy resin)
Dow Chemical Company) 100 parts by weight, 1 part by weight of Hoechstwax E as a mold release agent, 29 parts by weight of quartz powder as a filler.
0 heavy land parts, 250 parts by weight of fused silica glass powder, 2 parts by weight of triethylamine tetraphenylborate as a curing accelerator, and epoxy sila/KBM 5 as a coupling agent.
05 (manufactured by Shin-Etsu Chemical Co., Ltd.) and 1 part by weight of carbon black as a coloring agent were blended, roll-kneaded at 60 to 70°C for 10 minutes, cooled, and pulverized to obtain a molding material composition. Next, using these molding powders, (a) molded products (
Glass transition point and Young's modulus (after curing), ('b) heat cycle test, (e) stress measurement test for tightening, and (d) high temperature volume resistivity test of molded product (after curing) were conducted. However, the molding process was performed at 180°C for 2 minutes and then post cured at 180°C for 6 hours.

Heat cycle test was conducted using 5x511III MO8 type LE.
I-manufactured products (20 pieces each) were prepared and repeatedly subjected to a thermal shock test in which they were immersed in an oil bath at 150°C for 2 minutes and then immediately immersed in liquid nitrogen at -196°C for 2 minutes. Tightening stress was measured by modeling the stress generated when transfer molding was performed using a molding material. The model is a steel cylinder (outer diameter 10φ, thickness α5111m).
% height 20. ) and pasted the strain gauge on the inside of the
Molded. The thickness of the resin is 10 m''C.

After molding, the stress generated in the circumferential direction was determined from the amount of deformation of the steel. Further, the glass transition temperature, which is a criterion for determining heat resistance, was measured according to A8TM D-696. The results are shown in Table 2 together with comparative examples.

Examples 19 to 21 Silicone phenolic compound PI obtained in the example, 100 parts by weight of tolylene diisocyanate (TD technology manufactured by Sumitomo Bayer) as an isocyanate compound, mold release 1 part by weight of stearic acid as a filler, 290 parts by weight of quartz powder as a filler, 250 parts by weight of fused silica glass powder, 3 parts by weight of hexamethylenetetramine as a hardening accelerator, and epoxysilane IBM-505 (manufactured by Shin-Etsu Chemical Co., Ltd.) as a coupling agent. ) 2 parts by weight,
Adding 1 part by weight of carbon black as a coloring agent, 60
Roll kneading was carried out at ~70°C for 10 minutes to obtain a molding material composition. Next, using these molding materials, 170°C, 3
Various cured products (test pieces) were prepared in the same manner as in Example 18 by molding for minutes. The results are listed in Table 5.

Examples 22 to 24 Silicone phenolic compounds obtained in Examples
, 70 parts by weight of the addition type polyimide resin, 10 parts of N,N'-(methylene-p-phenylene) simaleimide, 1 part of stearic acid as a mold release agent, and 1 part of stearic acid as a filler, and quartz powder as a filler. 290 parts by weight,
250 parts by weight of fused silica glass powder, 3 parts by weight of hexamethylenetetramine as a hardening accelerator, 2 parts by weight of epoxysilane IBM-505 (manufactured by Shin-Etsu Chemical Co., Ltd.) as a coupling agent, and 1 part by weight of carbon black as a coloring agent, The mixture was kneaded under the same conditions as in Examples 19 to 21 to prepare specimens for characteristic testing of each building.

The results are listed in Table 3.

Examples 25-26 As a phenolic compound in 500 ml of methyl ethyl ketone, as a siloxane compound for 100 parts by weight of a condensate of novolac type pt-butylphenol and formaldehyde (average molecular weight 475): l-080, P
20 parts by weight of each of S-197 were added separately, heated, and reacted under reflux of methyl ethyl ketone for 3 hours to obtain two types of silicone phenol compounds (face state).

According to the results in Tables 2 and 5, we decomposed the resin of molded products with heat cycle defects with hot concentrated sulfuric acid at 200°C and analyzed the causes of the defects. Cracks were occurring. Some of the packages were broken.

〔Effect of the invention〕

As is clear from the above examples, by using the silicone phenol compound of the present invention, heat resistance,
It has a remarkable effect of being able to provide a cured resin product with excellent crack resistance.

Claims (1)

[Claims] 1. A repeating unit represented by the following general formula (A): ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(A) (in the formula, R represents hydrogen or a lower alkyl group) a novolak-type phenolic compound having
The following general formula (B): ▲There are mathematical formulas, chemical formulas, tables, etc.▼... (B) (In the formula, R_1 is the same or different, H, hydroxyl group, methyl group or phenyl group, Y is reactive with phenolic hydroxyl group The following general formula [
I〕：▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・〔I
] [In the formula, R and R_1 have the same meanings as the above formulas (A) and (B)] A silicone phenol compound containing a characteristic group, an epoxy compound, an addition type imide compound, an isocyanate compound or hexamethylenetetramine. 2. In a resin-encapsulated semiconductor device encapsulated with a synthetic resin encapsulant, the encapsulant has the following general formula (A): ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(A) A novolak-type phenol compound having a repeating unit represented by (in the formula, R represents hydrogen or a lower alkyl group),
The following general formula (B): ▲There are mathematical formulas, chemical formulas, tables, etc.▼... (B) (In the formula, R_1 is the same or different, H, hydroxyl group, methyl group or phenyl group, Y is reactive with phenolic hydroxyl group (x represents a number from 0 to 1000) with the following general formula
I〕：▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・〔I
] [In the formula, R and R_1 have the same meanings as the above formulas (A) and (B)] A silicone phenol compound containing a characteristic group, an epoxy compound, an addition type imide compound, an isocyanate compound or hexamethylenetetramine as an active ingredient.