JPH02180952A - Thermosetting resin composition - Google Patents

Abstract

PURPOSE:To obtain a composition excellent in processability, heat resistance, humidity resistance, electrical insulation properties and low stress properties by mixing a partially allyl-etherified phenolic novolac with a polymaleimide compound and a specified silicone resin. CONSTITUTION:A thermosetting resin composition comprising a partially allyl- etherified phenolic novolac (A), a polymaleimide compound (B) having at least two maleimide groups in the molecule and a silicone resin (C) of formula I or II (wherein R1 and R2 are each a methyl or a phenyl; R3 is H, an amino or an epoxy functional group; and l and m are each 0-400). In the above resin composition, the components may be in the form of a prepolymer prepared by prereacting phenolic novolac resin (A) modified with silicone resin (C) with polymaleimide resin (B). In this way, the moldability can be further improved, and a morphologically uniform cured product can be obtained to enhance the featured of this composition.

Description

Detailed Description of the Invention <Industrial Field of Application> The present invention relates to a resin composition for molding, and more specifically to a molding resin composition for use in electronic molding such as semiconductors having excellent processability, moisture resistance, heat resistance, low stress property, and electrical insulation properties. The present invention relates to a molding resin composition used for sealing parts, etc.

<Prior Art and its Problems> Conventionally, epoxy resins have been used as molding resin compositions used for encapsulating electronic components such as semiconductors.

This epoxy resin sealing is economically advantageous compared to hermetic sealing methods using glass, metal, or ceramic, and is therefore widely put into practical use. However, in recent years, the usage conditions for sealing materials have tended to become stricter, and in particular, the heat resistance and moisture resistance of the materials have become important characteristics. Therefore, in recent years, resin compositions with excellent heat resistance and moisture resistance have been proposed.However, as semiconductor devices tend to become larger and more highly integrated, semiconductors are encapsulated with conventional epoxy resin compositions. In such cases, thermal stress caused by the difference in linear expansion coefficient between the chip or lead frame and the encapsulating resin may cause problems such as cracks in the passivation film or encapsulating resin, or breakage of the bonding wire. became. Therefore, there has been a desire for a resin composition that has excellent heat resistance, moisture resistance, etc., and also has excellent low stress properties.

Measures to Solve the Problems> Against this background, the present inventor has conducted intensive studies on resin compositions with excellent processability, heat resistance, moisture resistance, electrical insulation properties, low stress properties, etc., and has found a specific The present inventors have discovered that a resin composition containing a novolac resin, a maleimide compound, and a silicone resin is suitable for the above purpose, and have completed the present invention.

That is, the present invention provides a thermosetting resin comprising a partially allyl etherified phenolic novolak resin (A), a polymaleimide compound (B) having two or more maleimide groups in the molecule, and a silicone resin (C'). The present invention relates to a synthetic resin composition.

The present invention will be explained in detail below.

The partially allyl etherified phenolic novolac resin (A) used in the present invention is an unsubstituted phenol or a phenol substituted with an alkyl group, an alkenyl group, an aryl group, an aralkyl group, or a halogen i atom, etc. Specifically, cresol, ethylphenol, isopropylphenol, butylphenol, octylphenobenzylphenol, chlorophenol, bromophenol, xylenol, methylbutylphenol (including isomers) or two or more of them together with formaldehyde, furfural, and acrolein. It is obtained by allyl etherification of a part of the hydroxyl groups of a novolak resin, which is obtained by condensing aldehydes such as the like by a known method and usually has an average number of nuclei of 2 to 15.

Allyl etherification is carried out, for example, by combining the novolac resin with an allyl halide such as allyl chloride, allyl bromide, or allyl iodide under conditions such that the number of moles of allyl halide is smaller than the number of moles of hydroxyl groups in the novolac resin. , by reacting in the presence of an alkali. In particular, it can be easily obtained by using allyl bromide or by carrying out an allyl etherification reaction in an aprotic polar solvent. The phenol novolak resin used is preferably a substituted phenol novolak resin, especially O-
Cresol novolac resin is preferred because it has excellent moisture resistance.

Here, the value of the ratio of unsubstituted hydroxyl groups to allyl etherified hydroxyl groups is preferably 1/0.2 to 9, more preferably 1/0.8 to 6. When this ratio is outside the above range, the compound contains two or more maleimide groups in the molecule, which is curable or heat-resistant.

(In the formula, R represents a hydrogen atom or a lower alkyl group.) Specific examples thereof include N,N'-bismaleimide compounds such as N,N'-diphenylmethane bismaleimide, N,N'-phenylene bismaleimide, , N, N'-
Diphenyl ether bismaleimide, N, N'-diphenylsulfone bismaleimide [do, N, N'-dicyclohexylmethane bismalei [do, N, N'-xylene bismaleimide], N, N'-tolylene bismaleimide, N ,
N' -xylylene bismalei [do, N, N'-diphenylcyclohexane bismalei [do, N, N' -4
2chlorodiphenylmethane bismalei [do, N, N'-
diphenylcyclohexane bismaleimide, N, N'-
Diphenylmethane bismethylmaleimide, N,N'-diphenyl ether bismethylmaleimide, N,N'-diphenylsulfone bismethylmaleimide (each including isomer), N.

N'-ethylene bismaleimide, N, N'-hexamethylene bismaleimide, N, N'-hexamethylene bismethylmaleimide, and the terminals obtained by adding these N, N' bismaleic acid compounds with diamines are N,
Examples include prepolymers having a N'-bismaleimide skeleton, and maleimides or methylmaleimides of aniline/formalin polycondensates. In particular, N,N'-diphenylmethane bismaleimide, N,N'-diphenyl ether bismaleimide, etc. preferable.

As the silicone resin 0 used in the present invention,
It is represented by the following general formula or 1).

(Ri and Rz each independently represent a methyl group or a phenyl group, '%R3 represents a hydrogen atom or a functional group containing an amide group or an epoxy group, and m is 0 to 40
Represents the number 0. ) (Ri and Rt each independently represent a methyl group or a phenyl group, R5 represents a hydrogen atom or a functional group containing an amide group or an epoxy group, and m is 0 to 400
represents the number of ) Since the compound of formula (1) tends to gel, the compound of formula (■) is preferable.

Furthermore, two or more of these silicone resins may be used in combination.

In particular, the combination of a hydrogen atom in the above general formula and a functional group containing an amine 7 group is preferably used because it has excellent mechanical properties and low stress properties.

Examples of silicone resins in which R4 is a hydrogen atom include X-21-7628 manufactured by Shin-Etsu Silicone Co., Ltd., and examples of silicone resins in which R5 is a functional group containing an amino group (hereinafter referred to as amine7-containing silicone resin) include Shin-Etsu Silicone. Company-made X
-22-161A or 5F-8 manufactured by Toshi Silicone Co., Ltd.
417, etc., and examples of those in which R5 is a functional group containing an epoxy group (hereinafter referred to as epoxy group-containing silicone resin) include BX16-855B manufactured by Toshi Silicone Co., Ltd.

The molecular weight is arbitrary, but the molecular weight is 500 to 300.
A value of about 00 is preferably used.

These silicone resins include partially allyl etherified phenol novolacs (A) and polymaleimide compounds (
Although ξ can be used by simply mixing it with B), it is preferable to react it with the partially allyl etherified phenol novolak (A) or the polymaleide compound (B) in advance.

The reaction between the hydrogen group-containing silicone resin and the allyl group in the partially allyl etherified phenolic novolak, which is component (A), is a hydrosilylation reaction, which can be easily carried out using a platinum-based catalyst according to a conventional method. Can be done.

Further, the epoxy group-containing silicone resin can be easily reacted with the hydroxyl group of the partially allyl etherified phenol novolafuku, which is the component (A), in the presence of a basic catalyst (eg, idazoles).

Furthermore, the silicone resin containing a[no] group can be easily reacted with the maleimide group of bismaleido, which is the component (B) in the composition of the present invention.

By carrying out these reactions, it is possible to prevent silicone from bleeding from the cured product and to obtain a low stress thermosetting resin composition in which silicone is morphologically uniformly dispersed in the cured product.

The quantitative ratio of each component in the resin composition of the present invention can be appropriately selected depending on the intended use, desired heat resistance, and the like.

However, in terms of quantity, the ratio of the double bonds of the polymaleimide compound (B) to the double bonds of the partially allyl etherified phenolic novolac resin (A) to the hydroxyl groups is 0.4 to 8. preferable.

If the amount of either component (A) or (B) exceeds the above range, curability and heat resistance will decrease.

In addition, the quantitative proportion of the silicone resin which is the component (C) is 8 to 80% of the total amount of N in the resin components (phenolic novolac resin + 0 polymaleimide compound + silicone resin Ω).
It is desirable to blend the components so that the amount is less than this, and the stress-lowering effect is poor if the amount is less than this, and the effect of reducing stress properties is poor if the amount is less than this, and the hardenability and heat resistance are reduced if the amount is more than this.

The phenolic novolak resin modified with silicone resin 0 and the polymaleimide resin (c) in the resin composition according to the present invention can be reacted in advance to form a prepolymer. As a result, moldability becomes even better, and a cured product that is morphologically uniform can be obtained, making it possible to further enhance the features of the present invention.

Describing the method of thermosetting the resin composition of the present invention,
Although it can be easily cured without a catalyst, it can be cured even more easily by using a curing accelerator. Examples of such catalysts include organic phosphine compounds such as tributylphosphine, tri-4-methylphenylphosphine, tri-4-methoxyphenylphosphine, tributylphosphine, trioctylphosphine, tri-2-cyanoethylphosphine, benzoyl peroxide, di- Radical polymerization initiators such as t-butyl peroxide, dicumyl peroxide, lauroyl peroxide, acetyl peroxide, methyl ethyl ketone peroxide, cyclohexanone peroxide, t-butyl hydroperoxide, azobisisobutyronitrile, and other tributyl amines, triethylamine,
Examples include tertiary amines such as triamylamine, quaternary ammonium salts such as benzyltriethylammonium chloride and benzyltrimethylammonium hydroxide, imidazoles, boron trifluoride complexes, and transition metal acetylacetonates. It is not limited to.

Among these, organic phosphine compounds and imidazoles are particularly preferred.

Further, in order to adjust the curing speed, it is also possible to use a known polymerization inhibitor in combination. To illustrate, 2.6-Gt
-butyl-4-methylphenol, 2.2'-methylenebis(4-ethyl-6-t-butylphenol), 4.
Phenols such as 4'-methylenebis(2,6-di-t-butylphenol), 4.47-thiobis(8-methyl-6-t-butylphenol), hydroquinone monomethyl ether, hydroquinone, catechol, pt
- Polyhydric phenols such as butylcatechol, 2.5-di-t-butylhydroquinone, methylhydroquinone, t-butylhydroquinone, pyrogallol, phenothiazine compounds such as phenothiazine, benzophenothiazine, acetamidophenothiazine, N-nitrodiphenylamine, There are N-nitrosoanes compounds such as N-nitrosodimethylamine.

A known epoxy resin and epoxy curing agent may be used in combination with the resin composition of the present invention. Examples of epoxy resins include phenol, novolak epoxy resin derived from novolac resin which is a reaction product of phenols such as O-cresol and formaldehyde, phloroglycine, tris-(4-hydroxyphenyl)- Glycidyl ether compounds derived from trihydric or higher phenols such as methane, 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane, dihydric phenols such as bisphenol A1 bisphenol F, hydroquinone, resorcinol, or Diglycidyl ether compounds derived from halogenated bisphenols such as tetrabromobisphenol A, p-aminophenol, m
-A[nophenol, 4-aminometacresol, 6-
Aminometacresol, 4.4'-Sia [nodiphenylmethane, 8.8'-diaminodiphenylmethane, 4.4
'-Sia [nodiphenyl ether, 8.4'-Sia [nodiphenyl ether, 1,4-bis(4-7minophenoxy)benzene, l, 4-bis(8-aminophenoxy)benzene, 1,8-bis(4 -aminophenoxy)benzene, 1,8-bis(8-aminophenoxy)benzene, 2゜2-bis(4-aminophenoxyphenyl)propane, p-phenylenecyan, m-phenylenediamine, 2,4-toluene Cyanine, 2゜6-toluenecyanene, p-xylylene diamine, m-xylylene diamine, 1,4-cyclohexane bis(methylamine),
1. Amine-based epoxy resin derived from 8-cyclohexane bis(methylamine) etc., p-oxybenzoic acid,
Glycidyl ester compounds derived from aromatic carboxylic acids such as m-oxybenzoic acid, terephthalic acid, and isophthalic acid, hydantoin epoxy resins derived from 6,6-dimethylhydantoin, etc., 2,2-bis(8 ,4
-epoxycyclohexyl)propane, 2,2-bis[
4-(2,8-epoxypropyl)cyclohexyl]propane, vinylcyclohexene dioxide, 8.4-
Alicyclic epoxy resins such as epoxycyclohexylmethyl-8,4-niboxycyclohexanecarboxylate and other N.

N-diglycidylaniline and the like are used, and one or more of these epoxy resins are used.

Also, known epoxy resin curing agents can be used, such as novolak resins such as phenol novolak and cresol novolak, aromatic polyamines such as diaminodiphenylmethane and diaminodiphenylsulfone, and acids such as pyromellitic anhydride and benzophenonetetracarboxylic anhydride. Examples include anhydrides, but are not limited to these.

Moreover, an inorganic filler can be added to the resin composition of the present invention. This is especially essential when used for encapsulating semiconductors. Examples of inorganic fillers include silica powder, alumina, talc, calcium carbonate, titanium white, clay asbestos, mica, red iron oxide, glass TS bags, etc.
Particularly preferred are silica powder and alumina. The blending ratio of the inorganic filler when used for encapsulating a semiconductor needs to be 25 to 90% by weight, preferably 60 to 80% by weight, based on the total amount of the resin composition.

In the present invention, other natural waxes, synthetic waxes, higher fatty acids and their metal salts, or release agents such as paraffin, coloring agents such as carbon black, and coupling agents may be added as necessary. . Additionally, flame retardants such as antimony dioxide, phosphorus compounds, and brominated epoxy resins may be added.

! Brominated epoxy resins are particularly preferred for their flame effect.

<Effects of the Invention> The molding resin composition of the present invention is mainly used for sealing electronic components such as semiconductors. The resin composition is excellent in processability, heat resistance, moisture resistance, and electrical insulation, and in particular has lower stress than conventionally known heat-resistant resin compositions, making it an extremely useful resin composition as a sealing pressure material.

<Example> This will be explained below using examples.

The functional group-containing silicone resins used in Examples are as follows.

・8.8 Reference Example 1 0-Cresol novolac resin 2 with a softening point of 90°C was placed in a reactor equipped with a thermometer, stirrer, dropping funnel, and reflux condenser.
After charging 86 parts (2 equivalents) and 840 parts of dimethyl sulfoxide as a reaction solvent and completely dissolving the resin,
Add 41 parts (1.0 equivalents) of 7% caustic soda and stir well. While maintaining the temperature of the reaction system at 40"C, 80 parts (1.05 equivalents) of allyl chloride was added dropwise over 1 hour, and then the temperature was 50"C.
and hold at the same temperature for 6 hours. Next, after distilling off the dimethyl sulfoxide, 800 parts of methyl isobutyl ketone was charged, the resin was dissolved, and the inorganic salts were removed by water washing and filtration, and the furnace solution was concentrated to obtain an allyl group free from nuclear substituted allyl groups. conversion rate 60%, OH equivalent 2
262 parts of a reddish brown semi-solid resin of 7 LHl/eq was obtained. (AlN) Reference Example 2 [Silicone Modification] 100 parts of ALN obtained in Reference Example 1 and a platinum catalyst (1%
2 parts of PT-containing platinum black) and 88% of xylene as the reaction solvent.
After completely removing water from the system by azeotropic dehydration, 42 parts of silicone resin (a) was charged at this temperature for about 1 hour. After completely removing the catalyst, the silicone resin was concentrated by concentrating the furnace liquid. A modified product was obtained (referred to as modified product-(a))
.

Reference Example 8 [Silicone modification] N,N'-diphenylmethane bismaleimide (hereinafter referred to as BM
100 parts of I) and 869 parts of 1,4-dioxane as a reaction solvent were charged, the temperature was raised to 100°C, and the BMI
After completely dissolving the silicone resin, 58 parts of silicone resin was added dropwise over about 1 hour, and the mixture was kept at this temperature for 1 hour.

Dioxane was then distilled off to obtain a modified silicone product (referred to as modified product-(b)).

Reference Example 4 [Silicone modification] 100 parts of ALN obtained in Reference Example 1, 0.08 part of 4-methylimidazole, and xylene 881 as a reaction solvent.
After heating to 140° C. to completely dissolve the resin, 42 parts of silicone resin (c) was added dropwise over about 1 hour, and the mixture was kept at this temperature for about 2 hours. Then, xylene was distilled off to obtain a modified silicone product (referred to as modified product (C)).

Reference Example 6 [Silicone Modification] 88 parts of ALN obtained in Reference Example 1, 868 parts of modified product-(a) of 1424 kg BMI obtained in Reference Example 2, and 770 parts of 1,4-dioxane as a reaction solvent were charged. , 80
Heat to °C and dissolve.

Thereafter, 80 parts of silicone resin (b) was added to 80 parts of 1.
A solution dissolved in 4-dioxane was added dropwise over about 1 hour and held at 80''C for 1 hour.Dioxane was then distilled off to obtain a modified silicone product (referred to as modified product-(d)).

Reference Example 6 [Silicone Modification] The amount of modified product (a) was changed to 196 parts, 770 parts of 1,4-dioxane was changed to 800 parts, the amount of silicone resin (b) and 30 parts of 1. A silicone modified product was obtained in the same manner as in Reference Example 5 except that the amount of 4-dioxane was changed to 29 parts (referred to as modified product (e)).

Reference Example 7 [Prepolymerization] Modified product - (a) IOLIB and B? vlI 183i11
#! The mixture was charged into a J-shaped flask, heated to 130° C., melted and mixed, and stirred and reacted at this temperature for about 1 hour to obtain a prepolymer. This will be referred to as Prepolymer 8.

Reference Example 8 [Prepolymerization] 301 parts of the modified product and 100 parts of ALN were charged into a four-round flask, heated to 130°C, melted and mixed, and stirred and reacted at this temperature for about 1 hour to form a prepolymer. I got it. This will be referred to as prepolymer B.

Reference Example 9 [Prepolymerization] Modification of $-(a) into the modified product obtained in Reference Example 4-(C)
A prepolymer was obtained in the same manner as in Reference Example 7 except that . This will be referred to as prepolymer C.

Examples 1 to 8 Silicone modified products obtained in Reference Examples 5 to 9 - (e), (
d) Pre-poly Y-A%B, C and 0-resin compositions were melt-kneaded using heated rolls under the conditions of 50 to 120"C x 6 minutes according to the formulations shown in Table 1, cooled and pulverized to obtain each resin composition. These compositions were then mixed into 175'cX 70kq
Transfer molded under the conditions of /dx8 minutes, 200'c
After XShr post-curing, physical properties were evaluated. The results are shown in Table-2.

Comparative Example 1 0-cresol novolac type epoxy resin (epoxy equivalent: 195 f/eq), phenol novolac resin (OH
equivalent weight 110 f/eq), a curing accelerator, a filler, a mold release agent, and a coupling agent according to the formulation shown in Table 1 and kneaded in the same manner as in the examples to obtain a resin composition. Next, this was transfer molded under the conditions of 176° C. and 70 g/cd.

The results are shown in Table-2.

(Margins below) Procedural Amendment Heisei (Voluntary) June 6, 1999 Contents of the Amendment (1) On page 9, line 12 of the specification, the phrase “contains an epoxy group” has been changed to “contains a glycidyl group, Contains an epochine group such as an alicyclic epoxy group.''

Above 1゜2゜3゜Indication of the case 1989 patent application No. 091554 Name of the invention Thermosetting resin composition Person who makes amendments Relationship to the case Patent applicant address 4-5-33 Kitahama, Chuo-ku, Osaka 4゜Name (209) Representative of Sumitomo Chemical Industries, Ltd.
Hideo Mori

Claims (2)

[Claims] (1) A partially allyl etherified phenolic novolac resin (A), a polymaleimide compound (B) having two or more maleimide groups in the molecule, and the following general formula
A thermosetting resin composition comprising a silicone resin (C) represented by I. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I) (R_1 and R_2 each independently represent a methyl group or a phenyl group, R_3 represents a hydrogen atom or a functional group containing an amino group or an epoxy group, and l and m is 0~
Represents the number 400. ) (2) A partially allyl etherified phenolic novolac resin (A), a polymaleimide compound (B) having two or more maleimide groups in the molecule, and the following general formula
A thermosetting resin composition comprising a silicone resin (C) represented by I. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I) (R_1 and R_2 each independently represent a methyl group or a phenyl group, R_3 represents a hydrogen atom or a functional group containing an amino group or an epoxy group, and l and m is 0~
Represents the number 400. )