JPS63230728A - Resin composition for semiconductor sealing - Google Patents

Abstract

PURPOSE:To obtain the title composition excellent in processability, moisture resistance, heat resistance and electrical insulation, by mixing a specified phenol novolac resin with a polymaleimide compound, a silicone resin and silica. CONSTITUTION:A phenol novolac resin (A) having an allyl-etherified phenolic hydroxyl group and a phenolic hydroxyl group having a compound having at least one epoxy group added thereto in the molecule is obtained by subjecting a novolac resin (a) of the average number of nuclei of 2-15 and an allyl halide (b) to dehydrohalogenation and performing an addition reaction of the product with a compound (c) having at least one epoxy group in the molecule. A mixture of component A with a polymaleimide compound (B) having at least two maleimide groups in the molecule and 2-20wt.% silicone resin (C) is optionally mixed with 50-90wt.% silica (D) which has been optionally subjected to coupling treatment and coated with component C and, optionally, an epoxy resin, an epoxy curing agent, a mold release, a colorant, etc. (F).

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a resin composition for semiconductor encapsulation that has excellent processability, moisture resistance, heat resistance, and electrical insulation properties.

<Prior art and its problems> Conventionally, epoxy resins have been used as resin compositions for semiconductor encapsulation.

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.

Conventionally, thermosetting polyimide resin compositions have been used to obtain such high heat resistance, but in terms of processability, they require heating at high temperatures for long periods of time, and also have insufficient moisture resistance. Although epoxy resin compositions with improved heat resistance have excellent processability, they are insufficient in high heat resistance performance such as mechanical properties at high temperatures, electrical properties, and long-term heat deterioration resistance.

<Means for Solving the Problems> Against this background, the inventors of the present invention have conducted intensive studies on resin compositions with excellent processability, heat resistance, moisture resistance, electrical insulation properties, etc., and have found that certain resins and maleimide-based The inventors discovered that a resin composition containing the compound satisfies the above objectives and completed the present invention.

That is, the present invention provides a phenolic novolac resin (A) having in its molecule a phenolic hydroxyl group added with a compound having an allyl etherified phenolic hydroxyl group and at least one epoxy group, and a phenolic novolac resin (A) having two or more phenolic hydroxyl groups in the molecule. Polymaleimide compound (B) having a maleimide group of
, a resin composition for semiconductor encapsulation consisting of silicone resin (C) and silica (D).

Phenol-cervical novolafuku resin (A
) is an alkyl group, aryl group, aralkyl group, alkenyl group, or phenols substituted with a halogen atom, or unsubstituted phenols, specifically phenol,
Cresol, ethylphenol, isopropylphenol, butylphenol, octylphenol, nonylphenol, vinylphenol, impropenylphenol, phenylphenol, benzylphenol, chlorophenol, bromophenol, xylenol, methylbutylphenol, methoxyphenol, ethoxyphenol, α-methyl One or more types of phenols such as benzylphenol, β-phenylethylphenol, dihydroxybenzene (each including isomers), and bisphenol A, formaldehyde, furfural,
A novolak resin, which usually has an average number of nuclei of 2 to 15, obtained by condensing aldehydes such as acrolein and glyoxal by a known method, and an allyl halide such as allyl chloride, allyl bromide, and allyl iodide; The reaction method is obtained by reacting a predetermined amount of each compound having at least one epoxy group in the molecule by a known method. First, a novolac resin and a predetermined amount of allyl halide are subjected to a dehydrohalogenation reaction. After that, the remaining phenolic hydroxyl group is subjected to an addition reaction with a compound having at least one epoxy group in the molecule in the presence or absence of an alkali, or vice versa,
Alternatively, there is a method of simultaneously reacting allyl halide and a compound having at least one epoxy group in the molecule.Compounds having at least one epoxy group in the molecule include phenols, alcohols, nitrogen-containing compounds, etc. Glycidyl ethers of carboxylic acids, glycidyl esters of carboxylic acids, epoxidized products of peroxides of olefins, etc. can be used, but especially allyl glycidyl ether, vinyl phenyl glycidyl ether, isopropenylphenyl glycidyl ether, propenylphenyl glycidyl ether, allyl phenyl glycidyl ether, etc. Ether, propenylmethoxyphenylglycidyl ether,
Epoxy compounds having an olefinic double bond such as allyl methoxyphenyl glycidyl ether, isopropenyl methoxyphenyl glycidyl ether, glycidyl acrylate, and glycidyl methacrylate can be preferably used. Here, the value of the ratio of hydroxyl groups added with a compound having at least one epoxy group to allyl etherified hydroxyl groups is preferably 110.1 to 19, more preferably 110.2 to 9.

Further, the polymaleimide compound (B) is a compound containing two or more maleimide groups represented by the general formula (1) in the molecule.

In the formula, R represents a hydrogen atom or a lower alkyl group. ) Specific examples thereof include N,N'-diphenylmethane bismaleimide, N,N'-7 enylene bismaleimide, N,N'-bismaleimide, and N,N'-bismaleimide.
-diphenyl ether bismaleimide, N,N'-diphenylsulfone bismaleimide, N,N'-dicyclohexylmethane bismaleimide, N,N'-xylene bismaleimide, N,No-tolylene bismaleimide,
N,N'-xylylene bismaleimide, N,N'-diphenylcyclohexane bismaleimide, N,N'-dichlorodiphenylmethane bismaleimide, N,N'-diphenylcyclohexane bismaleimide, N,N'-diphenylmethane bismethylmaleimide, N,N'-diphenyl ether and smethylmaleimide, N,N'-diphenylsulfone bismethylmaleimide (each including isomer), N,N-ethylene bismaleimide, N,
N'-hexamethylene bismaleimide, N, N'-hexamethylene bismethylmaleimide, and these N, N
Examples include a prepolymer having an N, N'-bismaleimide skeleton at the end obtained by adding a '-bismaleimide compound and a diamine, and a maleimide or methylmaleimide of an aniline/formalin polycondensate. Especially N, No-diphenylmethane bismaleimide, N
, No-diphenyl ether bismaleimide is preferred.

Component (C) used in the present invention is an epoxy-modified silicone intermediate, an ayono-modified silicone intermediate, a carboxylic acid-modified silicone intermediate, a hydroxyl-modified silicone intermediate, a polyether-modified silicone intermediate, and a glycol-modified silicone intermediate. All modified silicon compounds such as silicon intermediates can be used, but are not particularly limited, but amino acids 11,300 to 50
From the viewpoint of overall balance, it is preferable to use the aminosilicon intermediate of No. 00.

The quantitative ratio of each component of the resin composition of the present invention is not limited. However, it is generally preferred that the ratio of the double bonds of the polymaleimide compound (B) to the double bonds of the phenolic novolac resin (A) be 0.4 to 3.

In addition, the quantitative proportion of the silicone resin (C) in the resin (phenolic novolac resin (A), polymaleimide compound (
2 to 20% by weight of B) + silicone resin (C)) is preferred, more preferably 3 to 15% by weight.

As the silica (D) used in the present invention, both fused silica and crystalline silica can be preferably used, and the blending ratio thereof is preferably 50 to 90% by weight, more preferably 60 to 80% by weight of the resin composition. Weight%.

Furthermore, by coating silica (D) with one or more silicone resins after treating it with a coupling agent, it is possible to prevent the silicone resin from eluting, further enhancing the characteristics of the present invention. be able to.

Known coupling agents can be used at this time, and specifically, vinyltrichlorosilane, vinyltriethoxysilane, vinyltris(β-methoxyethoxy)silane, γ-methacryloxypropyltrimethoxysilane, β -(3,4-epoxycyclohexyl)
Ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, vinyltriacetoxysilane, r
-Mercaptopropyltrimethoxysilane, T-aminopropyltriethoxysilane, r-C bis(β-hydroxyethyl)aminopropyltriethoxysilane, N
-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, r-(β-aminoethyl)aminopropyldimethoxymethylsilane, N-()santoxysilylbrobyl)ethylenediamine, N-(dimethoxymethylsilylisopropyl) ) ethylenediamine, methyltrimethoxysilane, methyltrimethoxysilane, N-β-(N
-vinylbenzylaminoethyl)-γ-aminopropyltrimethoxysilane, ry lolopropyltrimethoxysilane, hexamethyldisilazane, T-anilinopropyltrimethoxysilane, vinyltrimethoxysilane, γ
- Silane coupling agents such as mercaptopropylmethyldimethoxysilane, or isopropyltriisostearoyl titanate, isopropyltris(dioctylpyrophosphate)titanate, isopropyltri(N-aminoethyl-aminoethyl)titanate, tetraoctylbis(ditridecylphosphate) phyto) titanate, tetra(2,2-diallyloxymethyl-1-butyl)bis(ditridecyl)phosphite titanate,
Bis(dioctyl pyrophosphate) oxyacetate titanate, bis(dioctyl pyrophosphate)
Ethylene titanate, isopropyltrioctanoyltitanate, isopropyldimethacrylisostearoyltitanate, isopropyltridedecylbenzenesulfonyltitanate, isopropylisostearoyldiacryltitanate, isopropyltri(dioctylphosphate)titanate, isopropyltricumylphenyltitanate, tetraisopropylbis(dioctylphosphate) A titanate-based coupling agent such as phyto) titanate, and one or more of these coupling agents are used. Among them, aminosilane, epoxysilane,
Mercaptosilane and vinylsilane are preferable from the overall balance.

The method for treating silica (D) with a coupling agent is to use the coupling agent as it is or dissolve it in an appropriate solvent, mix it with silica (D) in a high-speed mixer for about 30 minutes, and then heat it to a temperature of about 100 to 150°C. Heat and dry for about 5 hours. At this time, the amount of coupling agent added is silica (D)
For the silicone resin coating, 0.5 to 3% by weight of silica treated with the above coupling agent,
This can be carried out by mixing silicone resin dissolved in a suitable solvent in a mixer, followed by heating and drying for several hours.

By this method, the silica and the silicone resin are strongly bonded, the adhesion between the resin and the silica is improved, and a resin composition with excellent water resistance is obtained.

Furthermore, the phenolic novolak resin (A) and the polymaleimide compound (B) in the resin composition of the present invention can be reacted in advance to an extent that gelation does not occur to form a prepolymer. This improves moldability and
This makes it possible to further enhance the features of the present invention.

Describing the method of thermosetting the resin composition of the present invention,
It can be easily cured without a catalyst, and it can also be cured with organic peroxides,
It is also possible to heat cure using a radical polymerization initiator such as an azo compound. Examples of such radical polymerization initiators include benzoyl peroxide, di-1-butyl peroxide, dicumyl peroxide, lauroyl peroxide, acetyl peroxide, methyl ethyl ketone peroxide, cyclohexanone peroxide, 1-butyl hydroperoxide, Examples include azobisisobutyronitrile. In addition, tertiary amines such as tributylamine, triethylamine, and triamylamine, quaternary ammonium salts such as benzyltriethylammonium chloride and benzyltrimethylammonium hydroxide, imidazoles, boron trifluoride complexes, transition metal acetylacetonate, etc. are used in combination. It is also possible. Curing temperature is 100-250℃
is preferred.

Further, in order to control the curing rate, a known polymerization inhibitor can be used in combination. To illustrate, 2.6-Gt-
Butyl-4-methylphenol, 2.2″-methylenebis(4-ethyl-6-t-butylphenol), 4.4
Phenols such as '-methylenebis(2,6-di-t-butylphenol), 4,4-thiobis(3-methyl-6-t-butylphenol), hahydroquinone monomethyl ether, hydroquinone, catechol, pt-butylcatechol , 2. 5-'; -t-fluorhydroquinone, methylhydroquinone, t-butylhydroquinone, polyhydric phenols such as pyrogallol, phenothiazine compounds such as phenothiazine, benzophenothiazine, acetamidophenothiazine, N-nitrone diphenylamine, N-nitrone There are N-nitrone amine compounds such as dimethylamine.

Further, a known epoxy resin and epoxy curing agent may be used in combination with the sealing resin composition of the present invention. Examples of epoxy resins include phenol, novolak epoxy resin derived from novolak resin which is a reaction product of phenols such as 0-cresol and formaldehyde, phloroglycine, tris-(4-hydroxyphenyl)-methane, etc. , 1. i, 2,2-tetrakis (
Glycidyl ether compounds derived from trihydric or higher phenols such as 4-hydroxyphenyl)ethane, dihydric phenols such as bisphenol A1 bisphenol F1 hydroquinone, resorcinol, or halogenated bisphenols such as tetrabromobisphenol A. diglycidyl ether compound, p-aminophenol, m-aminephenol, 4-aminometacresol, 6-aminometacresol, 4.4°-diaminodiphenylmethane, 3.3′-diaminodiphenylmethane,
4.4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 1.4-bis(4-aminophenoxy)benzene, 1°4-bis(3-aminophenoxy)benzene, 1,3-bis(4- aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)
Benzene, 2.2-bis(4-aminophenoxyphenyl)propane, p-7 22enediamine, m-phenylenediamine, 2゜4-toluenediamine, 2.6-)luenediamine, p-xylylenediamine, m - Amine-based epoxy resin derived from xylylene diamine, 1,4-cyclohexane bis(methylamine), 1,3-cyclohexane bis(methylamine), etc., p-oxybenzoic acid, m-oxybenzoic acid, terephthalic acid , glycidyl ester compounds derived from aromatic carboxylic acids such as isophthalic acid, hydantoin epoxy resins derived from 5,5-dimethylhydantoin, etc., 2,2-bis(
3,4-epoxycyclohexyl)propane, 2゜2-
BisC4-(2,3-epoxypropyl)cyclohexyl]propane, vinylcyclohexene dioxide, 3
．． There are alicyclic epoxy resins such as 4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, as well as N,N-diglycidylaniline, 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 novolac and Talezol novolak, aromatic polyamines such as diaminodiphenylmethane and diaminodiphenylsulfone, and pyromellitic anhydride and benzophenonetetracarboxylic anhydride. Examples include acid anhydrides, but are not limited to these.

In the present invention, other natural waxes, synthetic waxes, higher fatty acids and their metal salts, or a release agent such as paraffin, or a coloring agent such as carbon black may be added as necessary. Also, antimony trioxide,
Flame retardants such as phosphorus compounds and brominated epoxy resins may also be added.

<Effects of the Invention> The sealing resin composition of the present invention has superior processability, heat resistance, moisture resistance, and electrical insulation properties than conventionally known heat-resistant resin compositions, and is extremely useful as a sealing material. A resin composition is provided.

<Example> This will be explained below using examples.

Reference Example 1 [Allyl etherification] O-cresol novolac resin 23 with a softening point of 90°C was placed in a reactor equipped with a thermometer, a stirrer, a dropping funnel, and a reflux condenser.
6 parts (2 equivalents) and 840 parts of dimethylformamide as a reaction solvent, and after completely dissolving the resin,
% caustic soda (41 parts 1.0 equivalent) and stir well. Allyl chloride 82 while keeping the temperature of the reaction system at 40°C.
(1.08 equivalents) was added dropwise over 1 hour, the temperature was raised to 50°C, and the temperature was maintained at the same temperature for 5 hours. Next, after distilling off dimethylformamide, 300 parts of toluene was added to dissolve the resin, and then the inorganic salts were removed by washing with water and filtration, and the filtrate was concentrated to obtain an allyl etherification rate of 50%, which does not have a nuclear substituted allyl group, and an OH 262 parts of a reddish-brown semisolid resin with an equivalent weight of 276 g/eq was obtained.

[Epoxy compound addition]

In a reactor equipped with a thermometer, a stirrer, and a reflux condenser, 220.8 parts (0.8 equivalents) of the above allyl ether compound and allyl glycidyl ether 94 having an epoxy equivalent of 116 g/eq were added.
．． 0 part (0.81 equivalent) and acetonitrile 730B as a reaction solvent, and after completely dissolving the resin,
Add 6.7 parts of an 8% aqueous solution of caustic soda, and maintain the temperature of the reaction system at 80° C. for 12 hours.

Next, after neutralizing with phosphoric acid, acetonitrile was distilled off, 730 parts of toluene was charged and the resin was dissolved, and then inorganic salts were removed by water washing and filtration, and the filtrate was concentrated to have a double bond equivalent of 196 g/eq. Brown viscous liquid resin 30
I got 8 copies. Reference Example 2 Using this resin as ALE-1 Same procedure as in Reference Example 1 except that 158 parts (0.81 equivalents) of m-isopropenylphenyl glycidyl ether with an epoxy equivalent of 195 g/eQ was used instead of allyl glycidyl ether. 370 parts of a brown semisolid resin with a double bond equivalent weight of 235 g/eq were obtained. This resin is ALE-2
shall be.

Reference Example 3 [Allyl etherification] Similar to Reference Example I except that 62 parts (1.5 equivalents) of 97% caustic soda and 120 parts (1.58 equivalents) of allyl chloride were used, but no nuclear substituted allyl group was used. 282 parts of a red-orange viscous liquid resin with an allyl etherification rate of 75% and an OH equivalent of 592 g/eq were obtained.

[Epoxy compound addition]

In Reference Example 1, 236.8 parts (0.4 equivalents) of the allyl etherified product and 30.8 parts (0.4 parts) of glycidol having an epoxy equivalent of 75 g/eq were used instead of allyl glycidyl ether.
, 41 equivalents) in the same manner except that double bond equivalents 2
262 parts of a brown viscous liquid resin of 23 g/eq was obtained. This resin is designated as ALE-3.

Reference Example 4 [Treatment of silica with silane coupling agent] An aminosilane coupling agent (T-aminopropylmethoxysilane; A-1100 manufactured by Nippon Unica Co., Ltd.) Log was dissolved in a mixed solvent of 10 g of water and 90 g of ethanol, and the solution was melted with this. Mix with 1000 g of silica (EF-10 manufactured by Hayashi Kasei Co., Ltd.) using a mixer for about 30 minutes. This is heated and dried in an open air at 130 to 140°C for about 5 hours.

[Silicone resin coating]

13 g of amino-modified silicone resin with an amino equivalent of 840 (X-22-161A manufactured by Shin-Etsu Chemical Co., Ltd.) was mixed with 3 parts of methylene chloride.
0g of silica, and mixed with 1000g of silica treated with the above-mentioned silane coupling agent in a mixer for about 1 hour. This was heated and dried in an oven at 130 to 140°C for 5 hours to obtain silicone resin-coated silica. This will be referred to as Silica-A.

Reference Example 5 A silicone resin-coated silica was obtained in the same manner as in Reference Example 4, except that the amount of amino-modified silicone resin was 25.7 g and the amount of methylene chloride was 60 g. This will be referred to as Silica-B.

Examples 1 to 5, Comparative Example 1 Phenolic novolak resin A obtained in Reference Examples 1 to 3
LE 1 to 3, N,N'-diphenylmethane bismaleimide (referred to as BMI), silicone resin coated silica (silica A-B) obtained in Reference Examples 4 to 5 or untreated fused silica, hardened as necessary. Accelerators and mold release agents are listed in the table below.
Each resin composition was obtained by melt-kneading with heated rolls at 50 to 120° C. for 5 minutes according to the formulation shown in 1. After cooling, the resin compositions were pulverized. Next, these compositions were heated at 175°C x 70k.
Transfer molding was carried out under the conditions of 20 g/cm" x 5 minutes.
After post-curing at 0°C for 5 hours, physical properties were evaluated. The results are shown in Table-2.

Comparative Example 2 0-cresol novolac type epoxy resin (epoxy equivalent: 195 g/eq), phenol novolac resin (O
A resin composition was obtained by kneading H equivalent (110 g/eQ), untreated fused silica, a curing accelerator, a mold release agent, and a coupling agent according to the formulation shown in Table 1 in the same manner as in the examples. Next, this was transfer molded under the conditions of 175°C x 70kg/am2 x 5 minutes, and after post-curing at 180°C x 5 hours, as is clear from Table 2, the cured product obtained with the composition of the present invention was excellent. It can be seen that the material has excellent heat resistance, moisture resistance, and electrical insulation properties.

Furthermore, it can be seen that the composition according to the present invention can be cured for a short time at a temperature of about 175°C, has good flowability, and has excellent processability.

Claims (3)

[Claims] (1) Phenolic novolac resin (A) having in its molecule a phenolic hydroxyl group added with a compound having an allyl etherified phenolic hydroxyl group and at least one epoxy group, and a phenolic novolac resin (A) having two or more maleimides in the molecule A resin composition for semiconductor encapsulation comprising a polymaleimide compound (B) having a group, a silicone resin (C) and silica (D). (2) The resin composition for semiconductor encapsulation according to claim 1, wherein silica (D) is treated with a coupling agent and further coated with a silicone resin. (3) The resin composition for semiconductor encapsulation according to claims 1 and 2, wherein the silicone resin (C) is an amino silicone resin.