JPS63230726A - Molding resin composition - Google Patents

Abstract

PURPOSE:To obtain a resin composition excellent in processability, moisture resistance, heat resistance and electrical insulation and useful for, e.g., sealing electronic components such as semiconductors, by mixing a specified phenol novolac resin with a polymaleimide compound and an epoxy compound. CONSTITUTION:The title composition comprising 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 (e.g., one obtained by subjecting a novolac resin and an allyl halide to dehydrohalogenation and performing addition reaction of the remaining phenolic hydroxyl groups with an epoxy compound), a polymaleimide compound (B) having at least two maleimide groups in the molecule and a compound (C) having at least one epoxy group in the molecule (e.g., novolac epoxy resin). This composition is more excellent than a conventional heat-resistant resin composition in processability, heat resistance, moisture resistance and electrical insulation and is suited as a sealing material for electronic components such as semiconductors.

Description

[Detailed Description of the Invention] <Industrial Application Field> The present invention relates to a resin composition for molding, and more specifically to the encapsulation of electronic components such as semiconductors with excellent processability, moisture resistance, heat resistance, and electrical insulation properties. The present invention relates to a molding resin composition used for, etc.

<Prior Art and its Problems> Conventionally, epoxy resins have been used as molding resin compositions used for sealing 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.

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.

In other words, this phenolic novolac resin (A) has an allyl etherified phenolic hydroxyl group and a small number of phenolic hydroxyl groups added with a compound having one or more epoxy groups (A). Polymaleimide compound (B) having two or more maleimide groups
and a molding resin composition used for sealing electronic parts such as semiconductors, which is made of a compound (C) having at least one epoxy group in the molecule.

Phenolic novolac resin (A
) is an alkyl group, an aryl group, an aralkyl group, an alkenyl group, or a phenol substituted with a halogen atom, or an unsubstituted phenol, specifically phenol,
Cresol, ethylphenol, isopropylphenol, butylphenol, octylphenol, nonylphenol, vinylphenol, impropenylphenol, phenylphenol, benzylphenol, chlorophenol, bromophenol, xylenol, methylbutylphenol, methoxyphenol, ethoxyphenol, α-methylbenzylphenol, One or more types of phenols such as β-phenylethylphenol, dihydroxybenzene (each including isomers), and bisphenol A are condensed with aldehydes such as formaldehyde, furfural, acrolein, and glyoxal by a known method. a novolac resin which usually has an average number of nuclei of 2 to 15 obtained by The reaction method is obtained by reacting a predetermined amount by a known method. First, a novolac resin and a predetermined amount of allyl halide are subjected to a dehydrohalogenation reaction, and then the remaining phenolic hydroxyl group is reacted with the remaining phenolic hydroxyl group in the presence of an alkali. Or, a method in which a compound having at least one epoxy group in the molecule is subjected to an addition reaction in the absence of the compound, or vice versa, or a method in which an allyl halide and a compound having at least one epoxy group in the molecule are reacted simultaneously. Examples of compounds having at least one epoxy group in the molecule used to make the phenolic novolac resin (A) include phenols, alcohols, glycidyl ethers of nitrogen-containing compounds, and carboxylic acids. Glycidyl esters, epoxidized products of olefin peroxides, etc. can be used, but especially allyl glycidyl ether, vinyl phenyl glycidyl ether, isopropenylphenyl glycidyl ether, propenylphenyl glycidyl ether, allyl phenyl glycidyl ether, propenyl methoxyphenyl glycidyl ether Epoxy compounds having an olefinic double bond such as , allylmethoxyphenylglycidyl ether, isopropenylmethoxyphenylglycidyl ether, glycidyl acrylate, and glycidyl methacrylate can be preferably used.

Here, the value of the ratio of the hydroxyl group added with the compound having at least one epoxy group to the allyl etherified hydroxyl group 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'-bismaleimide compounds such as N, N'-diphenylmethane bismaleimide, N, N'-phenylene bismaleimide ,N,N
'-diphenyl ether bismaleimide, N, N'
-diphenylsulfone bismaleimide, N,N'-dicyclohexylmethane bismaleimide, N,N'-xylene bismaleimide, N,N'-)rylene 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 bismethylmaleimide, N
, N'-diphenylsulfone bismethylmaleimide (each includes isomers), N, N'-ethylene bismaleimide, N, N'-hexamethylene bismaleimide, N, N''-hexamethylene bismethylmaleimide, and these Examples include a prepolymer whose end has an N,N'-bismaleimide skeleton obtained by adding an N,N'-bismaleimide compound and a diamine, and a maleimide or methylmaleimide of an aniline/formalin polycondensate. Particularly preferred are N,N'-diphenylmethane bismaleimide and NN+-diphenyl ether bismaleimide.

Examples of compounds having at least one epoxy group in the molecule which are component (C) of the present invention include phenols, alcohols, glycidyl ethers of nitrogen-containing compounds, glycidyl esters of carboxylic acids, and peroxides of olefins. Epoxidized products such as those prepared by E. et al. can be used, and in particular, epoxy compounds having an olefinic double bond such as allyl glycidyl ether, vinyl phenyl glycidyl ether, isopropenylphenyl glycidyl ether, glycidyl acrylate, and glycidyl methacrylate can be preferably used.

Epoxy resins having two or more epoxy groups in the molecule can also be used, such as phenol, novolak epoxy resins derived from novolac resins which are reaction products of phenols such as 0-cresol, and formaldehyde, and phloroglycin. , tris-(4-hydroxyphenyl)-methane, glycidyl ether compounds derived from trivalent or higher phenols such as 1.1.2.2-tetrakis(4-hydroxyphenyl)ethane, bisphenol A1 bisphenol F1 hydroquinone , dihydric phenols such as resorcinol, or tetrabromobisphenol A
diglycidyl ether compounds derived from halogenated bisphenols such as p-aminephenol, m-aminophenol, 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-phenylenediamine, m-phenylenediamine, 2,4-toluenediamine, 2.6-)luenediamine, p-xylylenediamine, m-xylylenediamine, 1°4-cyclohexanebis(methylamine), 1.
Amine-based epoxy resin derived from 3-cyclohexanebis(methylamine) etc., p-oxybenzoic acid, m-
Glycidyl ester compounds derived from aromatic carboxylic acids such as oxybenzoic acid, terephthalic acid, and isophthalic acid, hydantoin epoxy resins derived from 5,5-dimethylhydantoin, etc., 2,2-bis(3,4- epoxycyclohexyl)propane, 2,2-bisC4-
Alicyclic epoxy resins such as (2゜3-epoxypropyl)cyclohexyl]propane, vinylcyclohexene dioxide, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, and other N, N-diglycidylaniline, etc. For example, one or more of these epoxy resins may be used.

Among these, novolac-based epoxy resins are preferred.

The resin composition of the present invention may also contain an epoxy resin curing agent, such as novolac resins such as phenol novolak and cresol novolac, aromatic polyamines such as diaminodiphenylmethane and diaminodiphenylsulfone,
Examples include acid anhydrides such as pyromellitic anhydride and benzophenonetetracarboxylic anhydride, but are not limited thereto.

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 general, the ratio of the double bonds of the polymaleimide compound (B) to the double bonds of the phenolic novolac resin (A) is 0.4 to
It is preferable to select 3.

In addition, the quantitative ratio of the epoxy compound as component (C) is 3 to 20% in the resin (phenolic novolak resin (A) + polymaleimide compound (B) + epoxy compound (C)).
% by weight is preferred, more preferably 5-15% by weight. When the amount of the epoxy compound added is 3% by weight or less,
Moisture resistance and electrical insulation properties are reduced, and addition of 20% by weight or more results in a reduction in heat resistance.

Phenolic novolak resin in the resin composition of the present invention (
A) and the polymaleimide compound (B) can be reacted in advance to form a prepolymer. This improves moldability and 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-t-butyl peroxide, dicumyl peroxide, lauroyl peroxide, acetyl peroxide, methyl ethyl ketone peroxide, cyclohexanone peroxide, and -butyl hydroperoxide. , azobisisobutyronitrile, etc. Other tertiary amines such as tributylamine, triethylamine, and triamylamine, quaternary ammonium salts such as benzyltriethylammonium chloride and benzyltrimethylammonium hydroxide, imidazoles, triphenylphosphine, boron trifluoride complexes, and transition metal acetylacetonates. It is also possible to use them together.

Further, in order to control the curing rate, it is possible to use a known polymerization inhibitor in combination. To illustrate, 2,6-di-t-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, p-t-
Butylcatechol, 2. Polyhydric phenols such as 5-sheet t-butylhydroquinone, methylhydroquinone, t-butylhydroquinone, and pyrogallol; phenothiazine compounds such as phenothiazine, benzophenothiazine, and acetamidophenothiazine; -There are nitrosamine compounds.

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 the inorganic filler include silica powder, alumina, talc, calcium carbonate, titanium white, clay, asbestos, mica, red iron oxide, and glass fiber, with silica powder and alumina being particularly preferred. 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. .

In addition, brominated epoxy resins are particularly preferred in order to produce a flame retardant effect that may be supplemented with flame retardants such as antimony trioxide, phosphorus compounds, and brominated epoxy resins.

<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 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.

<Example> This will be explained below using examples.

Reference Example 1 [Allyl etherification] 0-cresol novolak resin 2 with a softening point of 90°C was placed in a reactor equipped with a temperature gauge, a stirrer, a dropping funnel, and a reflux condenser.
After charging 36 parts (2 equivalents) and 840 parts of dimethylformamide as a reaction solvent and completely dissolving the resin,
Add 41 parts (1.0 equivalents) of 7% caustic soda and stir. While keeping the temperature of the reaction system at 40°C, add 8 parts of allyl chloride.
After dropping 2 parts (1.08 equivalents) over 1 hour, the temperature was raised to 50°C and 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 9 with an epoxy equivalent of 116 g/eq were added.
Charge 4.0aB (0.81 equivalents) and 730 parts of acetonitrile as a reaction solvent, and after completely dissolving the resin, add 6.7 parts of a 48% caustic soda aqueous solution, and heat the reaction system at the same temperature while keeping it at 80°C. Hold for 12 hours.

Next, after neutralizing with phosphoric acid, acetonitrile was distilled off, 730 parts of toluene was charged, and the resin was dissolved. Inorganic salts were removed by water washing and filtration, and the filtrate was concentrated to obtain 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 [Allyl etherification] Same procedure as in Reference Example 1 except that 62 parts (1.5 equivalents) of 97% caustic soda and 120 parts (1°58 equivalents) of allyl chloride were used. 282 parts of a reddish-orange viscous liquid resin having an allyl etherification rate of 75% and an OH equivalent of 592 g/eQ, which does not have a nuclear substituted allyl group, was obtained.

[Epoxy compound addition]

In Reference Example 1, 236.8 parts (0.4 equivalents) of the above 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-2.

Reference Example 3 A double bond equivalent of 235 g/eQ was prepared in the same manner as in Reference Example 1 except that 158 parts (0.81 equivalents) of epoxy equivalent:) m-isopropenylphenyl glycidyl ether was used in place of allyl glycidyl ether. 370 parts of a brown semi-solid resin were obtained. This resin is ALE-3
shall be.

Reference Example 4 [Prepolymerization] 100 parts of ALE-1 obtained in Reference Example 1 and N,
137 parts of N'-diphenylmethane bismaleimide to 11 parts
The mixture was charged into a four-bottle flask, heated to 160° C., melted and mixed, and reacted at this temperature for 2 hours with stirring to obtain a prepolymer. This will be referred to as prepolymer A.

Reference Example 5 [Prepolymerization] Using 100 parts of ALE-2 instead of ALE-1, N,
The amount of N'-diphenylmethane bismaleimide was 102
A prepolymer was obtained in the same manner as in Reference Example 4 except that This will be referred to as prepolymer B.

Reference Example 6 [Prepolymerization] 100 parts of ALE-3 obtained in Reference Example 3 and N,
137 parts of N'-diphenylmethane bismaleimide in 10
The mixtures were melt-mixed using two rolls heated to 0°C and reacted for about 20 minutes to obtain a prepolymer. This is prepolymer C
shall be.

Examples 1 to 5, Comparative Example 1 Phenolic novolac resin ALE obtained in Reference Example 3
-3 and the prepolymers A-C obtained in Reference Examples 4 to 6, and N,N'-diphenylmethane bismaleimide, 0-
Talezorno.

Borac type epoxy resin, curing accelerator, filler, coupling agent, and mold release agent were added according to the formulation shown in Table 1.
Each resin composition was obtained by melt-kneading using heated rolls under the conditions of 0 to 120°C for 5 minutes, cooling, and pulverizing. Next, these compositions were transfer molded under the conditions of 175° C. x 70 kg/cm” x 5 minutes, and after post-curing at 200° C. for 5 hours, the 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 (OH
equivalent weight 110 g/eQ), a curing accelerator, a filler, a mold release agent, and a coupling agent were kneaded in the same manner as in Examples according to the formulation shown in Table 1 to obtain a resin composition. Next, this was transfer molded under the conditions of 175° C. x 70 kg/cm' x 5 minutes, and after post-curing for 180 t x 5 hr, the physical properties were evaluated. The results are shown in Table-2.

As is clear from Table 2, the cured product obtained from the composition according to the present invention 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 (2)

[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 molding comprising a polymaleimide compound (B) having a group and a compound (C) having at least one epoxy group in the molecule. (2) The resin composition for molding according to claim 1, wherein the compound (C) is a novolak epoxy resin.