JPH075821B2 - Electronic parts - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION <Field of Industrial Application> The present invention relates to an electric / electronic component having excellent heat resistance.

<Prior Art and Its Problems> Conventionally, electrical and electronic parts such as semiconductors, which are molded and sealed using an epoxy resin, have been widely used.

The epoxy resin encapsulation has been widely put into practical use because it is economically advantageous as compared with the hermetic sealing method using glass, metal, or ceramic. However, in recent years, the usage conditions of electronic parts have tended to be severe, and as a result, the heat resistance of the sealing material has become an important characteristic.

Conventionally, thermosetting polyimide resin encapsulation has been used for the purpose of obtaining such high heat resistance, but in terms of workability, heating at high temperature for a long time is required, which is a major drawback in terms of economy. have.

In addition, although the epoxy resin encapsulation with improved heat resistance has excellent workability, the electronic components encapsulated by this have high heat resistance such as mechanical properties at high temperature, electrical properties, and long-term heat deterioration resistance. It was not enough.

<Means for Solving Problems> From such a background, as a result of diligent study by the present inventor about electronic parts having excellent processability and heat resistance, the present inventors have sealed with a resin composition containing a specific resin and a maleimide compound. The inventors have found that the produced electronic parts meet the above-mentioned object and completed the present invention.

That is, the present invention is a resin composition comprising a partially allyl etherified substituted phenol novolac resin (A), a polymaleimide compound (B) having two or more maleimide groups in the molecule, and a filler (C). The present invention relates to an electronic component molded and sealed by a product.

The present invention will be described in detail below.

The partially allyl etherified substituted phenol novolac resin (A) used in the present invention is a phenol substituted with an alkyl group, an alkenyl group, an aryl group, an aralkyl group or a halogen atom, specifically, Of substituted phenols such as cresol, ethylphenol, isopropylphenol, butylphenol, octylphenol, nonylphenol, vinylphenol, isopropenylphenol, phenylphenol, pentylphenol, chlorophenol, bromphenol, xylenol, methylbutylphenol (including isomers) A novolak resin usually having an average number of nuclei of 2 to 15 obtained by condensation reaction of one or more kinds with aldehydes such as formaldehyde, furfural, acrolein, etc. by a known method, and a chloride. Lil, allyl bromide, obtained by reacting the presence of an alkali and allyl halide such as allyl iodide.

Here, the value of the ratio of the unsubstituted hydroxyl group to the allyl etherified hydroxyl group is preferably 1 / 0.2 to 9, more preferably 1 / 0.3.
~ 6. If this ratio exceeds the above range, the curability or heat resistance will decrease.

In the present invention, since the substituted phenols novolac is used as a raw material, the generation of the phenol hydroxyl group by Claisen transfer hardly occurs, and the major feature is that the allyl ether group and the hydroxyl group are present in different aromatic rings.

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 and N, N'-diphenylmethane bismaleimide.
N'-phenylene bismaleimide, N, N'-diphenyl ether bismaleimide, N, N'-diphenylsulfone bismaleimide, N, N'-dicyclohexylmethane bismaleimide, N, N'-xylene bismaleimide, N, N'- Tolylene bismaleimide, N, N'-xylylene bismaleimide, N, N'-diphenylcyclohexane bismaleimide, N, N'-dichlorodiphenylmethane bismaleimide, N, N'-diphenylcyclohexane bismaleimide, N, N'- Diphenylmethanebismethylmaleimide,
N, N′-diphenyl ether bismethylmaleimide, N,
N'-diphenylsulfone bismethylmaleimide (each including isomers), N, N'-ethylene bismaleimide,
N, N'-hexamethylene bismaleimide, N, N'-hexamethylene bismaleimide and N, N'-bismaleimide compound and the terminal obtained by adding diamines with N, N'-bismaleimide skeleton Examples thereof include a prepolymer, a maleimide compound or a methylmaleimide compound of an aniline / formalin polycondensation product. Especially N,
N'-diphenylmethane bismaleimide and N, N'-diphenyl ether bismaleimide are preferred.

The quantitative ratio of each component of the resin composition of the present invention can be appropriately selected depending on the application, desired heat resistance and the like. However, it is generally preferred that the ratio of the double bond of the partially allyl etherified phenol novolak resin (A) to the double bond of the polymaleimide compound (B) to the hydroxyl group is 0.4 to 8.

If either component is more than the above range,
Curability and heat resistance decrease.

Further, the phenolic novolak resin (A) and the polymaleimide resin (B) in the resin composition according to the present invention can be preliminarily reacted and prepolymerized. Thereby, the moldability is further improved, and the features of the present invention can be further enhanced.

As the filler (C) used in the present invention, fused silica,
Crystalline silica, alumina, talc, calcium carbonate, titanium white, clay, asbestos, mica, red iron oxide,
Examples include glass fibers, but among others, fused silica,
Crystalline silica and alumina are preferably used.

Further, when used for sealing a semiconductor, the blending ratio of the filler needs to be 25 to 90% by weight, preferably 60 to 80% by weight, based on the total amount of the resin composition.

The method of thermosetting the resin composition of the present invention will be described.
Although it can be easily cured without a catalyst, it can be further easily cured by using a curing accelerator. Examples of such a catalyst include triphenylphosphine, tri-4-methylphenylphosphine,
Organic phosphine compounds such as tri-4-methoxyphenylphosphine, tributylphosphine, trioctylphosphine and tri-2-cyanoethylphosphine, benzoyl peroxide, di-t-butyl peroxide,
Dicumyl peroxide, lauroyl peroxide, acetyl peroxide, methyl ethyl ketone peroxide,
Radical polymerization initiators such as cyclohexanone peroxide, t-butyl hydroperoxide and azobisisobutyronitrile, and other tertiary amines such as tributylamine, triethylamine and triamylamine, benzyltriethylammonium chloride, benzyltrimethylammonium hydroxide, etc. Examples thereof include quaternary ammonium salts, imidazoles, boron trifluoride complexes, transition metal acetylacetonates, and the like, but are not limited thereto.

Among these, organic phosphine compounds are particularly preferable.

It is also possible to use a known polymerization inhibitor together in order to adjust the curing rate. For example, 2,6-di-t-butyl-4-methylphenol, 2,2'-methylenebis (4-ethyl-6-t-butylphenol), 4,4'-
Methylenebis (2,6-di-t-butylphenol), 4,
Phenols such as 4′-thiobis (8-methyl-6-t-butylphenol) and high hydroquinone monomethyl ether, hydroquinone, catechol, pt-butylcatechol, 2,5-di-t-butylhydroquinone, methylhydroquinone, There are polyhydric phenols such as t-butylhydroquinone and pyrogallol, phenothiazine compounds such as phenothiazine, benzophenothiazine and acetamidophenothiazine, and N-nitrosamine compounds such as N-nitrosodiphenylamine and N-nitrosodimethylamine.

A known epoxy resin and epoxy curing agent may be used in combination in the resin composition used for molding and sealing the electronic component of the present invention. Illustrating these, examples of the epoxy resin include a novolac-based epoxy resin derived from a novolac resin, which is a reaction product of phenols such as phenol and o-cresol, and formaldehyde, phloroglysin, tris- (4-hydroxyphenyl)-. Methane, 1,
Glycidyl ether compounds derived from trihydric or higher phenols such as 1,2,2-tetrakis (4-hydroxyphenyl) ethane, dihydric phenols such as bisphenol A, bisphenol F, hydroquinone and resorcin, or tetrabromobisphenol A Diglycidyl ether compounds derived from halogenated bisphenols such as p-aminophenol, 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-toluenediamine, p-xylylenediamine, m-xylylenediamine, 1,4-cyclohexanebis (methylamine), 1,3-cyclohexanebis (methyl Amine-based epoxy resins, glycidyl ester-based compounds derived from aromatic carboxylic acids such as p-oxybenzoic acid, m-oxybenzoic acid, terephthalic acid and isophthalic acid, 5,5-dimethylhydantoin Hydantoin-based epoxy resin derived from etc., 2,2-bis (3,4-epoxycyclohexyl) propane, 2,2- The [4-
Alicyclic epoxy resins such as (2,3-epoxypropyl) cyclohexyl] propane, vinylcyclohexenedioxide, and 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate Other N, N
-Diglycidyl aniline and the like, and one or more of these epoxy resins are used.

Known epoxy resin curing agents can also be used, for example, novolac resins such as phenol novolac and cresol novolac, aromatic polyamines such as diaminodiphenylmethane and diaminodiphenylsulfone, and acids such as pyromellitic dianhydride and benzophenone tetracarboxylic anhydride. Examples thereof include anhydrides, but are not limited to these.

In the present invention, the resin composition may further include a silicone oil natural wax, a synthetic wax, a higher fatty acid and a metal salt thereof, a release agent such as paraffin or a colorant such as carbon black, and a coupling agent, if necessary. May be added. Also, antimony trioxide,
A flame retardant such as a phosphorus compound or a brominated epoxy resin may be added. The resin composition thus obtained can be compounded by melt-kneading with a general kneader such as a roll or a cokneader.

The electronic component of the present invention is 160-200 using this compound.
It can be easily prepared by transfer molding or compression molding at a temperature of about ° C.

<Effects of the Invention> Thus, the electronic component obtained by the present invention is extremely superior in heat resistance, low stress, etc., to the conventional electronic components.

<Examples> Examples will be described below.

Reference Example 1 236 parts (2 equivalents) of o-cresol novolac resin having a softening point of 90 ° C. and dimethyl sulfoxide 84 as a reaction solvent in a reactor equipped with a thermometer, a stirrer, a dropping funnel and a reflux condenser.
Charge 0 parts, completely dissolve the resin, add 28.7 parts (0.7 equivalents) of 97% caustic soda, and stir well. While maintaining the temperature of the reaction system at 40 ° C, 55.9 parts (0.74 equivalents) of allyl chloride was added dropwise over 1 hour, then the temperature was raised to 50 ° C and the temperature was raised to 5 ° C.
Hold for time. Then, after distilling off dimethylsulfoxide, 300 parts of methyl isobutyl ketone was charged and the resin was dissolved, then the inorganic salt was removed by washing with water and then by filtration, and the liquid was concentrated to concentrate allyl groups having a nucleus-substituted allyl group of 35%. , 230 parts of a reddish brown semi-solid resin having an OH equivalent of 208 g / eq was obtained. (ALN-1).

Reference Example 2 41 parts (1.0 equivalent) of caustic soda and 8 parts of allyl chloride
In the same manner as in Reference Example 1 except that 0 part (1.05 equivalent) was used,
262 parts of a reddish-brown semi-solid resin having an allyl etherification rate of 50% and an OH equivalent of 276 g / eq was obtained (designated ALN-2).

Reference Example 3 In the same manner as in Reference Example 1 except that the amount of caustic soda was 57.1 parts (1.4 equivalents) and the amount of allyl chloride was 111.7 parts (1.47 equivalents), the allyl etherification rate was 70% and the OH equivalent was 487 g / eq. 280 parts of a reddish brown viscous liquid resin was obtained (ALN-8).

Reference Example 4 [Prepolymerization] 100 parts of ALN-2 obtained in Reference Example 2 and 259 parts of N, N'-diphenylmethane bismaleimide were charged in a four-necked flask, heated to 130 ° C and melt-mixed. After that, the mixture was reacted with stirring at this temperature for about 1 hour to obtain a prepolymer. This is designated as prepolymer A.

Examples 1 to 4 Phenolic novolac resin AL obtained in Reference Examples 1 to 3
Prepolymers obtained in N-1 to 3 and Reference Example 4 and N, N '
-Diphenylmethane bismaleimide, o-cresol novolac type epoxy resin, curing accelerator, filler, coupling agent and mold release agent according to the formulation shown in Table-1.
Each resin composition was obtained by melt-kneading with a heating roll under the condition of 120 ° C x 5 minutes, cooling and pulverizing. Next, these compositions were transfer-molded under the conditions of 175 ° C. × 70 kg / cm ² × 5 minutes, post-cured at 200 ° C. × 5 hours, and then evaluated for physical properties. The results are shown in Table-2.

Comparative Example 1 o-cresol novolac type epoxy resin (epoxy equivalent 195 g / eq), phenol novolac resin (OH equivalent 110 g / eq)
eq), a curing accelerator, a filler, a release agent, and a coupling agent were kneaded in the same manner as in the examples according to the formulations shown in Table 1 to obtain a resin composition. Next, this is 175 ℃ × 70kg / cm ²
Transfer molding was performed under the condition of × 5 minutes, and after curing at 180 ° C. for 5 hours, the physical properties were evaluated.

The results are shown in Table-2.

N, N-diphenylmethane bismaleimide; Sumitomo Chemical Co., Ltd. ESCN-195XL; Sumitomo Chemical Co., Ltd. epoxy resin (epoxy equivalent
195g / eq) Aminosilane coupling agent; A-1100 epoxy silane coupling agent manufactured by Nippon Unica; SH manufactured by Toray Silicone
6040 Fused silica; FS-891 manufactured by Denki Kagaku As is clear from Table-2, the molded product obtained from the resin composition used for the electronic component of the present invention has far superior heat resistance as compared with the case of using the conventional epoxy resin.

Moreover, the curability and flowability are the same as when using the epoxy resin, and it can be seen that it has excellent processability.

 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Yu Hasegawa 3-98 Kasugadechu, Konohana-ku, Osaka City, Osaka Prefecture Sumitomo Chemical Co., Ltd. (56) Reference JP-A-62-207354 (JP, A) ) JP-A-63-230729 (JP, A) JP-A-63-230728 (JP, A) JP-A-63-3033 (JP, A) JP-A-62-207354 (JP, A) JP-A-62- 138534 (JP, A)

Claims (1)

[Claims] 1. A resin composition comprising a partially allyl etherified substituted phenol novolac resin (A), a polymaleimide compound (B) having two or more maleimide groups in the molecule, and a filler (C). Electronic components that are molded and sealed by.