JPH07316399A - Thermosetting resin composition and electronic part - Google Patents

Abstract

PURPOSE:To obtain the composition, containing an epoxy resin, a curing agent for the epoxy resin and a specific additive, excellent in processability, heat and moisture resistances, adhesion and suitable as a sealing material for electronic parts. CONSTITUTION:This composition contains (A) an epoxy resin having >=2 epoxy groups in the molecule (e.g. a novolak type epoxy resin), (B) a curing agent for the epoxy resin (preferably a novolak resin of phenols) and (C) an additive capable of chelating with copper and allay 42 (an allay of Fe and Ni containing 42% Ni) (preferably anthranilic acid, aminophenol, gallic acid, a gallic acid ester, malonic acid or malic acid). Furthermore, (D) a filler is preferably further contained therein.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermosetting resin composition which is particularly useful as a sealing material for electronic parts and an electronic part molded and sealed with the composition.

[0002]

2. Description of the Related Art Recently, LSIs, ICs, transistors, etc.
Transfer molding with an economically useful epoxy resin is performed for sealing a semiconductor. Especially recently
The surface mounting of LSIs is performed, and the number of cases in which they are directly immersed in a solder bath is increasing. At that time, the sealing material is 20
Since it is exposed to a high temperature of 0 ° C. or higher, the moisture absorbed in the encapsulant expands, causing problems such as cracking and peeling at the interface with the die pad. Therefore, the resin sealing material is required to have heat resistance and adhesiveness, and particularly high adhesiveness. Currently, o-
The mainstream is a sealing material using glycidyl ether of cresol novolac and phenol novolac as a curing agent, but due to the above problems, it is practically used in a moisture-proof package.

[0003]

The encapsulant mainly composed of glycidyl ether of o-cresol novolac and phenol novolac is well balanced in terms of heat resistance and hygroscopicity, but adhesiveness and adhesion However, there is a problem in solder cracking property.
The object of the present invention is excellent in workability, heat resistance and moisture resistance,
It is an object of the present invention to provide a thermosetting resin composition which is particularly excellent in adhesion and adhesiveness as compared with conventionally known resin compositions and which is useful as a composition for a sealing material.

[0004]

In view of such circumstances, the present inventors have found that the epoxy resin composition has a well-balanced epoxy resin composition having excellent adhesion and adhesiveness, and also excellent processability, heat resistance and moisture resistance. As a result of diligent study, the resin composition composed of the epoxy resin and the epoxy resin curing agent has an adhesive force with copper and 42 alloy (an alloy of Fe and Ni containing 42% Ni) of the lead frame. The present inventors have found that the resin composition obtained by blending the additive for enhancing the above-mentioned purpose is suitable for the above purpose, and have completed the present invention.

That is, the present invention is as follows. (1) A resin containing (A) an epoxy resin having two or more epoxy groups in a molecule, (B) an epoxy resin curing agent, and (C) an additive capable of chelating copper and 42 alloy. And a thermosetting resin composition. (2) A thermosetting resin composition which further contains (D) a filler in addition to the components (A), (B), and (C). (3) An electronic component formed by molding and encapsulating the thermosetting resin composition as described in (1) or (2) above.

The present invention will be described in detail below. Known epoxy resins can be used for the component (A) used in the present invention, and specific examples thereof are reaction products of phenols such as phenol, o-cresol, and naphthol with formaldehyde. Novolac-based epoxy resin derived from novolac resin,
Phloroglysin, Tris- (4-hydroxyphenyl)
A glycidyl ether compound derived from a trivalent or higher phenol such as methane, 1,1,2,2, -tetrakis (4-hydroxyphenyl) ethane, bisphenol A, bisphenol F, hydroquinone, resorcin,
Glycidyl ether compounds derived from dihydric phenols such as 1,1′-bis (3-t-butyl-6-methyl-4-hydroxyphenyl) butane, tetramethylbiphenol, naphthalenediol or tetrabromobisphenol A Diglycidyl ether compounds derived from halogenated bisphenols,

Glycidyl ether compounds of polyhydric phenol obtained by condensation reaction of phenols and aromatic carbonyl compounds, 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 ( Amine-based epoxy resin derived from methylamine),

Glycidyl ester compounds derived from aromatic carboxylic acids such as p-oxybenzoic acid, m-oxybenzoic acid, terephthalic acid and isophthalic acid, and hydantoin epoxy compounds derived from 5,5-dimethylhydantoin and the like. , 2,2-bis (3,4-epoxycyclohexyl) propane, 2,2-bis [4- (2,3-epoxypropyl) cyclohexyl] propane, vinylcyclohexenedioxide, 3,4-epoxycyclohexylmethyl-3 There are alicyclic epoxy resins such as 1,4-epoxycyclohexanecarboxylate, N, N-diglycidylaniline and the like, and one or more of these epoxy resins are used. Among these, a glycidyl ether type epoxy resin is preferable from the viewpoint of moisture resistance, and among them, o
A cresol novolac epoxy resin, tetramethyl biphenol, and a glycidyl ether compound of a polyhydric phenol obtained by a condensation reaction of a phenol and an aromatic carbonyl compound are preferable from the viewpoint of curability and heat resistance or hygroscopicity.

As the epoxy resin curing agent as the component (B), known ones can be used. Examples of these are bisphenol A, tetrabromobisphenol A, bisphenol F, bisphenol S, bis (4-hydroxyphenyl) cyclohexane, bis (4-hydroxyphenyl) ethane, 1,3,3-trimethyl-1-m-hydroxy. Phenylindane-5 or 7
-Ol, 1,3,3-trimethyl-1-p-hydroxyphenylindan-6-ol, resorcin, hydroquinone, catechol and phenol, phenols such as o-cresol and phenol novolak which is a reaction product of formaldehyde Polyphenol compounds such as maleic acid, phthalic acid, nadic acid, methyl-tetrahydrophthalic acid, methyl nadic acid and the like, and their anhydrides,

Diaminodiphenylmethane, diaminodiphenyl sulfone, diaminodiphenyl ether, phenylenediamine, diaminodicyclohexylmethane, xylylenediamine, toluenediamine, diaminodicyclocyclohexane, dichloro-diaminodiphenylmethane (including isomers), ethylenediamine, hexamethylenediamine, etc. Examples of the polyamine compound include the active hydrogen-containing compound capable of reacting with an epoxy group, such as dicyandiamide and tetramethylguanidine. Among them, phenolic novolac resins are preferably used from the viewpoint of curability and moisture resistance.

In the composition of the present invention, regarding the mixing ratio of the epoxy resin as the component (A) and the curing agent for the epoxy resin as the component (B), the equivalent ratio of epoxy groups to active hydrogen is 0.7 to 1. .2 equivalents are preferred. If it deviates significantly from this range, the moisture resistance, curability and the like are deteriorated, which is not preferable.

The method of heat-curing the resin composition of the present invention will be described. Although it can be cured without a catalyst, it can be more easily cured by using a curing accelerator (catalyst). Examples of such catalysts include triphenylphosphine, tri-4-methylphenylphosphine, tri-4-methoxyphenylphosphine, tributylphosphine, trioctylphosphine,
Organic phosphine compounds such as tri-2-cyanoethylphosphine and salts thereof, tertiary amines such as tributylamine, triethylamine, 1,8-diazabicyclo (5,4,0) undecene-7 and triamylamine, benzyltrimethylammonium chloride Examples thereof include, but are not limited to, quaternary ammonium salts such as benzyltrimethylammonium hydroxide and triethylammonium tetraphenylborate, imidazoles, boron trifluoride complex, transition metal acetylacetonate, and the like.
Among these, organic phosphine compounds, imidazoles and salts thereof (specifically, tetraphenylphosphonium tetraphenylborate, 4-methylimidazole tetraphenylborate, etc.) or triethylammonium tetraphenylborate are particularly preferable.

The additive (C) used in the present invention is a compound capable of chelating with copper and 42 alloy, and is generally a compound having two or more carboxylic acid groups, hydroxyl groups or amino groups in the molecule. Alternatively, these are esterified products (the functional groups do not necessarily have to be the same), and if these are exemplified, anthranilic acid, aminophenol,
Examples thereof include gallic acid, gallic acid esterified products, malonic acid, malic acid, 8-quinolinol, and n-butylphenol maleate, but are not limited thereto.
These 1 type (s) or 2 or more types are used. Among these, gallic acid esterified products and malonic acid are particularly preferable.

In the present invention, the compounding amount of the component (C) is preferably 0.1 to 5 parts by weight, more preferably 0.1 part by weight based on 100 parts by weight of the total amount of the components (A) and (B).
5 to 3 parts by weight. If the amount is less than this range,
The effect of improving the adhesiveness is poor, and if it is too large, the mechanical properties and heat resistance tend to decrease.

Examples of the filler (D) used in the present invention include fused silica, crystalline silica, alumina, talc, calcium carbonate, titanium white, clay, asbestos, mica, red iron oxide, glass fiber and the like. Fused silica, crystalline silica and alumina are preferably used.

The blending ratio of the filler can be appropriately determined according to the purpose, but when it is used for encapsulating a semiconductor, it is preferably 30 to 94% by weight of the total amount of the resin composition, and more preferably. It is 65 to 92% by weight. When the amount of the filler is less than 30% by weight, the moisture resistance is inferior, and 9
If it exceeds 4% by weight, problems occur in moldability.

In the present invention, if necessary, a natural wax, a synthetic wax, a higher fatty acid and a metal salt thereof, a releasing agent such as paraffin or a coloring agent such as carbon black, and a surface treatment such as a silane coupling agent. Agents and the like may be added. Further, a flame retardant such as antimony trioxide, a phosphorus compound and a brominated epoxy resin may be added. A brominated epoxy resin is particularly preferable for producing a flame retardant effect.

Further, for example, in order to reduce the stress, various elastomers may be added or reacted in advance and used. Specific examples thereof include addition type or reaction type elastomers such as polybutadiene, butadiene-acrylonitrile copolymer, silicone rubber and silicone oil.

The resin composition thus obtained can be compounded by melt mixing with a general kneader such as a roll or a cokneader. In order to seal electronic parts such as semiconductors using the resin composition according to the present invention, curing molding may be carried out by a conventionally known molding method such as transfer molding, compression molding, injection molding or the like.

[0020]

The resin composition of the present invention is mainly used for sealing electronic parts such as semiconductors. Further, it is excellent in workability, heat resistance and moisture resistance, particularly excellent in adhesion and adhesiveness as compared with conventionally known resin compositions, and is extremely useful as a composition for a sealing material.

[0021]

EXAMPLES Examples of the present invention will be shown below, but the present invention is not limited thereto. The evaluation method of the cured molding is
It is as follows. -Gel time: the kneaded products obtained in Examples and Comparative Examples
0.5 g was taken in the concave portion of the hot plate at 180 ° C., and the time until gelation was measured.

Glass transition temperature: thermomechanical analyzer (SH
It was measured using IMADZU DT-30). Bending strength and flexural modulus: Measured with an Instron universal material testing machine (SHIMADZU IS-10T) according to JIS K-6911.
The measurement temperature is 20 ° C and 240 ° C.

Water absorption rate: The weight change was measured under the conditions of 85 ° C./85% RH by using a constant temperature and constant humidity (TABAI PR-2).・ Spiral flow: 190 according to EMMI-1-66
It was carried out under the condition of ° C / 70 kg / cm ² .

Hardness developing property (Burcol hardness): 190
It was carried out under the molding conditions of ° C / 120 seconds. -Adhesion test: A compound was molded using a pull-out strength measuring frame (see Fig. 1) made of copper and 42 alloy, and after the post-curing, the pull-out strength of the frame was evaluated.

Adhesion evaluation test: simulated IC (52-pin QFP
Package: Package thickness 2.05mm) 85 ℃ / 85% RH / 48
Peeling area measured with an ultrasonic probe imager (AT5000 manufactured by Hitachi Construction Machinery Co., Ltd.) after measuring the degree of peeling on the back surface of the die pad immediately after absorbing moisture under the conditions of time and immediately immersing it in a solder bath at 240 ° C for 30 seconds. It is evaluated by the ratio. Evaluation criteria are: ○: peeling area 0 to 30%, △: peeling area 31 to 70%, ×: peeling area 71 to
100%. Average of 10 test individuals.

Examples 1 to 6 Glycidyl ether of o-cresol novolac (trade name: Sumiepoxy ESCN-195XL, manufactured by Sumitomo Chemical Co., Ltd., epoxy equivalent 196 g / equivalent, hydrolyzable chlorine 330 ppm) and phenols as epoxy resin Glycidyl ether compound of the condensate of carbonyl and aromatic carbonyl compound (trade name
Sumiepoxy ESX-221, Sumitomo Chemical Co., Ltd., epoxy equivalent 213.1 g / equivalent, hydrolyzable chlorine 170 ppm), phenol novolac as an epoxy resin curing agent (Gunei Chemical Co., Ltd., trade name PSM-4261) , OH equivalent =
106 g / eq), n-propyl gallate as a chelating agent, malonic acid, o-aminophenol, triphenylphosphine as a curing accelerator, and crushed fused silica as a filler (trade name FS-891, Electrochemical Industry ( Co., Ltd.), spherical fused silica (trade name FB-74, manufactured by Denki Kagaku Co., Ltd.),
Carnauba wax as a release agent, γ-glycidoxypropyltrimethoxysilane as a coupling agent (trade name SH-6
040, manufactured by Toray Dow Corning Silicone Co., Ltd. was blended in the amounts (parts by weight) shown in Table 1, heated and kneaded with a roll, and transfer molding was performed.

Post cure at 180 ° C. for 5 hours,
A cured molded product was obtained. Tables 1 and 2 show the compounding formulation, the physical properties of the obtained resin composition, and the physical properties of the cured moldings thereof.

Comparative Examples 1 and 2 Cured molded articles were obtained in the same manner as in Examples 1 to 6 except that the chelating agent was not used. The compounding recipe and the physical properties of the cured molded product are shown in Tables 1 and 2.

[0029]

[Table 1]

[0030]

[Table 2]

[Brief description of drawings]

FIG. 1 is a plan view of a pull-out strength measuring frame.

[Explanation of reference numerals] 1: Place where the resin-cured molded product is formed (hatched portion) 2: Drawing piece 3, 4: Grasping part for performing drawing operation

Claims (5)

[Claims] 1. A composition comprising (A) an epoxy resin having two or more epoxy groups in a molecule, (B) an epoxy resin curing agent, and (C) an additive capable of chelating copper and 42 alloy. A thermosetting resin composition comprising: 2. An additive (C) capable of chelating copper and 42 alloys is one or more selected from anthranilic acid, aminophenol, gallic acid or ester of gallic acid, malonic acid and malic acid. The thermosetting resin composition according to claim 1, which is a compound of 1. 3. The thermosetting resin composition according to claim 1, wherein the epoxy resin (A) is a novolac type epoxy resin obtained by condensation of phenols and aldehydes. 4. The thermosetting resin composition according to claim 1, further comprising (D) a filler. 5. An electronic component, which is molded and sealed with the thermosetting resin composition according to claim 1, 2, 3 or 4.