JPH07268076A - Thermosetting resin and electronic component - Google Patents

Abstract

PURPOSE:To obtain the subject composition excellent in adhesion, humidity resistance and heat resistance. CONSTITUTION:This resin composition comprises a polymaleimide compound having at least two maleimido groups in the molecule, an epoxy resin having at least two epoxy groups in the molecule, an epoxy resin curing agent and a liquid polybutadiene (e.g. liquid epoxidized polybutadiene).

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 Conventionally, electrical and electronic parts such as semiconductors, which are molded and sealed using a thermosetting epoxy resin, have been widely used. This epoxy resin has been widely put into practical use because it is economically advantageous as compared with the hermetic sealing method using glass, metal, or ceramic. Among them, a polyfunctional epoxy resin typified by orthocresol novolac type epoxy resin, a novolac type phenolic resin, and a resin composition containing an inorganic filler as a main component are said to be excellent in workability, moldability, and reliability. However, in recent years, with the miniaturization of electronic devices, the higher integration of semiconductors, and the higher density of semiconductors, surface mounting methods have become mainstream that can mount as many elements as possible in a small space. As a result,
During the soldering process, the sealing material itself is exposed to the harsh conditions of solder bath temperature. Therefore, the heat resistance of the sealing material has become an important characteristic. Recently, thermosetting polyimide resin encapsulation has been proposed for the purpose of obtaining high heat resistance. However, thermosetting polyimide resins have major drawbacks in terms of adhesiveness and moisture resistance as compared with epoxy resins. In particular, if the adhesiveness is low, the adhesiveness to the lead frame is poor and the moisture resistance reliability is deteriorated, which is a serious problem.

[0003]

An object of the present invention is to provide a thermosetting resin composition having excellent adhesiveness, moisture resistance and heat resistance.

[0004]

From such a background, the present inventor has conducted diligent studies, and as a result, a polyimide-based compound having excellent heat resistance, and a resin composition composed of an epoxy resin, copper and a lead frame material The inventors have found that a resin composition obtained by blending a polymer that enhances the adhesive strength with 42 alloy (an alloy of Fe and Ni containing 42% Ni) is suitable for the above purpose, and completed the present invention.

That is, the present invention is as follows. (1) (A) Polymaleimide compound having two or more maleimide groups in the molecule, (B) Epoxy resin having two or more epoxy groups in the molecule, (C) Epoxy resin curing agent, and (D) A thermosetting resin composition comprising liquid polybutadiene.

(2) Further, the above (A), (B),
A thermosetting resin composition containing a filler (E) in addition to the components (C) and (D).

(3) An electronic component characterized by being molded and sealed with the thermosetting resin composition as described in (1) or (2) above.

The present invention will be described in detail below. The component (A) used in the present invention is a compound containing two or more maleimide groups represented by the following general formula 4 in the molecule.

[0009]

[Chemical 4] (In the formula, R ₁ represents a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms.)

The polymaleimide compound used in the present invention includes diphenylmethane bismaleimide, phenylene bismaleimide, diphenyl ether bismaleimide, diphenylsulfone bismaleimide, dicyclohexylmethane bismaleimide, xylene bismaleimide,
Tolylene bismaleimide, diphenylmethane bismethyl maleimide, diphenyl ether bismethyl maleimide, diphenyl sulfone bismethyl maleimide (including isomers), ethylene bismaleimide, hexamethylene bismaleimide, hexamethylene bismethyl maleimide, and these bismaleimide compounds and diamines Prepolymer having a bismaleimide skeleton at the terminal, which is obtained by adding compounds, 1,1,2,2-tetrakis (4-maleimidophenyl) ethane, 1,4-bis [bis (4-maleimidophenyl) methyl] Benzene, Tris [4- (4
Examples thereof include maleimide compounds such as aralkylaniline resins and methylmaleimide compounds prepared from a xylene derivative such as -maleimidophenoxy) phenyl] methane, aniline / formalin polycondensate, or aniline / α, α'-xylenedichloride.

Further, a polymaleimide compound made from bisaminophenoxy is used. It is the following general formula 5

[0012]

[Chemical 5] [In the formula, Ar is represented by the formula 6

[Chemical 6](In the formula, R₃, R_FourAre each independently a hydrogen atom or charcoal
Represents a hydrocarbon group having a prime number of 1 to 5, R_FiveHas 1 to 1 carbon atoms
5 divalent hydrocarbon group, or -CO-, -S-,-
C (CF₃)₂-, -SO₂-Or -O- divalent group
Indicates. Also, R _FiveMay be a single bond. )
R is a group₁, R₂Are each independently a hydrogen atom.
Or represents a hydrocarbon group having 1 to 5 carbon atoms. ] Is represented.

Examples of these are 2,7-bis (4,4'-aminophenoxy) naphthalene bismaleimide, 2,7-bis (3,3'-aminophenoxy) naphthalene bismaleimide, 2,7-bis ( 3,4'-aminophenoxy) naphthalene bismaleimide, 1,6-bis (4,
4'-aminophenoxy) naphthalene bismaleimide,
1,6-bis (3,3'-aminophenoxy) naphthalene bismaleimide, 1,6-bis (3,4'-aminophenoxy) naphthalene bismaleimide, 1,1-bis [4- (4
-Aminophenoxy) -3-t-butyl-6-methylphenyl] butane bismaleimide, 1,1-bis [4- (4
-Aminophenoxy) -3-t-butyl-6-methylphenyl] propane bismaleimide, 1,1-bis [4-
(4-Aminophenoxy) -3-t-butyl-6-methylphenyl] ethane bismaleimide, 1,1-bis [4-
(4-Aminophenoxy) -3-t-butyl-6-methylphenyl] methane bismaleimide, 1, 1, 1, 3, 3, 3
-Hexafluoro-2,2-bis [4- (4-aminophenoxy) -3-t-butyl-6-methylphenyl] propane bismaleimide,

2,2'-bis [4- (4-aminothiophenoxy) phenyl] propane bismaleimide, 4,4'-
Bis (4-aminophenoxy) benzophenone bismaleimide, 1,3-bis (4,4′-aminophenoxy) benzene bismaleimide, 1,3-bis (3,3′-aminophenoxy) benzenebismaleimide, 1,4 -Bis (4,
4'-aminophenoxy) benzene bismaleimide, 1,
4-bis (3,3'-aminophenoxy) benzene bismaleimide, 4,4'-bis (4-aminophenoxy) biphenyl bismaleimide, 4,4'-bis (3-aminophenoxy) biphenyl bismaleimide, 4, 4'-bis (4-aminophenoxy) -3,3 ', 5,5'-tetramethylbiphenyl bismaleimide, 4,4'-bis (3-aminophenoxy) -3,3', 5,5'- Tetramethylbiphenyl bismaleimide, 1,1-bis [4- (4-aminophenoxy) phenyl] cyclohexane bismaleimide, 1
-Phenyl-1,1'-bis [4- (4-aminophenoxy) phenyl] methane bismaleimide,

Bis [4- (4-aminophenoxy) phenyl] menthane bismaleimide, bis [2- (4-aminophenoxy) phenyl] menthane bismaleimide, 1
-[2- (4-Aminophenoxy) phenyl] -8-
[4- (4-aminophenoxy) phenyl] menthane bismaleimide, bis [4- (3-aminophenoxy) phenyl] menthane bismaleimide, bis [2- (3-aminophenoxy) phenyl] menthane bismaleimide,
1- [2- (3-aminophenoxy) phenyl] -8-
[4- (3-aminophenoxy) phenyl] menthane bismaleimide, bis [4- (4-aminophenoxy)-
3-Methylphenyl) menthane bismaleimide, bis [4- (4-aminophenoxy) -3,5-dimethylphenyl] menthane bismaleimide, bis [4- (4-aminophenoxy) -3-butyl-6-methylphenyl ] Menthane bismaleimide, bis [4- (4-amino-5-
Methylphenoxy) -3-methylphenyl] menthane bismaleimide, bis [4- (4-amino-5-methylphenoxy) -3,5-dimethylphenyl] menthane bismaleimide, bis [4- (4-amino-5- Methylphenoxy) -3-butyl-6-methylphenyl] menthane bismaleimide,

Bis [2- (4-aminophenoxy) -3
-Methylphenyl] menthane bismaleimide, 1- [2
-(4-Aminophenoxy) -3-methylphenyl]-
8- [4- (4-aminophenoxy) -3-methylphenyl] menthane bismaleimide, bis [4- (4-aminophenoxy) phenyl] dicyclopentane bismaleimide, bis [2- (4-aminophenoxy) phenyl ]
Dicyclopentane bismaleimide, [2- (4-aminophenoxy) phenyl]-[4- (4-aminophenoxy) phenyl] dicyclopentane bismaleimide, bis [4- (3-aminophenoxy) phenyl] dicyclopentane Bismaleimide, bis [2- (3-aminophenoxy) phenyl] dicyclopentane bismaleimide,
[2- (3-aminophenoxy) phenyl]-[4- (3
-Aminophenoxy) phenyl] dicyclopentane bismaleimide, bis [4- (4-aminophenoxy)-
3-methylphenyl) dicyclopentane bismaleimide,

Bis [4- (4-aminophenoxy) -3,
5-Dimethylphenyl] dicyclopentane bismaleimide, bis [4- (4-aminophenoxy) -3-butyl-6-methylphenyl] dicyclopentane bismaleimide, bis [4- (4-amino-5-methylphenoxy) )
-3-Methylphenyl] dicyclopentane bismaleimide, bis [4- (4-amino-5-methylphenoxy)
-3,5-Dimethylphenyl] dicyclopentane bismaleimide, bis [4- (4-amino-5-methylphenoxy) -3-butyl-6-methylphenyl] dicyclopentane bismaleimide, bis [2- (4 -Aminophenoxy) -3-methylphenyl] dicyclopentane bismaleimide, [2- (4-aminophenoxy) -3-methylphenyl]-[4- (4-aminophenoxy) -3-methylphenyl] dicyclopentane Examples include bismaleimide.

As the component (B) used in the present invention, a known epoxy resin can be used. Specific examples of these include phenol, o-cresol, naphthol, 3-methyl-6-tert-ary. A novolac-based epoxy resin derived from a novolac resin that is a reaction product of phenols such as butylphenol and formaldehyde, phloroglysin, tris- (4-hydroxyphenyl) -methane, 1,1,2,2, -tetrakis (4 −
Glycidyl ether compounds derived from trihydric or higher phenols such as (hydroxyphenyl) ethane, bisphenol A, bisphenol F, hydroquinone, resorcin, 1,1'-bis (3-t-butyl-6-methyl-4-)
Glycidyl ether compounds derived from dihydric phenols such as (hydroxyphenyl) butane, tetramethylbiphenol and naphthalenediol, or diglycidyl ether compounds derived from halogenated bisphenols such as tetrabromobisphenol A, phenols and aromatic carbonyls A glycidyl ether compound of polyhydric phenol obtained by a condensation reaction with a compound,

P-aminophenol, m-aminophenol, 4-aminometacresol, 6-aminometacresol, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenylether, 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 compounds derived from, etc., 2,2-bis (3,4
-Epoxycyclohexyl) propane, 2,2-bis [4
Alicyclic epoxy resin such as-(2,3-epoxypropyl) cyclohexyl] propane, vinylcyclohexenedioxide, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, N, N-
There is diglycidyl aniline and the like, and one or more of these epoxy resins are used. Of these, o-cresol novolac epoxy resins, tetramethylbiphenol, and glycidyl ether compounds of polyhydric phenols obtained by condensation reaction of phenols with aromatic carbonyl compounds are preferable from the viewpoint of curability and heat resistance or adhesiveness.

As the epoxy curing agent as the component (C), 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-hydroxyphenylindan-5 or 7-ol, 1,3,3-trimethyl-1-p-hydroxyphenylindan-6-ol, resorcin, hydroquinone, catechol and phenol, phenols such as o-cresol Polyphenol compounds such as phenol novolak, which is a reaction product of formaldehyde, and a reaction product of dicyclopentadiene and phenol,

Polycarboxylic acids such as maleic acid, phthalic acid, nadic acid, methyl-tetrahydrophthalic acid and methyl nadic acid and their anhydrides, diaminodiphenylmethane,
Polyamine compounds such as diaminodiphenyl sulfone, diaminodiphenyl ether, phenylenediamine, diaminodicyclohexylmethane, xylylenediamine, toluenediamine, diaminodicyclocyclohexane, dichloro-diaminodiphenylmethane (each containing isomers), ethylenediamine, hexamethylenediamine,
Furthermore, active hydrogen-containing compounds capable of reacting with an epoxy group such as dicyandiamide and tetramethylguanidine can be exemplified. Of these, phenol novolac resins are preferably used from the viewpoint of curability and moisture resistance.

In the composition of the present invention, the quantitative ratio of each component of the resin can be appropriately selected depending on the application, desired heat resistance and the like. However, it is generally preferable to select the content rate of the bismaleimide compound {(A) / [(A) + (B) + (C)]} to be 90% to 10%. More preferably, 7
It is between 30% and 30%. If the blending ratio of the bismaleimide compound deviates from the above range, the moisture resistance and the heat resistance decrease, which is not preferable.

The mixing ratio of the epoxy resin as the component (B) and the curing agent as the component (C) is 0.
It is preferable to mix 5 to 1.2 equivalents, and more preferable to mix equivalents. If the blending ratio of the component (B) and the component (C) deviates from the equivalence ratio, the moisture resistance, the curability, etc. 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. It is indispensable especially when it is used as a sealing material. Examples of such catalysts include triphenylphosphine, tri-4-methylphenylphosphine and tri-4-
Methoxyphenylphosphine, tributylphosphine,
Organic phosphine compounds such as trioctylphosphine and tri-2-cyanoethylphosphine, tributylamine, triethylamine, 1,8-diazabicyclo (5,5)
4,0) Undecene-7, tertiary amines such as triamylamine, quaternary ammonium salts such as benzyltrimethylammonium chloride, benzyltrimethylammonium hydroxide, triethylammonium tetraphenylborate, imidazoles, boron trifluoride complex, transition Metal acetylacetonate, benzoyl peroxide, di-t-butyl peroxide, dicumyl peroxide, lauroyl peroxide, acetyl peroxide, methyl ethyl ketone peroxide, cyclohexanone peroxide, t-butyl hydroperoxide, azobisbutyronitrile Examples of the radical initiator include, but are not limited to, these. Among these, organic phosphine compounds, imidazoles and salts thereof (specifically, tetraphenylphosphonium tetraphenylborate, 4
-Methylimidazole tetraphenylborate etc.) or triethylammonium tetraphenylborate are particularly preferable.

Further, in order to adjust the curing speed, it is possible to use a known polymerization inhibitor together. 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), 4,4'-thiobis (3-methyl-6-t-butylphenol), hydroquinone Phenols such as monomethyl ether, hydroquinone, catechol, pt
-Polyphenols such as -butylcatechol, 2,5-di-t-butylhydroquinone, methylhydroquinone, t-butylhydroquinone and pyrogallol, phenothiazine compounds such as phenothiazine, benzophenothiazine and acetamidophenothiazine, N-nitrosodiphenylamine, N- There are N-nitrosamine-based compounds such as nitrosodimethylamine.

The liquid polybutadiene which is the component (D) used in the present invention is preferably a liquid polybutadiene having a molecular weight of 300 to 5000 obtained by polymerization of butadiene. It is preferable that these polybutadienes have a functional group such as an acid anhydride group, an epoxy group, a phenolic hydroxyl group, a carboxylic acid group, an acryl group and a methacryl group in the molecule from the viewpoint of adhesiveness. Among them, shown by the following general formula 7,
Epoxy group-containing polybutadiene is particularly preferably used.

[0027]

[Chemical 7] (In the formula, h and k represent a number of 1 to 50, and m and n are 0.
Represents a number from -50. Further, the above formula represents a random or block copolymer. )

In the present invention, the blending amount of the component (D) is preferably 2 to 30 parts by weight, and more preferably 5 to 100 parts by weight of the total amount of the components (A), (B) and (C). 20 parts by weight. If the amount is less than this range, the effect of improving the adhesiveness is poor, and if the amount is too large, the mechanical properties and heat resistance tend to deteriorate.

Examples of the filler (E) 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. Silica, crystalline silica and alumina are preferably used.

Further, 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 92% by weight, and more preferably the total amount of the resin composition. Is 60 to 90% by weight. If the amount of the filler is less than 30% by weight, the moisture resistance is inferior, and if it exceeds 92% by weight, there is a problem in moldability.

In the present invention, if necessary, a natural wax, a synthetic wax, a higher fatty acid and its metal salt, a releasing agent such as paraffin or a coloring agent such as carbon black, and a surface of a silane coupling agent or the like. A treating agent or 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 or injection molding.

[0035]

The thermosetting resin composition of the present invention is mainly used for sealing electronic parts such as semiconductors. And workability,
The cured product has excellent heat resistance, particularly strength and adhesiveness when heated, and more excellent moisture resistance than conventionally known heat resistant resin compositions, and is extremely useful as a composition for a sealing material.

[0036]

EXAMPLES Examples of the present invention will be shown below, but the present invention is not limited thereto. The evaluation of the cured molded product is as follows.

Gel time: 0.5 g of the kneaded product obtained in each of the examples and comparative examples was placed in a recess of a hot plate at 180 ° C., and the time until gelation was measured.

Glass transition temperature: thermomechanical analyzer (S
HIMADZU DT-30).

Bending strength, flexural modulus: JIS K-6
According to 911, Instron Universal Material Testing Machine (SHIM
ADZU IS-10T). Measurement temperature is 2
0 ° C and 240 ° C.

Water absorption rate: constant temperature and humidity (TABAI PR
-2) was used to measure the weight change under the conditions of 85 ° C./85% RH.

Spiral flow: EMMI-1-66
Was carried out under the conditions of 190 ° C./70 kg / cm ² .

Barcol hardness: 190 ° C./120 seconds molding conditions.

Adhesion test: A compound was molded using a pull-out strength measuring frame made of copper and 42 alloy, and after post-curing, the pull-out strength of the frame was used for evaluation.

Solder cracking property: Simulated IC (52-pin QFP package: package thickness 2.05 mm) 8
The number of individual IC's with cracks after moisture absorption under conditions of 5 ° C./85% RH / 72 hours and immediately after immersion in a solder bath at 240 ° C. for 30 seconds. 10 test individuals.

Adhesion evaluation: The peeling of the back of the die pad of the simulated IC after the solder cracking test was evaluated by the ultrasonic probe imager (AT-5000, Hitachi Construction Machinery Co., Ltd.) in the ratio of the peeled area.

Reference Example 1 Synthesis of N, N′-bis (4-aminophenoxyphenyl) menthane bismaleimide: A 5 liter four-necked flask was charged with 237.3 g of maleic anhydride and 2373 g of chlorobenzene and dissolved by stirring under a nitrogen stream. Let 1625.1 g of a dimethylacetamide (DMAc) solution of bis (4-aminophenoxyphenyl) menthane (concentration 34.3% by weight) was added dropwise to the flask at 25 ± 5 ° C. over 2 hours using a dropping funnel. The reaction was continued at 35 ° C. for 2 hours to complete the amidation reaction. Then p-toluenesulfonic acid monohydrate 10.46
Add g and perform azeotropic dehydration under reduced pressure at 100 ° C for 1 hour, 110 ° C for 1 hour, and then gradually return to normal pressure.
The dehydration ring closure reaction was performed at 5 ° C for 4 hours. Generated water
The reaction proceeded while separating it from the system using an-Stark azeotropic dehydrator.

Then, under reduced pressure, chlorobenzene and then D
A total of 89% of MAc was recovered. Subsequently, 2200 g of methyl isobutyl ketone (hereinafter abbreviated as MIBK) was added and dissolved. The solution was cooled to 60 ° C., and sodium bicarbonate and 1000 g of water, which were weighed so that the pH of the aqueous layer was 5 to 7, were added to neutralize, followed by washing and liquid separation. Further, 1000 g of 15% saline at 60 ° C
It was washed twice with water and separated, then azeotropically dehydrated under reduced pressure, and filtered to remove salts. The filtrate was concentrated under reduced pressure, and after finally reaching the condition of 150 ° C / 5Torr, the product was taken out from the flask in a molten state to obtain a light brown solid in a yield of 724 g.
(Yield 98.7%) (Product is MPD).

Mass spectrum M + = 666 Melting point 96-98 ° C. 1H-NMR spectrum δ: 0.6-2.1 ppm (m, aliphatic), 2.8 ppm (m, methine), 6.8 ppm (s, imido group), 6.9-7.4ppm (m, aromatic) ・ Infrared absorption spectrum: 1238 cm ^-1 (ether bond),
1712 cm ^-1 (imide bond)

Reference Example 2 Synthesis of N, N'-bis [4- (4-aminophenoxy) -3,5-dimethylphenyl] dicyclopentane bismaleimide: Maleic anhydride 58.8 in a 1-liter four-necked flask.
g and 137.2 g of acetone were charged, and they were dissolved by stirring under a nitrogen stream. While keeping the temperature between room temperature and 35 ° C,
Dicyclopentane oligomer having-(4-aminophenoxy) -3,5-dimethylphenyl group [DXP-L-9-1 (Nippon Sekiyu KK-made reaction product of 2,6-xylenol and dicyclopentadiene. Equivalent amount 191 g / eq) is reacted with p-chloronitrobenzene and then the nitro group is reduced. 90% of bis [4- (4-aminophenoxy) -3,5-dimethylphenyl] dicyclopentane measured by GPC
Including. Amine equivalent 275 g / eq)] 150.0 g in acetone 3
The solution dissolved in 50 g was added dropwise to the flask over 2 hours. Stirring was continued for another 3 hours. Then triethylamine 16.6g
Was added and stirred at room temperature for half an hour, then nickel acetate 0.58 g
Was added and the temperature was raised to 40 ° C. After 72.4 g of acetic anhydride was added dropwise over 1 hour, the mixture was kept at the same temperature until the reaction was completed.
After the reaction was completed, the reaction mixture was discharged into 1000 g of pure water. The crystals were collected by filtration, washed with water and then with methanol, heated under reduced pressure and dried (product is designated as MXP). Yellow crystals. Yield 189.4 g (Yield 97.9%)

Examples 1 to 6 MPD, MXP and N, obtained in Reference Examples 1 and 2 above,
N'-diphenylmethane bismaleimide (Sumitomo Chemical Co., Ltd., trade name Bestlex BH-180), glycidyl ether of o-cresol novolac as an epoxy resin (trade name Sumiepoxy ESCN-195XL, Sumitomo Chemical Co., Ltd.), Epoxy equivalent 196g / equivalent, hydrolyzable chlorine
330 ppm) and glycidyl ether of brominated phenol novolac (trade name: Sumiepoxy ESBP-280, Sumitomo Chemical Co., Ltd., epoxy equivalent 285 g / equivalent, hydrolyzable chlorine 440 ppm), phenol novolac as an epoxy curing agent (Guneiei) Chemical Industry Co., Ltd., trade name PSM-426
1, OH equivalent 106 g / eq), Nisseki Polybutadiene E-1800-6.5 as epoxidized liquid polybutadiene
(Nippon Petrochemical Co., Ltd., epoxy equivalent 246 g / eq) and E
-1000-8.0 (Nippon Petrochemical Co., Ltd., epoxy equivalent 200 g / eq), triphenylphosphine and tetraphenylphosphonium tetraphenylborate as a curing accelerator, and crushed fused silica (trade name FS) as a filler. -8
91, manufactured by Denki Kagaku Co., Ltd., spherical fused silica (trade name: FB-7)
4, Electrochemical Co., Ltd., carnauba wax as a release agent, coupling agent (γ-glycidoxypropyltrimethoxysilane, trade name SH-6040, manufactured by Toray Dow Corning Silicone Co., Ltd. and N-phenyl -Γ-Aminopropyltrimethoxysilane, trade name KBM-573, manufactured by Shin-Etsu Chemical Co., Ltd. was added in an amount (g) shown in Table 1, heated and kneaded with a roll, and transfer molding was performed. In addition, 20
Post-cure was performed at 0 ° C. for 5 hours to obtain a cured molded product. 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 to 3 Cured moldings were obtained in the same manner as in Examples 1 to 6 except that the epoxidized liquid polybutadiene was not used. The compounding recipe and the physical properties of the cured molded product are shown in Tables 1 and 2. Table 1
In, the arrow indicates that it is the same as the column on the left.

[0052]

[Table 1]

[0053]

[Table 2]

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Reference number within the agency FI Technical display location C08L 63/00 NJW H01L 23/29 23/31 (72) Inventor Kazuo Takebe 6 Kitahara, Tsukuba, Ibaraki Prefecture Sumitomo Chemical Co., Ltd. (72) Inventor Noriaki Saito 6 Kitahara, Tsukuba, Ibaraki Prefecture Sumitomo Chemical Co., Ltd.

Claims (7)

[Claims] 1. A polymaleimide compound having (A) two or more maleimide groups in a molecule, (B) an epoxy resin having two or more epoxy groups in a molecule, (C) an epoxy resin curing agent, and ( D) A thermosetting resin composition comprising liquid polybutadiene. 2. A liquid polybutadiene which is the component (D) is a polybutadiene having in the molecule one or more functional groups selected from acid anhydride groups, epoxy groups and phenolic hydroxyl groups. The thermosetting resin composition according to claim 1. 3. The thermosetting resin composition according to claim 1, wherein the liquid polybutadiene as the component (D) is an epoxidized liquid polybutadiene represented by the following general formula 1. [Chemical 1] (In the formula, h and k represent a number of 1 to 50, and m and n are 0.
Represents a number from -50. Further, the above formula represents a random or block copolymer. ) 4. The thermosetting resin composition according to claim 1, 2 or 3, wherein the polymaleimide compound (A) is a polymaleimide compound represented by the following general formula 2. [Chemical 2] [In the formula, Ar is represented by the following formula: (In the formula, R ₃ and R ₄ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms, and R ₅ represents 1 to 1 carbon atoms.
5 divalent hydrocarbon groups, or -CO-, -S-,-
_{C (CF 3) 2 -,} - shows a or a divalent group of -O- - SO _2. Further, R ₅ may be a single bond. ), R ₁ and R ₂ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms. ] 5. The thermosetting resin composition according to claim 4, wherein R _{5 in the} formula 3 according to claim 4 is a group selected from menthane and dicyclopentane. 6. The thermosetting resin composition according to claim 1, further comprising (E) a filler. 7. An electronic component, which is molded and sealed with the thermosetting resin composition according to claim 1, 2, 3, 4, 5 or 6.