JPH06329762A - Thermosetting resin composition and electronic component - Google Patents

Abstract

(57) [Abstract] [Purpose] To provide a thermosetting resin composition having excellent adhesiveness, moisture resistance and heat resistance. [Structure] (A) Polymaleimide compound having two or more maleimide groups in a molecule, (B) Epoxy resin having two or more epoxy groups in a molecule, (C) Epoxy resin curing agent, and (D) A thermosetting resin composition comprising an adhesive resin containing a specific acrylic resin-based adhesive resin or a thermoplastic copolyester resin, and an electronic component molded and sealed with the composition.

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.

[0003]

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. The purpose of the present invention is to
It is intended to provide a thermosetting resin composition having excellent adhesiveness, moisture resistance and heat resistance.

[0004]

Means for Solving the Problems As a result of intensive investigations, the present inventors have found that a resin composition composed of a polyimide compound and an epoxy resin having excellent heat resistance is bonded to copper and 42 alloy, which are the materials of the lead frame. The present inventors have found that a resin composition obtained by blending an additive that enhances strength meets the above-mentioned object, and completed the present invention. That is, the present invention is as follows.

(1) (A) a polymaleimide compound having two or more maleimide groups in the molecule, (B) an epoxy resin having two or more epoxy groups in the molecule, (C) an epoxy resin curing agent, and (D) (a) 10 to 50% by weight
Acrylonitrile or methacrylonitrile or a mixture thereof, (b) 45 to 85% by weight of ethyl acrylate, butyl acrylate or 2-ethylhexyl acrylate or a mixture thereof, and (c)
A thermosetting resin composition comprising 2 to 10% by weight of an acrylic resin adhesive resin which is a copolymer of acrylic acid, methacrylic acid, or itaconic acid or a mixture thereof.

(2) (A) a polymaleimide compound having two or more maleimide groups in the molecule, (B) an epoxy resin having two or more epoxy groups in the molecule, (C) an epoxy resin curing agent, and (D ′) 40 to 100 mol% of terephthalic acid as a dicarboxylic acid component and 0 to 60 mol% of other aromatic dicarboxylic acid, and 1,4 butanediol 40 to 10 as a low molecular weight glycol component.
0 mol% and diethylene glycol or 1,6-
A thermoplastic copolymer polyester resin (d) comprising 0 to 60 mol% of hexanediol and 0 to 10 mol% of polytetramethylene glycol having a molecular weight of 600 to 6000, based on the total dicarboxylic acid, an epoxy group and a carboxylic acid. Ethylene (e) containing one or more functional groups selected from the group or dicarboxylic acid anhydride groups, or another type of thermoplastic resin (f) added with these, if necessary. ) And a polyfunctional epoxy compound (g), and a thermosetting resin composition.

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

(4) 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 3 in the molecule.

[Chemical 3]

[0010] (In the formula, R ₆ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.)

As the polymaleimide compound used in the present invention, 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'-tolylene bismaleimide, N,
N'-diphenylmethanebismethylmaleimide, N,
N'-diphenyl ether bismethyl maleimide, N,
N′-diphenylsulfone bismethylmaleimide (including isomers), N, N′-ethylene bismaleimide, N, N′-hexamethylene bismaleimide, N,
N′-hexamethylenebismethylmaleimide, and a prepolymer having an N, N′-bismaleimide skeleton at the end, which is obtained by adding these N, N′-bismaleimide compounds and diamines, and aniline / formalin polycondensation Examples thereof include maleimide compounds and methylmaleimide compounds.

In the present invention, a polymaleimide compound represented by the following general formula 4 is used, which is prepared from bisaminophenoxy as a raw material.

[Chemical 4]

[0013] [In the formula, R ₁ and R ₂ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms, and Ar is represented by the formula 5

[Chemical 5]

[0014] (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 is 1 carbon atom.
~ 15 divalent hydrocarbon groups, or -CO-, -S
_{-, - C (CF 3)} 2 -, - SO 2 - or -O- 2
Indicates a valence group. Further, R ₅ may be directly bonded by a single bond. )] Examples of these compounds include N, N′-
Bis (aminophenoxy) naphthalene bismaleimide,
N, N'-bis (aminophenoxy) biphenyl bismaleimide, N, N'-bis (aminophenoxy) diphenylmethane bismaleimide, N, N'-bis (aminophenoxy) diphenylsulfone bismaleimide, N,
N'-bis [(aminophenoxy) -3-t-butyl-
6-methylphenyl] butane bismaleimide, N, N ′
-Bis (aminophenoxyphenyl) menthane bismaleimide, N, N'-bis (aminophenoxyphenyl)
Examples thereof include dicyclopentane bismaleimide (each including an isomer).

As the component (B) used in the present invention, known epoxy resins can be used. Specific examples of these are reaction products of phenols such as phenol and o-cresol with formaldehyde. Trihydric or higher phenols such as novolac epoxy resins derived from certain novolac resins, phloroglysin, tris- (4-hydroxyphenyl) -methane, 1,1,2,2, -tetrakis (4-hydroxyphenyl) ethane Glycidyl ether compounds derived from bisphenol, 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 and tetramethylbiphenol, or halogenated bisphenols such as tetrabromobisphenol A Diglycidyl ether compounds derived from bisphenols, glycidyl ether compounds of polyhydric phenols 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'-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 A hydantoin-based epoxy compound derived from

2,2-bis (3,4-epoxycyclohexyl) propane, 2,2-bis [4- (2,3-epoxypropyl) cyclohexyl] propane, vinylcyclohexenedioxide, 3,4-epoxycyclohexylmethyl There are alicyclic epoxy resins such as -3,4-epoxycyclohexanecarboxylate, N, N-diglycidylaniline 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, polycarboxylic acids such as maleic acid, phthalic acid, nadic acid, methyl-tetrahydrophthalic acid, methyl nadic acid and their anhydrides, diaminodiphenylmethane, diaminodiphenylsulfone, diamino Diphenyl ether, phenylenediamine, diaminodicyclohexylmethane, xylylenediamine, toluenediamine, diaminodicyclocyclohexane, dichloro-diaminodiphenylmethane (each containing isomers), Examples thereof include polyamine compounds such as tolylenediamine and hexamethylenediamine, and further active hydrogen-containing compounds capable of reacting with an epoxy group such as dicyandiamide and tetramethylguanidine. Above all,
Phenolic novolac resins are preferably used in terms of curability and moisture resistance.

In the composition of the present invention, the quantitative ratio of each component of the resin excluding the components (D) and (D ') is the purpose of use,
It can be appropriately selected according to desired heat resistance and the like. However, in general, the content rate of the bismaleimide compound {(A) /
It is preferable to select [(A) + (B) + (C)]} to be 90% to 10%. More preferably, it is 70 to 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.

Regarding the mixing ratio of the epoxy resin which is the component (B) and the curing agent which is the component (C), it is preferable to mix them in equal amounts. If the blending amount of the component (B) and the component (C) deviates from the equimolar amount, the moisture resistance, the 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. 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.

It is also possible to use a known polymerization inhibitor together in order to adjust the curing speed. 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 adhesive resin (D) or (D ') used in the present invention is an adhesive resin containing an acrylic resin-based adhesive resin or a thermoplastic copolyester resin. Acrylic resin adhesive resin (a) 10 ~
50% by weight of acrylonitrile or methacrylonitrile or a mixture thereof, (b) 45 to 85% by weight of ethyl acrylate, butyl acrylate, or 2-ethylhexyl acrylate or a mixture thereof and (c) 2 to 10% by weight of acrylic acid, Copolymers of methacrylic acid or itaconic acid or mixtures thereof are used, preferably (a) 20-40% by weight acrylonitrile, (b) 50-80% by weight butyl acrylate,
(C) 2 to 10% by weight of a copolymer of methacrylic acid is used. This resin can be synthesized by a method such as emulsion polymerization, suspension polymerization or solution polymerization according to a usual radical polymerization method. As specific examples of these acrylic resin-based adhesive resins, Permatac AW-060, Permatac AW-030, Permatac K-4 (these are trade names, manufactured by Sumitomo Chemical Co., Ltd.) and the like are commercially available products. Can be mentioned.

The adhesive resin containing the thermoplastic copolyester resin will be described below. In the thermoplastic copolyester resin (d), the dicarboxylic acid component is 40 to 100 mol% of terephthalic acid, and other aromatic dicarboxylic acid. It is composed of 0 to 60 mol% of acid. Examples of other aromatic dicarboxylic acids include isophthalic acid, orthophthalic acid, and 2,6-naphthalenedicarboxylic acid. Isophthalic acid is most suitable from an industrial viewpoint. On the other hand, as the low molecular weight glycol component, 1,4-
It is composed of 40 to 100 mol% of butanediol and 0 to 60 mol% of diethylene glycol or 1,6-hexanediol, and polytetramethylene glycol having a molecular weight of 600 to 6000 is composed of 0 to 10 mol% based on the total dicarboxylic acid component. The melting point of the thermoplastic copolyester resin (d) is not particularly limited, but is preferably about 60 to 150 ° C. in terms of handling.

One or two selected from an epoxy group, a carboxylic acid group or a dicarboxylic acid anhydride group.
The ethylene copolymer (e) containing one or more functional groups is
Monomers copolymerizable with ethylene and ethylene having the above-mentioned functional group by a known method such as a high-pressure radical polymerization method, a solution polymerization method or an emulsion polymerization method, for example, α, β-unsaturated glycidyl ester, α, β-unsaturated monomer. It is obtained by copolymerizing with an unsaturated monomer such as saturated glycidyl ether, α, β-unsaturated carboxylic acid and its anhydride. Specific examples of unsaturated monomers include glycidyl methacrylate, glycidyl acrylate, allyl glycidyl ether, 2-methylallyl glycidyl ether, acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, maleic anhydride, itaconic anhydride. , Hymic acid anhydride and the like are exemplified. The amount of these unsaturated monomers is about 0.01 to about 20 mol%, preferably about 0.1 to about 10 mol%. Moreover,
A copolymer produced by grafting the above-mentioned unsaturated monomer having a functional group onto a homopolymer or copolymer of ethylene can also be used. Among these ethylene copolymers, an epoxy group-containing ethylene copolymer is preferable from the viewpoint of adhesiveness.

Preferred as another type of thermoplastic resin (f) are ethylene polymers, polyolefin elastomers, vinyl aromatic hydrocarbon polymers or copolymers, (meth) acrylic acid ester polymers or copolymers. One or more resins selected from the polymers. Specific examples of these, as the ethylene-based polymer, ethylene-vinyl acetate copolymer, ethylene-vinyl ester copolymer, ethylene-methyl methacrylate copolymer, ethylene-ethyl acrylate copolymer and the like. As the polyolefin-based elastomer, ethylene-propylene copolymer rubber, ethylene-
Examples thereof include propylene-non-conjugated diene copolymer rubber and ethylene-butene copolymer rubber. The vinyl aromatic hydrocarbon polymer is polystyrene, polyvinyltoluene, styrene-acrylonitrile butadiene copolymer, or the like, and the (meth) acrylic acid ester-based polymer is methyl acrylate polymer, methyl methacrylate. Examples thereof include polymers, butyl acrylate copolymers, methyl methacrylate-butyl acrylate copolymers, and the like.

As the polyfunctional epoxy compound (g), the same epoxy resin as the above-mentioned component (B) is preferably used. Specific examples of the adhesive resin containing these thermoplastic copolyester resins include Bond First 2
Examples of commercially available products include A, Bond First 2B, Bond First 7B, Bond First E, Bond First G (above, trade name, manufactured by Sumitomo Chemical Co., Ltd.).

Regarding the quantitative ratio of each component in the adhesive resin containing the thermoplastic copolyester resin, the thermoplastic copolyester resin (d) component is 40%.
To 80% by weight, preferably 50 to 70% by weight, and the total amount of the ethylene copolymer (e) component and the different thermoplastic resin (f) component is 60 to 20% by weight, preferably 50 to 30% by weight. And the proportion of the (e) component in the total amount of the (e) component and the (f) component is 5 to 100% by weight, preferably 1
It is 0 to 80% by weight. Further, the polyfunctional epoxy compound (g) component is a component (d), a component (e) and a component (f).
The total amount of the components is preferably 0.5 to 100 parts by weight.
20 parts by weight.

In the present invention, the content of the component (D) or (D ') can be appropriately selected. However, in general, the content of the (D) or (D ') component {(D) or (D') / [(A) + (B) + (C) + (D) or (D ')] } Is preferably selected to be 3% to 30%. More preferably, it is 5 to 20%. 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. Furthermore, the blending ratio of the filler can be appropriately determined according to the purpose, but when used for sealing a semiconductor, it is preferably 30 to 90% by weight, more preferably 60 to 90% by weight based on the total amount of the resin composition. It is 85% by weight. When the amount of the filler is less than 30% by weight, the moisture resistance is inferior, and 9
If it exceeds 0% 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 a metal salt thereof, 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, injection molding or the like.

[0034]

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

[0035]

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: 18 kneaded materials obtained in Examples and Comparative Examples
0.5 g was taken in the recess of the hot plate at 0 ° C., and the time until gelation was measured.

Glass transition temperature: thermomechanical analyzer (SH
It was measured using IMADZU DT-30).

Bending strength, flexural modulus: Instron universal material testing machine (SHIMADZU IS-10T) according to JIS K-6911
). The measurement temperature is 20 ° C (normal state) and 2
It is 40 ° C (when hot).

Moisture absorption rate: The change in weight was measured under the conditions of 85 ° C./85% RH using a constant temperature and constant humidity chamber (TABAI PR-2).

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 on a copper foil (18 μm: manufactured by Furukawa Circuit Wheels Co., Ltd.) and an aluminum foil (20 μm), and evaluated by peeling strength after post-curing.

Solder cracking property: Simulated IC (52-pin QF
P package: Package thickness 2.05mm) 85 ℃ / 85% RH / 7
The number of individual ICs with cracks after absorbing moisture for 2 hours and immediately immersing them in a 240 ° C solder bath for 30 seconds. 10 test individuals.

Reference Example 1 Synthesis of N, N'-2,7-bis (4,4'-aminophenoxy) naphthalene bismaleimide Maleic anhydride 157.5 g in a 2-liter four-necked flask.
950.8 g of acetone and acetone were charged and dissolved by stirring under a nitrogen stream. 250.0 g of 2,7-bis (4,4'-aminophenoxy) naphthalene was added as powder in two hours while maintaining the temperature at room temperature to 35 ° C. The stirring was further continued for 3 hours, and the completion of the reaction was confirmed (first step reaction). Subsequently, 44.3 g of triethylamine was added and stirred at room temperature for half an hour, 1.55 g of nickel acetate was added, and the temperature was raised to 40 ° C. After 193.9 g of acetic anhydride was added dropwise over 1 hour, the reaction was continued at the same temperature (second step reaction). After the reaction,
The reaction mixture was discharged into 1 liter of water. Subsequently, the crystals were collected by filtration. The crystals were washed with water and then with methanol, heated under reduced pressure and dried to obtain the desired product (hereinafter referred to as M
27N). Yellow crystals. Yield 359.4 g (98.
0%). This product was recrystallized from a mixed solvent of methyl cellosolve / isopropyl alcohol and had a melting point of 98-
It was 101 ° C.

Reference Example 2 Synthesis of N, N'-bis [4- (4-aminophenoxy) -3,5-dimethylphenyl] dicyclopentane bismaleimide Maleic anhydride 58.8 g in a 1-liter four-necked flask
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 ℃,
Dicyclopentane oligomer having (4-aminophenoxy) -3,5-dimethylphenyl group [manufactured by Nippon Oil Co., Ltd.
DXP-L-9-1 (reaction product of 2,6-xylenol and dicyclopentadiene. Hydroxyl equivalent 191 g / eq) was reacted with p-chloronitrobenzene and then the nitro group was reduced. It contains 90% of bis [4- (4-aminophenoxy) -3,5-dimethylphenyl] dicyclopentane by GPC measurement. Amine equivalent 275 g / eq)] 150.0 g with acetone 350
The solution dissolved in 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 pure 1000 g. The crystals were collected by filtration, washed with water and then with methanol, heated under reduced pressure and dried (hereinafter referred to as MXP). Yellow crystals. Yield 189.4 g (97.9% yield).

Reference Example 3 Synthesis of N, N'-bis (4-aminophenoxyphenyl) menthane bismaleimide A 300-ml four-necked flask was charged with 10.8 g of maleic anhydride and 25.2 g of acetone and stirred under a nitrogen stream. Dissolved. 25.3 g of bis (4-aminophenoxyphenyl) menthane (amine equivalent of 253
(g / eq) was dissolved in 59.1 g of acetone and the solution was added dropwise over 2 hours. Stirring was continued for another 3 hours. Next, after adding 3.04 g of triethylamine and stirring at room temperature for half an hour, 0.11 g of nickel acetate was added and the temperature was raised to 40 ° C. Acetic anhydride 13.
After 3 g was added dropwise for 1 hour, the reaction was continued at the same temperature. After completion of the reaction, 200 g of pure was added dropwise to precipitate crystals from the reaction mixture. The crystals were collected by filtration, washed with water and then with methanol, heated under reduced pressure and dried. This was recrystallized from methyl cellosolve / isopropanol to obtain yellow crystals (hereinafter referred to as MPD). Yield 23.5 g (Yield 70.
6%).

Examples 1 to 7 M27N, MXP and MP obtained in Reference Examples 1 to 3 above
D and N, N'-diphenylmethane bismaleimide (Sumitomo Chemical Co., Ltd., trade name Bestlex BH-
180), acrylic adhesive resin (Sumitomo Chemical Co., Ltd.)
Manufactured by trade name Permatac AW-060 and Permatac K-4), thermoplastic polyester copolymer-containing adhesive resin (Sumitomo Chemical Co., Ltd., trade name Bond First 2A and Bond First 2B), as epoxy resin o-cresol novolac glycidyl ether (Sumitomo Chemical Co., Ltd., trade name Sumiepoxy ESCN-195XL,
Epoxy equivalent 196 g / equivalent, hydrolyzable chlorine 330 ppm) and glycidyl ether compound of brominated phenol novolac (Sumitomo Chemical Co., Ltd., trade name Sumiepoxy ESBP)
-280, epoxy equivalent 285g / equivalent, hydrolyzable chlorine 440pp
m), and phenol novolac as an epoxy curing agent (manufactured by Gunei Chemical Industry Co., Ltd., trade name PSM-4261, OH equivalent = 106 g)
/ eq), triphenylphosphine as a curing accelerator,
4-Methylimidazole and tetraphenylphosphonium tetraphenylborate, crushed fused silica as a filler (trade name FS-891, manufactured by Denki Kagaku), spherical fused silica (trade name FB-74, electrochemical (stock) )), A carnauba wax as a release agent, a coupling agent (γ-glycidoxypropyltrimethoxysilane, trade name SH-6040, manufactured by Toray Dow Corning Silicone Co., Ltd. and (N-phenyl-γ-aminopropyl). Trimethoxysilane, trade name
KBM-573, manufactured by Shin-Etsu Chemical Co., Ltd., in the amounts shown in Table 1 (g
), A roll pulling agent (SH-6040 Toray Dow Corning Silicone was heated and kneaded, and subjected to transgranular spher molding. Further, post-curing was performed at 200 ° 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 4 Cured moldings were obtained in the same manner as in Examples 1 to 7 except that the acrylic adhesive resin and the thermoplastic polyester copolymer-containing adhesive resin were not used. Tables 3 and 4 show the compounding formulation and the physical properties of the cured molded product.

[0048]

[Table 1]

[0049]

[Table 2]

[0050]

[Table 3]

[0051]

[Table 4]

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁵ Identification number Reference number within the agency FI Technical indication location H01L 23/29 23/31 (72) Inventor Shinichiro Kitayama 6 Kitahara, Tsukuba-shi, Ibaraki Sumitomo Chemical Co., Ltd. Within

Claims (5)

[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) 10 to 50% by weight of acrylonitrile or methacrylonitrile or a mixture thereof, (b) 45 to 85% by weight of ethyl acrylate, butyl acrylate or 2-ethylhexyl acrylate or a mixture thereof, and (c) 2. ~ 1
A thermosetting resin composition comprising 0% by weight of an acrylic resin-based adhesive resin which is a copolymer of acrylic acid, methacrylic acid, or itaconic acid or a mixture thereof. 2. 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 ') consisting of 40 to 100 mol% of terephthalic acid as a dicarboxylic acid component and 0 to 60 mol% of other aromatic dicarboxylic acid, and 40 to 100 mol% of 1,4-butanediol and diethylene glycol or 1 as a low molecular weight glycol component. , 6-hexanediol from 0 to 60 mol% and a molecular weight of 60
0 to 6000 polytetramethylene glycol is selected from the thermoplastic copolymerized polyester resin (d) consisting of 0 to 10 mol% with respect to the total dicarboxylic acid, and an epoxy group, a carboxylic acid group or a dicarboxylic acid anhydride group. And an ethylene copolymer (e) containing one or more functional groups, or a thermoplastic resin (f) and a polyfunctional epoxy compound (g) which are further added as necessary. A thermosetting resin composition comprising the following adhesive resin. 3. The thermosetting resin composition according to claim 1, wherein the maleimide compound (A) is a polymaleimide compound represented by the following general formula 1. [Chemical 1] [(Wherein, R ₁ and R ₂ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms, and Ar is represented by the following formula 2] (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 is 1 carbon atom.
~ 15 divalent hydrocarbon groups, or -CO-, -S
_{-, - C (CF 3)} 2 -, - SO 2 - or -O- 2
Indicates a valence group. Further, R ₅ may be directly bonded by a single bond. )] 4. The thermosetting resin composition according to claim 1, which further comprises (E) a filler. 5. An electronic component, which is molded and sealed with the thermosetting resin composition according to claim 1, 2, 3 or 4.