JPH06157754A - Resin composition - Google Patents

Abstract

PURPOSE:To obtain a resin composition having excellent crack resistance in soldering and moisture resistance by blending mainly a modified reactional product obtained by reacting a specified polymaleimide with a silane coupling agent. CONSTITUTION:This resin composition is manufactured by modifying (A) a polymaleimide containing >=2 maleimide groups in one molecule (e.g. N,N'- ethylenebismaleimide) by reacting 100 pts.wt. of (A) with 0.1-25 pts.wt. of (B) a silane coupling agent of the formula (Y is univalent organic acid containing amino group; R1 to R3 are H, phenyl, OR (R is H or 1-5C alkyl), etc.; at least one of R1 to R3 is OR) (e.g. 3-aminopropyltrimethoxysilane) and blending the modified product with an epoxy resin containing >=2 epoxy groups in one molecule and a hardener. Optionally the component A is mixed with a phenol resin, in advance.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a resin composition having excellent heat resistance and moisture resistance. In particular, the present invention relates to a resin composition suitable for encapsulating a semiconductor device such as a surface-mounting type semiconductor device that requires soldering heat resistance.

[0002]

2. Description of the Related Art In recent years, resin compositions having excellent heat resistance, crack resistance and moisture resistance have been demanded in the fields of electric / electronic parts, semiconductors and the like. For example, in the field of electric and electronic parts, especially semiconductors, downsizing of equipment and devices using them,
As the device becomes thinner, the mounting density on the wiring board for mounting components tends to increase, and the components themselves also tend to be multifunctional. As a material for sealing this, development of a resin composition having excellent heat resistance against high-temperature solder in the step of soldering to a wiring board is strongly desired. Conventionally, as a resin composition for such applications, a so-called semiconductor encapsulating resin composition, an epoxy resin represented by o-cresol-novolak type epoxy resin, and a phenol novolac resin and silica as a curing agent as main components. The resin composition to be used is excellent in moldability and reliability, and has become the mainstream in this field. "Kakiuchi Hiroshi, Ed., Epoxy resin P80, Shokoido Co., Ltd."

[0003]

However, regarding the resin-sealed semiconductor device, the surface-mounted semiconductor device is being changed due to the above-mentioned trend of high-density mounting.
In such a surface mount type semiconductor device, unlike the conventional insertion type semiconductor device, the entire semiconductor device is exposed to a soldering temperature of 200 ° C. or higher in the step of soldering to the substrate. By the way, a resin composition made of an epoxy resin has a glass transition temperature lower than the soldering temperature, so that the strength is drastically reduced at the soldering temperature, and particularly when soldering is performed while the sealed resin absorbs moisture, It cannot withstand the stress due to the rapid expansion of the absorbed moisture, and cracks occur in the sealing resin, greatly reducing the reliability of the semiconductor device. "Magazine; Nikkei Electronics, June 13, 1988, pages 114-118" Therefore, JP-A-1-213335 and JP-A-2-2
As described in JP-A-54735 and JP-A-2-32117, the present inventors aim to raise the glass transition temperature of a sealing resin and to have sufficient resin strength to overcome the stress generated by the expansion of water. Then, the research which applied the imide resin to the resin composition for sealing has been repeated. As a result, the strength at high temperature can be increased by applying the imide resin, and the crack resistance at the time of soldering is improved, but the imide resin is inferior in the adhesiveness to the semiconductor element and the heat at the time of soldering. There is a problem that the impact causes peeling at the interface between the surface of the element and the resin, and the moisture resistance thereafter decreases. An object of the present invention is to improve the solder crack resistance at the time of mounting and the moisture resistance after mounting, so that a resin composition for encapsulation that can be applied to a surface mounting type semiconductor device in which reflow and flow soldering are performed. To provide.

[0004]

Means for Solving the Problems The inventors of the present invention have conducted extensive studies in order to solve the above problems, and as a result, modified a polymaleimide compound with a silane coupling agent having an amino group to obtain a semiconductor device surface. The inventors have found that the adhesiveness between the resin and the resin is improved and have completed the present invention. That is, the present invention provides (1) a polymaleimide compound and a compound represented by the general formula (1):

[0005]

[Chemical 2] (In the formula, Y is a monovalent organic group containing an amino group, R ₁ and R ₂
And R ₃ is a hydrogen atom, a phenyl group, an alkyl group having 1 to 6 carbon atoms, or an OR group (R is a hydrogen atom or a carbon number 1
The alkyl groups of 5 are shown. ) And at least one of R ₁ , R ₂ and R ₃ is an —OR group), and a thermosetting resin mainly composed of a modified reaction product obtained by modifying the silane coupling agent. A resin composition comprising an inorganic filler, (2) a thermosetting resin composition as described in (1) above, wherein the polymaleimide compound contains a phenol resin in advance, (3) the above (1) or ( 2) The thermosetting resin composition described above and 1
A resin composition comprising an epoxy resin having at least two epoxy groups in the molecule, (4) mainly containing the resin composition described in (1), (2) or (3) above. A resin composition for semiconductor encapsulation comprising (5) and a resin composition for semiconductor encapsulation mainly containing the resin composition according to (1), (2) or (3) above and an inorganic filler. is there. The polymaleimide compound used in the present invention is represented by the general formula (a)

[0006]

[Chemical 3] (In the formula, R ₄ is a k-valent organic group having at least 2 carbon atoms, and k is a positive integer of 2 or more), and is a polymaleimide compound, and 2 or more are contained in one molecule. Any compound having a maleimide group can be used. Examples of such polymaleimide compounds include N, N'-ethylene bismaleimide, N, N'-hexamethylene bismaleimide, N, N '-(1,3-phenylene) bismaleimide, N, N'- [1,3- (2-Methylphenylene)] bismaleimide, N, N '-(1,4-phenylene) bismaleimide, bis
(4-maleimidophenyl) methane, bis (3-methyl-4-
Maleimidophenyl) methane, bis (4-maleimidophenyl) ether, bis (4-maleimidophenyl) sulfone, bis (4-maleimidophenyl) sulfide, bis
(4-maleimidophenyl) ketone, bis (4-maleimidocyclohexyl) methane, 1,4-bis (4-maleimidophenyl) cyclohexane, 1,4-bis (maleimidomethyl)
Cyclohexane, 1,4-bis (maleimidomethyl) benzene, 1,3-bis (4-maleimidophenoxy) benzene, 1,
3-bis (3-maleimidophenoxy) benzene, bis [4-
(3-Maleimidophenoxy) phenyl] methane, bis [4-
(4-maleimidophenoxy) phenyl] methane, 1,1-bis [4- (3-maleimidophenoxy) phenyl] ethane, 1,
1-bis [4- (4-maleimidophenoxy) phenyl] ethane, 1,2-bis [4- (3-maleimidophenoxy) phenyl]
Ethane, 1,2-bis [4- (4-maleimidophenoxy) phenyl] ethane, 2,2-bis [4- (3-maleimidophenoxy) phenyl] propane, 2,2-bis [4- (4-maleimide) Phenoxy) phenyl] propane, 2,2-bis [4- (3-maleimidophenoxy) phenyl] butane, 2,2-bis [4- (4-maleimidophenoxy) phenyl] butane, 2,2-bis [4- (3-maleimidophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, 2,2-bis [4- (4-maleimidophenoxy)
Phenyl] -1,1,1,3,3,3-hexafluoropropane, 4,4 '
-Bis (3-maleimidophenoxy) biphenyl, 4,4'-
Bis (4-maleimidophenoxy) biphenyl, bis [4-
(3-Maleimidophenoxy) phenyl] ketone, bis [4-
(4-maleimidophenoxy) phenyl] ketone, bis [4-
(3-maleimidophenoxy) phenyl] sulfide, bis [4- (4-maleimidophenoxy) phenyl] sulfide,
Bis [4- (3-maleimidophenoxy) phenyl] sulfoxide, Bis [4- (4-maleimidophenoxy) phenyl] sulfoxide, Bis [4- (3-maleimidophenoxy) phenyl] sulfone, Bis [4- (4-maleimide) Phenoxy) phenyl] sulfone, bis [4- (3-maleimidophenoxy) phenyl] ether, bis [4- (4-maleimidophenoxy)
Phenyl] ether, 1,4-bis [4- (4-maleimidophenoxy) -α, α-dimethylbenzyl] benzene, 1,3-bis
[4- (4-maleimidophenoxy) -α, α-dimethylbenzyl] benzene, 1,4-bis [4- (3-maleimidophenoxy)-
α, α-Dimethylbenzyl] benzene, 1,3-bis [4- (3-
Maleimidophenoxy) -α, α-dimethylbenzyl] benzene, 1,4-bis [4- (4-maleimidophenoxy) -3,5-dimethyl-α, α-dimethylbenzyl] benzene, 1,3-bis [4 -(4-maleimidophenoxy) -3,5-dimethyl-α, α
-Dimethylbenzyl] benzene, 1,4-bis [4- (3-maleimidophenoxy) -3,5-dimethyl-α, α-dimethylbenzyl] benzene, 1,3-bis [4- (3-maleimidophenoxy)
-3,5-Dimethyl-α, α-dimethylbenzyl] benzene, general formula (2)

[0007]

[Chemical 4] (In the formula, n is an average value of 0 to 10), and a polymaleimide compound represented by the general formula (3)

[0008]

[Chemical 5] (In the formula, m is an average value of 0 to 10) and the like. These polymaleimide compounds may be used alone or in combination of two or more. The silane coupling agent used in the present invention is represented by the above general formula (1).

Specific examples of the silane coupling agent include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyldimethoxymethylsilane, 3-aminopropyldiethoxymethylsilane and 3-amino. Propyldimethylethoxysilane, 2-aminoethylaminomethyltrimethoxysilane, 3- (2-aminoethylaminopropyl) trimethoxysilane, 3- (2-aminoethylaminopropyl)
Dimethoxymethylsilane, 3- [2- (2-aminoethylaminoethylamino) propyl] trimethoxysilane, 3-phenylaminopropyltrimethoxysilane,
3-benzylaminopropyltrimethoxysilane, 3-
Cyclohexylaminopropyltrimethoxysilane, N
-(3-triethoxysilylpropyl) urea, N-
(3-Triethoxysilylpropyl) -p-nitrobenzamide, 2- (2-aminoethylthioethyl) triethoxysilane, 2- (2-aminoethylthioethyl) diethoxymethylsilane, 3-piperazinopropyltri Methoxysilane, dimethoxymethyl-3-piperazinopropylsilane, 3-dibutylaminopropyltrimethoxysilane and the like can be mentioned, and these can be used alone or
Used in seeds and above. The modification reaction of the polymaleimide compound and the silane coupling agent is carried out by heating and mixing the polymaleimide compound and the silane coupling agent, or the polymaleimide compound, the phenol resin and the silane coupling agent. In this case, the mixing ratio of the polymaleimide compound and the silane coupling agent is 100
Parts (parts by weight, the same applies hereinafter) to silane coupling agent
It is in the range of 0.1 to 25 parts, and the mixing ratio of the phenol resin to the polymaleimide compound is not particularly limited, but about 1 to 50% by weight of the total amount thereof is preferable and practical. When the amount of the silane coupling agent is less than 0.1 part, the modification reaction is insufficient, and when it exceeds 25 parts, the reaction of the silane coupling agent alone occurs, which adversely affects the moisture resistance.

An imide resin, which has excellent heat resistance, has problems in flexibility and moldability when used alone. Therefore, it is possible to balance the moldability and heat resistance by using it together with other resins. it can. From this point of view, the combined use with an epoxy resin is particularly preferable, and any epoxy resin having at least two epoxy groups in one molecule can be used. These are illustrated below. Phenol,
A novolac type epoxy resin derived from a novolac resin which is a reaction product of a phenol such as cresol, resorcinol, naphthol and an aldehyde such as formaldehyde, acetaldehyde, benzaldehyde, hydroxybenzaldehyde, glyoxal, alkanedial, and the above phenols. An aralkyl-type epoxy resin derived from an aralkyl resin, which is a reaction product of an aralkyl alcohol derivative, is preferable in terms of heat resistance and electric characteristics.

In addition, an epoxy resin derived from a compound having two or more active hydrogen groups in one molecule, for example,
Bisphenol A, bisphenol F, resorcin, bishydroxydiphenyl ether, 4,4'-bishydroxy-3,3 ', 5,5'-tetramethylbiphenyl, tetrabromobisphenol A, dihydroxynaphthalene, trihydroxyphenylmethane, tetrahydroxyphenyl Polyhydric phenols such as ethane and alkane tetrakisphenol; polyhydric alcohols such as ethylene glycol, neopentyl glycol, glycerin, trimethylolpropane, pentaerythritol, diethylene glycol, polypropylene glycol; ethylenediamine, aniline, bis (4-aminophenyl) Amines such as methane;
Examples thereof include epoxy resins obtained by reacting polycarboxylic acids such as adipic acid, phthalic acid, and isophthalic acid with epichlorohydrin or 2-methylepichlorohydrin, and one or more of these epoxy resins are used.

The epoxy resin is oily,
It can also be used after being modified with a silicone compound such as rubber. For example, JP-A-62-270617 and JP-A-62-2732
As disclosed in No. 22, a silicone-modified epoxy resin produced by dispersing fine particles of a silicone polymer in a reaction product of an epoxy resin and a vinyl polymer. As the curing agent for the epoxy resin, known compounds such as phenols, amines and acid anhydrides can be used, but phenol resins are most preferably used. For example, phenols such as phenol, cresol, resorcinol, naphthol and formaldehyde,
Acetaldehyde, benzaldehyde, hydroxybenzaldehyde, gluoxal, novolak resin which is a reaction product with aldehydes such as alkanedial, and aralkyl resin which is a reaction product of the above-mentioned phenols and aralkyl alcohol derivative, trihydroxyphenylmethane, tetra Examples thereof include polyhydric phenols such as hydroxyphenylethane and tetrakisphenol, and one type or two or more types thereof are used. In the composition of the present invention, when a modified reaction product obtained by modifying the polymaleimide compound and the silane coupling agent represented by the general formula (1) is used in combination with an epoxy resin, 100 parts by weight of the modified reaction product is added. On the other hand, the total amount of the epoxy resin and the curing agent is 10 to 500 parts by weight, preferably 25 to 300 parts by weight. In addition, the ratio of the epoxy resin and the curing agent is 0 in an equivalent ratio of the curing agent to the epoxy group of the epoxy resin.
It is in the range of 1 to 10, preferably in the range of 0.5 to 2.0.

The inorganic filler used in the composition of the present invention may be an inorganic powder or a fibrous material. Examples thereof include crystalline silica, fused silica, alumina, silicon nitride, silicon carbide and talc. , Calcium silicate,
Powders of calcium carbonate, mica, clay, titanium white and the like; fiber bodies such as glass fibers and carbon fibers are available, but crystalline and fusible silica powders are preferable from the viewpoint of thermal expansion coefficient and thermal conductivity. Further, spherical or a mixture of spherical and amorphous silica powder is preferable from the viewpoint of fluidity during molding. The blending amount of the inorganic filler needs to be 100 to 900 parts by weight, and preferably 200 to 600 parts by weight, based on 100 parts by weight of the thermosetting resin mainly composed of the modified reaction product. In addition, the above-mentioned inorganic filler, if necessary, in addition to the silane coupling agent used in the present invention, its surface is preliminarily treated with a surface treatment agent such as a silane-based, titanate-based, aluminate-based and zircoaluminate-based coupling agent. May be modified. Among them, the silane coupling agent is preferable, and the silane coupling agent having a reactive functional group is particularly preferable.

Examples of such silane coupling agents are vinyltrimethoxysilane, vinyltriethoxysilane, N- (2-aminoethyl) 3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) 3-.
Aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-anilinopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4- Epoxycyclohexyl) ethyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane and the like can be mentioned, and one type or two or more types thereof are used.

In the present invention, when the resin composition is cured, it is desirable to include a curing accelerator,
As such a curing accelerator, 2-methylimidazole,
Imidazoles such as 2-methyl-4-ethylimidazole and 2-heptadecylimidazole; amines such as triethanolamine, triethylenediamine and N-methylmorpholine; organic phosphines such as tributylphosphine, triphenylphosphine and tritolylphosphine ;
Tetraphenylphosphonium tetraphenylborate,
And tetraphenylboron salts such as triethylammonium tetraphenylborate; 1,8-diaza-bicyclo (5,4,0) undecene-7 and its derivatives. These curing accelerators may be used alone or in combination of two or more, and if necessary, an organic peroxide or an azo compound may be used in combination. The content of these curing accelerators is 0.01 to 10 parts by weight with respect to 100 parts by weight of the thermosetting resin mainly composed of the modified reaction product.

The resin composition of the present invention contains, in addition to the above-mentioned various components,
Reactive diluents commonly used for imide resins such as diallyl phthalate, triallyl isocyanurate and o, o'-diallyl bisphenol A as required; various silicone oils; fatty acids, fatty acid salts, waxes, etc. Release agent; flame retardant such as bromine compound, antimony, phosphorus; coloring agent such as carbon black, etc. are mixed, mixed and kneaded,
It can be a molding material.

[0017]

EXAMPLES The present invention will be specifically described below with reference to examples. In the examples, the method of testing the performance of the composition is as follows.・ Glass transition temperature: TMA method ・ Bending strength: JIS K-6911 ・ Solder immersion test: 85 semiconductor devices for test 85
After leaving it in a constant temperature and humidity chamber of 85 ° C. and 85% for 168 hours, it was immediately immersed in a molten solder bath at 260 ° C. for 10 seconds, and then the number of semiconductor devices in which cracks had occurred in the package resin was counted.・ Moisture resistance test after solder immersion: In the solder immersion test, 12 test semiconductor devices were tested without cracks.
It is left in a pressure cooker tester at 1 ° C and 2 atm, and electrical continuity is checked at regular intervals, and the time at which the rate of occurrence of defects due to corrosion of aluminum wiring reaches 50% is measured.

Production Examples A to G (Production of Modified Reaction Products A to G) The polymaleimide compound was inserted into a reaction vessel equipped with a stirrer, a thermometer and a condenser, and heated to 160 ° C. The silane coupling agent was inserted so as to have the compositions of A to G, the reaction was carried out for 3 minutes, and the reaction products were immediately cooled to obtain modified reaction products A to G.

Production Examples H to K (Production of Modified Reaction Products H to K) A polymaleimide compound and a phenol resin were inserted into a reaction vessel equipped with a stirrer, a thermometer, and a cooler.
After heating to 0 ° C., a silane coupling agent is inserted so that the composition of H to K in Table 1 [Table 1] is introduced, the mixture is reacted for 5 minutes, and immediately cooled to obtain modified reaction products A to G. It was

[0020]

[Table 1]

Examples 1 to 9 and Comparative Examples 1 to 8 The compositions (parts by weight) shown in Table 2 [Table 2] were mixed in a Henschel mixer, and further heated on a hot roll at 100 to 130 ° C. for 3 minutes. Melted and kneaded. This mixture was cooled, pulverized, and tableted to obtain a molding resin composition. The first,
The raw materials used in Table 2 were as follows. -Polymaleimide compound (1); bis (4-maleimidophenyl) methane (manufactured by Mitsui Toatsu Chemicals, Inc.)-Polymaleimide compound (2); 4,4'-bis (3-
Maleimidophenoxy) biphenyl (manufactured by Mitsui Toatsu Chemicals, Inc.)-Epoxy resin; o-cresol novolac type epoxy resin (EOCN-1020, manufactured by Nippon Kayaku Co., Ltd.)-Brominated epoxy resin; Brominated phenol novolac type Epoxy resin (BREN-S, Nippon Kayaku Co., Ltd.)
Hardener; Novolac type phenolic resin (PN-80
, Nippon Kayaku Co., Ltd.-Inorganic filler (1); Spherical fused silica with an average particle size of 20μ (Halmic S-CO, manufactured by Micron Co., Ltd.)-Inorganic filler (2); Average particle size of 13μ Amorphous fused silica (Fuselex RD-8 manufactured by Tatsumori Co., Ltd.)-Silane coupling agent; 3- (2-aminoethylaminopropyl) trimethoxysilane (KBM603, manufactured by Shin-Etsu Chemical Co., Ltd.)-Silane Coupling agent; 3- (2-aminoethylaminopropyl) methyldimethoxysilane (KBM602,
Shin-Etsu Chemical Co., Ltd.-Silane coupling agent; 3-phenylaminopropyltrimethoxysilane (SZ-6083, Toray Dow Corning Silicone Co., Ltd.)-Silane coupling agent; 3-glycidoxypropyl Trimethoxysilane (A-187, Nippon Unicar Co., Ltd.)
・ Flame retardant aid (antimony oxide; Sumitomo Metal Mining Co., Ltd.) ・ Curing accelerator (C ₁₇ Z; Shikoku Kasei Co., Ltd.)

[0022]

[Table 2] -Curing accelerator (TPP-K; manufactured by Kitako Chemical Co., Ltd.)-Release agent (Hoechst wax OP; manufactured by Hoechst Japan Co., Ltd.)-Coloring agent (carbon black; manufactured by Mitsubishi Kasei Co., Ltd.) A test piece for measuring physical properties was molded by transfer molding (180 ° C., 30 kg / cm ² , 3 minutes) using the molding resin composition thus obtained. In addition, the element mounting portion of the lead frame for the flat package type semiconductor device is connected to the aluminum bonding pad portions of 100 μ × 100 μ and the thickness of 1 μ at the four corners, and the width is 1
Test element with 0μ aluminum wiring (10mm
A test semiconductor device was obtained by connecting the lead frame and the bonding pad portion with a gold wire having a size of × 10 mm square mounted thereon, and then performing transfer molding (180 ° C., 30 kg / cm ² , 3 minutes). These test molded articles were post-cured at 180 ° C. for 6 hours before performing each test. The test results are shown in Table 3 [Table 3].

[0023]

[Table 3]

[0024]

As described in Examples and Comparative Examples, the resin composition according to the present invention is a resin composition having excellent crack resistance during mounting and moisture resistance after that. Therefore, when a surface mount type semiconductor device to which a reflow and flow soldering method is applied is sealed with this resin composition, it exhibits excellent solder crack resistance and moisture resistance, and is a highly reliable resin-sealed semiconductor. This is an industrially advantageous invention because the device can be obtained.

(72) Inventor Motoyuki Torikai 1190 Kasama-cho, Sakae-ku, Yokohama, Kanagawa Mitsui Toatsu Chemical Co., Ltd. (72) Kotaro Asahina 1190, Kasama-cho, Sakae-ku, Yokohama, Kanagawa Mitsui Toatsu Chemical Co., Ltd. Within

Claims (5)

[Claims] 1. A polymaleimide compound having two or more maleimide groups in one molecule and a compound represented by the general formula (1) [Chemical Formula 1] [In the formula, Y is a monovalent organic group containing an amino group, R ₁ and R ₂
And R ₃ is a hydrogen atom, a phenyl group, an alkyl group having 1 to 6 carbon atoms, or an OR group (R is a hydrogen atom or a carbon number 1
The alkyl groups of 5 are shown. And at least one of R ₁ , R ₂ and R ₃ is an —OR group]. A thermosetting resin mainly containing a modification reaction product obtained by modifying the silane coupling agent. Composition. 2. The thermosetting resin composition according to claim 1, wherein the polymaleimide compound contains a phenol resin in advance. 3. A resin composition comprising the thermosetting resin composition according to claim 1 or 2 and an epoxy resin having at least two epoxy groups in one molecule. 4. A resin composition for semiconductor encapsulation, which mainly contains the resin composition according to claim 1, 2, or 3. 5. A resin composition for semiconductor encapsulation, which mainly contains the resin composition according to claim 1, 2 or 3 and an inorganic filler.