JPH04328118A - Resin composition - Google Patents

Abstract

PURPOSE:To obtain a composition having excellent heat-resistance, soldering cracking resistance, etc., and suitable as a sealing material for semiconductor device by compounding an inorganic filler to an organic component composed of a polymaleimide resin, a specific epoxy compound and a phenolic compound. CONSTITUTION:This composition is produced by compounding (A) an inorganic filler (preferably a mixture of spherical silica powder and amorphous silica powder) to an organic component composed mainly of (B) a polymaleimide compound of formula I (R1 is >=2C m-valent organic group; m>=2) (e.g. N,N'- ethylenebismaleimide), (C) an epoxy compound of formula II or epoxy compounds containing 30-100% compound of formula II and (D) a phenolic compound having plural phenolic hydroxyl groups. The compound of formula II is preferably produced by condensing 2mol of 1,6-dihydroxynaphthalene and 1mol of formaldehyde and reacting the condensation product with epichlorohydrin. The component (D) is preferably a novolak phenolic resin of formula III (R3 is H, OH, etc.; r>=1).

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition having excellent heat resistance and crack resistance. In other words, it is related to resin compositions that aim to improve heat resistance and crack resistance as insulating materials, laminate materials, and resin sealing materials for electronic/electrical parts, semiconductor fields, etc., and particularly requires solder crack resistance. The present invention relates to a resin composition suitable for encapsulating semiconductor devices.

0002

BACKGROUND OF THE INVENTION In recent years, there has been a demand for resin compositions with excellent heat resistance and crack resistance in the fields of electric/electronic parts, semiconductors, etc. For example, in the field of electrical and electronic components, especially semiconductors, as equipment and equipment that use these components become smaller and thinner, there is a trend toward higher mounting density on wiring boards to which components are attached. There is also a trend toward multifunctionality. As a material for sealing this, there is a strong desire to develop a resin composition that has excellent heat resistance against high-temperature soldering in the soldering process to wiring boards.

Conventionally, resin compositions for such uses, so-called semiconductor encapsulation resin compositions, have been made using epoxy resins such as O-cresol novolac type epoxy resins, phenol novolac resins and silica as curing agents. The resin composition as the main component has excellent moldability and reliability, and has become the mainstream in this field. "Edited by Hiroshi Kakiuchi; Epoxy resin, P80, Shokodo Co., Ltd."

0004

However, resin-sealed semiconductor devices are being replaced by surface-mounted semiconductor devices due to the above-mentioned trend toward high-density packaging. In such a surface mount type semiconductor device, unlike a conventional insertion type semiconductor device, the entire semiconductor device is exposed to a soldering temperature of 200° C. or higher during the soldering process to a substrate. At this time, a problem has arisen in that cracks occur in the sealing resin, significantly reducing the reliability of the semiconductor device. “Magazine; Nikkei Electronics June 13, 1988 Issue 11
Pages 4-118'' These cracks during soldering occur when the moisture absorbed during storage of the semiconductor device expands explosively at temperatures above 200°C, generating stress, and when this exceeds the strength of the sealing resin, cracks occur. occurs. At this time, the stress applied to the resin is approximately expressed by the following equation. "Narioka, Niwa, Yamada, Shiraishi (eds.); Structural Mechanics III, Maruzen" σ=k・
p・a2/t2 where σ: stress applied to the resin k: constant p: water vapor pressure a: length of the short side of the die pad t: thickness of the resin at the bottom of the die pad As shown in JP-A-254735 and JP-A-2-32117, imide-based resins have been considered. However, the cured product of imide resin tends to have an increased water absorption rate, which, considering the above equation, increases the stress applied to the resin and makes it impossible to take advantage of the high strength characteristic of imide resin. Therefore, lowering the water vapor pressure during soldering by reducing the water absorption rate is an effective means for suppressing the occurrence of cracks.

An object of the present invention is to provide a resin composition that has excellent heat resistance, crack resistance, and low moisture absorption and can be applied to resin-encapsulated semiconductor devices that require solder crack resistance during mounting. Another object of the present invention is to provide a resin composition that can be widely applied to electronic and electrical parts for improving the heat resistance and crack resistance of insulating materials, laminates, and the like.

[0006]

[Means for Solving the Problems] In order to solve the above problems, the present inventors, as a result of intensive research, have used polymerimide, which can be cured at a relatively low temperature as an imide resin, and have further improved the water absorption. By using an epoxy compound having a naphthalene ring with a low carbon content, they succeeded in significantly improving the strength of the sealing resin without increasing its water absorption rate, thereby completing the present invention.

That is, the present invention provides an organic component containing a polymaleimide represented by the general formula (1), an epoxy compound having a naphthalene ring represented by the general formula (2), and a compound having two or more phenolic hydroxyl groups, and an inorganic filler.

More specifically, (1). (A) As the component, (a) general formula (1);

[0009]

A polymaleimide compound represented by the formula (wherein R1 represents an m-valent organic group having at least 2 carbon atoms, and m represents a positive integer of 2 or more) and (b) the general formula (2);

0
010]

Epoxy compound represented by embedded image or the compound 30 to 100
%, (c) an organic component mainly composed of a phenol compound having two or more phenolic hydroxyl groups, and (B) an inorganic filler as a component, a resin composition comprising: 2). A resin composition for semiconductor encapsulation consisting essentially of the resin composition described in item (1), (3).
The resin composition according to item (1) or (2), wherein the total amount of components (b) and (c) is 10 to 500 parts by weight based on 100 parts by weight of the polymaleimide compound of component (a);
4). (1) or (2) where the ratio of component (b) to component (c) is that the ratio of phenolic hydroxyl group in component (c) to epoxy group in component (b) is in the range of 0.1 to 10; The resin composition described in Section (5). The resin composition according to item (1) or (2), wherein the amount of the inorganic filler as component (B) is 100 to 900 parts by weight based on 100 parts by weight of the total amount of organic components as component (A); 6). The polymaleimide compound of component (a) has the general formula (3) [Chemical formula 3]

[0011]

It is characterized by containing a polymaleimide represented by
The resin composition described in item 1) or (2), (7). (b)
(1) or (2) characterized by containing 0 to 70% by weight of an epoxy compound represented by general formula (4), (5) and/or (6) in the component epoxy compounds.
The resin composition described in

0012

[Chemical formula 16]

[0013]

[Chemical formula 17]

[0014]

[Chemical formula 18] (8). The phenol compound of component (c) has the general formula (7)
(1) or (2) characterized by containing an aralkyl resin represented by , (8), (9), (10) or (11) and/or a dicyclopentadiene phenol resin represented by general formula (12). ), the resin composition described in

[0015]

[Chemical formula 19]

[0016]

[C20]

[0017]

[C21]

[0018]

[C22]

[0019]

[C23]

[0020]

[Chemical formula 24] (9). The inorganic filler of component (B) is crystalline silica, fused silica, alumina, silica nitride, silica carbide, talc,
Calcium silicate, calcium carbonate, mica, clay,
At least one member selected from the group consisting of titanium white, glass fiber, and carbon fiber (1) or (
This is the resin composition described in item 2).

[0021] In the composition of the present invention, the organic component (A)
The component (a) used as is a polymaleimide compound represented by general formula (1). The polymaleimide compound represented by the general formula (1) is a compound having two or more maleimide groups in one molecule.

Examples of such polymaleimide compounds include N,N'-ethylene bismaleimide, N,N
'-Hexamethylene bismaleimide, N,N'-(1
,3-phenylene) bismaleimide, N,N'-(1
,4-phenylene) Bismaleimide, bis(4-maleimidophenyl) Methane, bis(4-maleimidophenyl) Ether, bis(3-chloro-4-maleimidophenyl) Methane, bis(4-maleimidophenyl) Sulfone, 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-
maleimidophenoxy) 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- Maleimidophenoxy) Phenyl] Sulfone, Bis [4-(3- Maleimidophenoxy) Phenyl] Ether, Bis [4-(4-
maleimidophenoxy) phenyl] ether, polymaleimidophenylmethylene, and general formula (3):

[0023]

Examples include polymaleimide compounds represented by the following formula (wherein l is an average value of 0 to 10). Further, these polymaleimide compounds may be used alone or in combination of two or more types.

[0024] Furthermore, in the composition of the present invention, an organic component (
Component (b) used as A) is an epoxy compound represented by general formula (2) or epoxy compounds containing this compound. In other words, as component (b), the general formula (
The epoxy compound represented by 2) may be used alone or in combination with other epoxy compounds.

The epoxy compound represented by the general formula (2) is a bis(1,
It is obtained by reacting methane (6-dihydroxynaphthyl) with epichlorohydrin. As polyvalent epoxy compounds used in combination with the epoxy compound represented by general formula (2), which is an essential component, from the viewpoint of heat resistance and electrical properties, phenol and reaction products of substituted phenols and aldehydes are recommended. General formula (4) derived from a novolac type phenolic resin;

[0026]

The epoxy resin represented by the formula (wherein R4 represents a hydrogen atom or an alkyl group having 1 to 9 carbon atoms, and p represents an integer of 1 or more) is most preferably used; Any compound having at least two epoxy groups can be used. Specifically, epoxy resins derived from compounds having two or more active hydrogens in one molecule, such as bisphenol A, bisphenol F, resorcinol,
Polyhydric phenols such as bishydroxydiphenyl ether, bishydroxybiphenyl, tetrabromobisphenol A, trihydroxyphenylmethane, tetrahydroxyphenylethane, alkanetetrakisphenol; ethylene glycol, neopentyl glycol, glycerin, trimethylolpropane, pentaerythritol, diethylene glycol , polyhydric alcohols such as polypropylene glycol; ethylenediamine, aniline,
Amines such as bis(4-aminophenyl)methane; epoxy resins obtained by reacting polyhydric carboxylic acids such as adipic acid, phthalic acid, and isophthalic acid with epichlorohydrin or 2-methylepichlorohydrin; and general formula (5), (6);

[0027]

[C27]

[0028]

embedded image (wherein x represents an integer of 0 to 5), and one or more of these epoxy resins are used. Further, the above-mentioned epoxy resin can also be used after being modified with an oil-like, rubber-like silicone compound, or the like. For example, as disclosed in JP-A-62-270617 and JP-A-62-273222, silicone-modified epoxy resins are produced by dispersing fine particles of silicone polymer in a reaction product of epoxy resin and vinyl polymer. It is.

In the composition of the present invention, the phenol compound having two or more phenolic hydroxyl groups in one molecule as component (C) is a reaction product of phenol or a substituted phenol with an aldehyde. General formula (7)

[0030]

A novolac type phenol resin represented by the formula (wherein R3 represents a hydrogen atom, a hydroxyl group, or an alkyl group having 1 to 9 carbon atoms, and r represents an integer of 1 or more) is most preferably used, Other phenolic compounds, such as general formula (8
), (9), (10) or (11);

[0031]

[C30]

[0032]

[Chemical formula 31]

[0033]

[C32]

[0034]

[Chemical formula 33] (In each formula, q represents an integer of 0 to 5.) Aralkyl resin represented by general formula (12)

[0035]

Dicyclopentadiene phenol resin represented by (wherein, R2 represents a hydrogen atom or an alkyl group having 4 or less carbon atoms, and n represents an integer of 0 to 5), and trihydroxyphenylmethane , tetrahydroxyphenylethane, alkane tetrakisphenol, and the like. These phenol compounds can be used alone or in combination of two or more.

In the composition of the present invention, the component (a) is a polymaleimide compound represented by the general formula (1), the component (b) is an epoxy compound represented by the general formula (2), or an epoxy compound containing the compound. The blending amount of the compounds and the phenolic compound having two or more phenolic hydroxyl groups of component (c) is such that the total amount of components (b) and (c) is 10 to 100 parts by weight of component (a). The amount is 500 parts by weight, preferably 25 to 300 parts by weight, and 2 or more of component (c) is added to the epoxy compound represented by general formula (2) of component (b) or epoxy compounds containing this compound. The equivalent ratio of the compound having a phenolic hydroxyl group is 0.1 to 1
0, preferably 0.5 to 2.0.

In the present invention, the resin composition may be blended and kneaded in a conventional manner, or the polymaleimide compound may be added to a part or all of the above component (b) or a mixture of components (b) and (c). They may be dissolved in advance, or they may be used as a reacted prepolymer.

The inorganic filler used as component (B) in the composition of the present invention can be an inorganic powder or fiber, such as crystalline silica, fused silica, alumina, silicon nitride, etc. , silicon carbide, talc, calcium silicate, calcium carbonate, mica, clay, titanium white, and other powders; fibrous materials such as glass fiber and carbon fiber, but from the viewpoint of thermal expansion coefficient and thermal conductivity, crystalline , fusible silica powder is preferred. Furthermore, from the viewpoint of fluidity during molding, spherical silica powder or a mixture of spherical and irregularly shaped silica powders are preferred.

The amount of the inorganic filler (B) component is (a
) a polymaleimide compound represented by the general formula (1) as the component, an epoxy compound represented by the general formula (2) as the component (b) or epoxy compounds containing this compound, and two or more of the component (c). 100 to 900 parts per 100 parts by weight of the total amount of phenolic compounds having phenolic hydroxyl groups
It is necessary that the amount is in parts by weight, preferably 200 to 6 parts by weight.
00 parts by weight.

[0040] The above inorganic filler also has mechanical strength,
From the point of view of heat resistance, it is preferable to use a coupling agent in combination with the resin to improve adhesion to the resin. Examples of such coupling agents include silane-based, titanate-based, aluminate-based, and zircoaluminate-based couplings. agent can be used. Among them, silane coupling agents are preferred, and particularly silane coupling agents having a reactive functional group are most preferred.

Examples of such silane coupling agents include vinyltrimethoxysilane, vinyltriethoxysilane, N-(2-aminoethyl)3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)3-
Aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-anilinopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2-(3,4- Examples include epoxycyclohexyl)ethyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, and 3-mercaptopropyltrimethoxysilane, and one or more of these may be used. These silane coupling agents are preferably fixed in advance on the surface of the inorganic filler by adsorption or reaction.

In the present invention, when curing the resin composition, it is desirable to contain a curing accelerator.
Such curing accelerators include 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,
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 types, and if necessary, an organic peroxide or an azo compound can also be used in combination.

The content of these curing accelerators is determined by the amount of the component (a), the polymaleimide compound represented by the general formula (1), and the component (b).
) 0.01 to 10 with respect to the total amount of the epoxy compound represented by the general formula (2) or the epoxy compounds containing this compound as the component and the compound having two or more phenolic hydroxyl groups as the component (c). % by weight.

[0044] In addition to various components, the resin composition of the present invention contains, if necessary, reactive compounds commonly used for imide resins such as diallyl phthalate, triallyl isocyanurate, and o,o'-diallyl bisphenol A. Diluents; various silicone oils; mold release agents such as fatty acids, fatty acid salts, and wax; flame retardants such as bromine compounds, antimony, and phosphorus;
A coloring agent such as carbon black can be blended, mixed and kneaded to form a molding material.

[0045]

[Examples] The present invention will be specifically explained below using examples. In addition, in the examples, the test method for the performance of the composition is as follows.・Glass transition temperature: TMA method ・Bending strength and flexural modulus: JIS K-6911
Water absorption rate: using a test piece for bending test, 65 C, 95
Weight increase after being left in a constant temperature and humidity chamber for 168 hours
Measure the addition.・VPS test: test semiconductor device at 65 C, 95
After being left in a constant temperature and humidity chamber for 168 hours, the semiconductor devices were immediately placed in a molten solder bath at 260 C, and the number of semiconductor devices with cracks in the package resin was counted. (The molecule is the number of cracked semiconductor devices,
(The denominator is the total number of semiconductor devices tested). Synthesis example of epoxy compound In a reaction vessel equipped with a thermometer, stirrer and cooler, 320 g of 1,6-dihydroxynaphthalene, 81 g of a 37% aqueous formalin solution and 4.3 g of sodium p-toluenesulfonate were charged, and the mixture was heated at 150 C. The reaction was allowed to proceed for 6 hours while stirring. After the reaction was completed, water was removed under reduced pressure of 5 mmHg to obtain bis(1,6-dihydroxynaphthyl)methane.

In a reactor equipped with a thermometer, a stirrer, a separating tube and a dropping funnel, 83 g of the above bis(1,6-dihydroxynaphthyl)methane was mixed with 945 g of epichlorohydrin.
Dissolved in g. Next, the mixture was heated to 60 C, and 150 g of a 40% aqueous sodium hydroxide solution was continuously added dropwise over 2 hours. During this time, epichlorohydrin and water were azeotropically liquefied and separated into an organic layer and an aqueous layer using a separation tube.The aqueous layer was removed from the system and the organic layer was circulated into the system. After the reaction is completed, distillation under reduced pressure (1
After removing unreacted epichlorohydrin at 50 C and 5 mmHg, the reaction product was dissolved in methyl isobutyl ketone. Next, after the by-product salt was filtered off, methyl isobutyl ketone was removed by distillation to obtain an epoxy compound. This compound had a softening point of 93 C and an epoxy equivalent of 161. Examples 1 to 4 and Comparative Examples 1 and 2 Blends having the compositions (parts by weight) shown in Table 1 were mixed in a Henschel mixer, and further melted and kneaded for 3 minutes with a heated roll at 100 to 130 C. This mixture was cooled, pulverized, and tableted to obtain a molding resin composition.

[0047] Among the raw materials used in Table 1 other than those in the synthesis examples, the following were used.・Polymaleimide compound (1); Bis(4-maleimidophenyl)methane (manufactured by Mitsui Toatsu Chemical Co., Ltd.) ・Polymaleimide compound (2); 4,4'-bis(3-maleimidophenoxy)biphenyl (Mitsui Toatsu Chemical Co., Ltd.)・Epoxy resin; o-cresol novolac type epoxy resin (EOCN-1020, manufactured by Nippon Kayaku Co., Ltd.) ・Phenol compound; Novolac type phenol resin (PN
-80, manufactured by Nippon Kayaku Co., Ltd.) inorganic filler; 50 parts by weight of spherical fused silica (Halimic S-CO, manufactured by Micron Co., Ltd.) and amorphous fused silica (Fuse Rex)
Using the molding resin composition obtained as above, a mixture with 50 parts by weight of RD-8 (manufactured by Tatsumori Co., Ltd.) and a silane coupling agent (SZ-6083, manufactured by Dow Corning Toray Silicone Co., Ltd.) was used. transfer molding (1
80 C, 30 kg/cm2, 3 minutes) to form a test piece for measuring physical properties. In addition, after mounting a test element (10 mm x 10 mm square) on the element mounting part of a lead frame for a flat package type semiconductor device, a semiconductor device for test was obtained by transfer molding (180 C, 30 kg/cm2, 3 minutes). Ta. These test moldings were post-cured at 180 C for 6 hours before each test. The test results are shown in Table 2.

[0048]

[Table 1]

[0049]

[Table 2]

[0050]

[Effects of the Invention] As explained in the Examples and Comparative Examples, the resin composition according to the present invention can efficiently impart the heat resistance of an imide resin without impairing the water absorption resistance.

Therefore, when a surface-mounted semiconductor device to which reflow and flow soldering methods are applied is encapsulated with this resin composition, the resin-encapsulated semiconductor device exhibits excellent solder crack resistance and is highly reliable. It is an industrially useful invention.

Claims (9)

[Claims] Claim 1: As component (A), (a) general formula (1);
[Formula 1] (wherein R1 represents an m-valent organic group having at least 2 carbon atoms, and m represents a positive integer of 2 or more) and (b) a general formula (2); Epoxy compound represented by [Chemical formula 2] or the compound 30 to 100
%, (c) an organic component mainly consisting of a phenol compound having two or more phenolic hydroxyl groups, and (B) an inorganic filler as a component. 2. A resin composition for semiconductor encapsulation consisting essentially of the resin composition according to claim 1. Claim 3: Component (a) Polymaleimide compound 100
The total amount of component (b) and component (c) is 1 part by weight.
The resin composition according to claim 1 or 2, wherein the amount is 0 to 500 parts by weight. 4. A claim in which the ratio of component (b) to component (c) is such that the ratio of phenolic hydroxyl group in component (c) to epoxy group in component (b) is in the range of 0.1 to 10. 1 or 2
The resin composition described. Claim 5: The blending amount of the inorganic filler as component (B) is (A
) 100 to 100 parts by weight of the total amount of organic components of the components
The resin composition according to claim 1 or 2, wherein the amount is 900 parts by weight. 6. The resin composition according to claim 1 or 2, wherein the polymaleimide compound as component (a) contains a polymaleimide represented by the general formula (3). 7. In the epoxy compounds of component (b), 0 to
70% by weight of general formula (4), (5) and/or (6
) The resin composition according to claim 1 or 2, characterized in that it contains an epoxy compound represented by: [Chemical formula 4] [Chemical formula 5] [Chemical formula 6] 8. The phenol compound of component (c) is an aralkyl resin represented by general formula (7), (8), (9), (10) or (11) and/or general formula (12).
3. The resin composition according to claim 1, comprising a dicyclopentadiene phenol resin represented by: [Formula 7] [Formula 8] [Formula 9] [Formula 10] [Formula 11] [Formula 12] 9. The inorganic filler of component (B) is crystalline silica,
3. At least one member selected from the group consisting of fused silica, alumina, silica nitride, silica carbide, talc, calcium silicate, calcium carbonate, mica, clay, titanium white, glass fiber, and carbon fiber. resin composition.