JPS62187752A - Heat-resistant resin composition and resin-sealed semiconductor device - Google Patents

Abstract

PURPOSE:To provide a heat-resistant resin compsn. which has excellent resistance to heat and moisture, can impart low stress and is suitable for use ass a sealing resin for semiconductor devices, containing a bisphenol/novolak type resin having a specified unit as a main component. CONSTITUTION:Bisphenol A, Bisphenol F, etc. are condensed with formalin in the presence of an acid catalyst (e.g., hydrochloric acid), IF desired, the resulting resin is reacted with epichlorohydrin or cyanogen chloride in the presence of an alkali to obtain a bisphenol/novolak type resin having a unit of the formula (wherein R1 and R2 are each H, methyl or trifluoromethyl; X is H or glycidyl; Y is H, glycidyl or cyano; and n/0). The resin is blended with a curing agent (e.g., a novolak type phenolic resin, N,N'-4,4'-diphenylmethane bis-maleimide), etc., to form the desired heat-resistant resin compsn.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a resin composition that can impart heat resistance, moisture resistance, and low stress, and particularly relates to a resin composition sealed with the resin composition. The present invention relates to a resin-sealed semiconductor device.

[Prior Art] Electrical equipment, electronic components, and other components are becoming smaller and lighter, have higher performance, have higher reliability, and are more multifunctional. For the insulating materials, laminated materials, sealing materials, etc. used in these materials, there is a strong desire to develop resin systems with even better heat resistance, moisture resistance, electrical insulation properties, and adhesive properties. In particular, as resin-sealed, positive-type semiconductor devices are increasingly being used in industrial applications, there is a strong demand for the development of products that can withstand use in harsher environments.

Conventionally, the mainstream of the sealing resin composition has been an epoxy material cured with a novolac phenol resin.

・ [Problems to be solved by the invention] However, in this system, when trying to achieve a balance between heat resistance and low stress, either one of them may be impaired, or there may be problems with moldability, especially appearance and mold stains. There was a problem that occurred.

An object of the present invention is to provide a heat-resistant resin composition capable of imparting heat resistance, moisture resistance, and low stress, and a resin-sealed semiconductor device sealed with the resin composition. There is a particular thing.

[Means for solving problems]

To summarize the present invention, the first invention of the present invention relates to a heat-resistant resin composition, which comprises the following general formula (wherein R1 and R are the same or different, hydrogen, methyl group, or trifluoromethyl group, or hydrogen or glycidyl group, Y represents hydrogen, glycidyl group, or cyanide group, n is 0
It is characterized by containing a bisphenol novolac type resin containing units represented by (indicating a larger number).

In addition, inventions v and 2 of the present invention relate to a resin-sealed semiconductor device, in which at least a part of the semiconductor element and the IJ-wire are sealed with the heat-resistant resin composition of the first invention. It is characterized by being molded.

The composition of the present invention has the above formula! It may include a resin in which X and Y are hydrogen, and a resin in which X and Y are groups other than hydrogen.

Further, the composition of the present invention uses a novolac type phenolic resin, poly p-hydroxystyrene, and holly p-
(4-hydroxyphenyl)styrene and polyfunctional N
- May contain substituted maleimides.

The bisphenol novolac type resin in which the groups X and Y are hydrogen in the general formula I can be synthesized, for example, by a reaction according to the reaction equation below.

R, i.e., bisphenol F (Ft, Fl, = H)
, bisphenol A (R,R snow=-Q)i, group),
Trifluoromethyl type bisphenol A (RIR,
= -0F3 group) fk, E is obtained by condensation reaction of formalin and an acidic catalyst such as hydrochloric acid or oxalic acid.

The resulting resin has a molecular size distribution with n up to about 8.

In addition, in the general formula (3), an epoxy resin in which at least one of the groups X and Y is a glycidyl group and the remainder is hydrogen can be, for example, the above-mentioned bisphenol novolac type resin, shrimp chlorohydrin, sodium hydroxide, etc. It can be synthesized by reacting in the presence of an alkali.

Similarly, in the above general formula I, at least one of the groups X and Y is a cyano group and the remainder is hydrogen. It can be synthesized by reacting in the presence of

Naturally, by performing both reactions simultaneously or sequentially, it is also possible to obtain a resin into which both groups are introduced.

In the present invention, novolac type phenolic resins include phenol, cresols such as o+, m+, and p-, xylenols such as o-, m-, and p-, catechol, resorcinol, It refers to a resin obtained by dehydration condensation of biphenols such as hydroquinone and phloroglucin with aldehydes such as formaldehyde in the presence of an acidic catalyst, and resins with an average molecular weight of 280 to 550 are preferred.

In addition, in the present invention, poly-p-hydroxystyrene is VljtIFK having a repeating unit represented by the following formula:
The number average molecular weight is preferably in the range of 1.000 to 2 cL000.

Moreover, the button 17 p + (4
-Hydroxyphenyl)styrene or its copolymer is a polymer having a repeating unit represented by the following formula: It is a compound represented by [wherein R represents an alkylene group, an arylene group, or a divalent organic group substituted thereof]. For example, N, N'-ethylene bismaleimide, N
, N'-hexamethylene bismaleimide, N, N'-dodecamethylene bismaleimide, N, N'-m-phenylene bismaleimide, N, N'-4,4'-cyphenyl ether bismaleimide)", N, N'-4,4'-diphenylmethane bismaleimide)", N, N'-4,4'-dicyclohexylmethane bismaleimide, N, N'-4,
4'-Metaxylene bismaleimide, N, N'-4゜4
'-Diphenylcyclohexane bismaleimide, 2.2
- His(a-(4-maleimidophenoxy)phenyl)furopane, 2,2-bisC5-mef-4-(4-maleimidophenoxy)phenyl]propane, 2,2-bis[3-chloro-4-( 4-maleimidophenoxy)phenyl]propane, 2,2-bis[3-bromo a-(
4-maleimidophenoxy)phenyl]furopane, 2.
2-bis[5-ethyl-4-(4-maleimidophenoxy)phenyl]propane, 2-bis[3-propyl-
4-(4-maleimidophenoxy)phenyl]furopane, 2,2-bis[3-improbyl-4-(4-maleimidophenoxy)phenyl]propa7,'2,2-bis[3-butyl-a-( 4-Maleimidophenoxy)phenyl]furopane, 2,2-bis[3-sec-butyl-
4-(4-maleimidophenoxy)phenyl]propane, 2.2-bis[3-methoxy-4-(4-maleimidophenoxy)phenyl]propane, 1.1-bisC4-
(4-maleimidophenoxy)phenyl]ethane, 1.1-bis[5-methyl-4-(4-maleimidophenoxy)phenyl]ethane, 1.1-bis[5-chloro-4
-(4-maleimidophenoxy)phenyl]ethane, 1
゜1-bis[3-bromo-4-(4-maleimidophenoxy)phenyl]ethane, bis(a-(4-maleimidophenoxy)phenylcomethane, bis[3-methyl-4
-(4-maleimidophenoxy)phenylcomethane, bis[3-chloro-4-(4-maleimidophenoxy)phenylcomethane, bis[3-bromo-4-(4-maleimidophenoxy)phenylcomethane, 1,1 ．． tAA3
-Safluoro2,2-bisC4-(4-maleimidophenoxy)phenyl]propane, 1. t1sho”
3-hexachloro-2,2-bis(-4-(<-male is dophenoxy)phenyl]propane, 5-bis(4
-(4-maleimidophenoxy)phenyl]pentane,
1.1-bis(4-(4-maleimidophenoxy)phenyl)propane, 1,1.1.1lS-hexafluoro-2,2-bis[5-dibromo-4-(4-maleimidophenoxy)phenyl] Propane, 1.1.1.3
,5-hexafluoro-2,2-bis[5-methyl-4
-(4-maleimidophenoxy)phenyl]propane, etc., and two or more of these can also be used in combination. Furthermore, mixtures of mono-substituted maleimide, tri-substituted maleimide, tetra-substituted maleimide and the above-mentioned substituted bismaleimide can also be used as appropriate.

In the W resin composition of the present invention, the use of a conventionally known epoxy resin and its additives does not impair the effects of the present invention.

Usable epoxy resins include, for example, diglycidyl ether of bisphenol A, 44-epoxycyclohexylmethyl-(he4-epoxy)cyclohexanecarboxylate, vinylcyclohexane dioxide, 4.
4'-di(1,2-epoxyethyl)diphenyl ether, 4.4'-(1,2-epoxyethyl)biphenyl, 2.2-bis(&4-epoxycyclohexyl)propane, glycidyl ether of resorcin, diphenyl ether of phloroglucin. Glycidyl ether, diglycidyl ether of methylphloroglucin, bis-(2,5-epoxycyclopentyl) ether, 2-(t,a-epoxy)cyclohexane-5-spiro(!1,4-epoxy)-cyclohexane- m-dioxane, bis-(3゜4-epoxy-6-methylcyclohexyl)adipate, N, N'
-Bifunctional epoxy compounds such as m-phenylenebis(4,5-diboxy1,2-cyclohexane)dicarboximide, triglycidyl ether of para-aminophenol, polyallyl glycidyl ether, 1.45-
tri(1,2-epoxyethyl)benzene, 2. λI
Epoxy compounds having five or more functionalities such as a, al-tetraglycidoxybenzophenone, tetraglycidoxytetraphenylethane, polyglycidyl ether of phenol formaldehyde novolak, triglycidyl ether of glycerin, triglycidyl ether of trimethylolpropane are used. .

One or more of the above compounds can also be used in combination. When using these epoxy compounds, a curing agent that causes a crosslinking reaction is also used.

They are written by Hiroshi Shinnai: Eboxy Resin (September 1970, published by Shokodo), pp. 109-149, Lee.

Epoxy Re8ins by Lse, Neville, New York City, McGraw-Hill Book Company, Inc. (Me Graw-Hill Bo)
OK Company Engineering nc) (Published in 1957) pp. 63-141, P, E, Prunis (P, 1. Bru
nis) Author: Epoxy Resin Technology (
11! poxy Re5tns Technology
) New York City, Interscience Publishing.
(Published in 1968) Compounds described in the 45th to 111th members, such as aliphatic polyamines, aromatic polyamines, amines including secondary and tertiary amines,
Carboxylic acids, esters such as trimellidic triglyceride, carboxylic anhydrides, aliphatic and aromatic polyamide oligomers and polymers, boron trifluoride-amine complexes, phenolic resins, melamine resins, urea resins, urethane resins, etc. In addition, there are synthetic resin initial condensates such as dicyandiamide, carboxylic acid hydrazide, and polyaminomaleimide.

One or more of the above curing agents can be used depending on the use and purpose.

In particular, 1-phenol novolak resin is suitable as the curing agent component of the semiconductor encapsulation material from the viewpoint of the adhesiveness of the cured resin to the metal insert and the workability during molding.

For the resin q1 composition, a known catalyst known to be effective in accelerating the curing reaction between an epoxy compound and a novolac type phenol resin can be used.

Such catalysts include, for example, triethanolamine,
Tertiary amines such as tetramethylbutanediamine/, tetramethylpentanediamine, tetramethylhexanediamine, triethylenediamine, dimethylaniline, oxyalkylamines such as dimethylaminoethanol, dimethylaminopentanol, and tris(dimethylaminomethyl)phenol , N-/tylmorpholine, and N-ethylmorpholine.

Also, cetyltrimethylammonium bromide, cetyltrimethylammonium chloride, dobsilt 11
Methylammonium iodide, trimethyldodecyl ammonium chloride, benzyldimethyltetradecylammonium chloride, benzyldimethylpalmitylammonium chloride, allyldodecyltrimethylammonicum promide, benzyldimethylstearylammonium bromide, stearyltrimethylammonium chloride, p/zyldimethyltetradecyl There are quaternary ammonium salts such as ammonium acetate.

Also, 2-methylimidazole, 2-ethylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-methyl-4-ethylimidazole, 1
-butylimidazole, 1-furopyru-2-methylimidazole, 1-benzyl-2-methylimidazole, 1
-Imidazoles such as cyanethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-azine-2-methylimidazole, and 1-azine-2-undecylimidazole , triphenylphosphine tetraphenylborate, tetraphenylphosphonium tetraphenylborate, triethylamine tetraphenylborate, N-methylmorpholinetetraphenylborate, 2-ethyl-4-methylimidazoletetraphenylborate, 2-ethyl-1,4-dimethylimidazole Examples include tetraphenylboron salts such as tetraphenylborate.

The above-mentioned catalysts can be used in combination of two or more thereof, and may be used in a weight ratio of rL01 to 20 with respect to 100 parts of the polyfunctional epoxy compound.

[Implementation f! AJ] Hereinafter, the present invention will be explained in more detail with reference to Examples.
The invention is not limited to these examples.

Incidentally, FIG. 1 shows a cross-sectional view of a resin molded semiconductor device according to an embodiment of the present invention.

In FIG. 1, numeral 1 is an LSI element, 2 is a lead wire,
3 means a wire bonding acid, and 4 means a sealing resin composition.

Examples 1 to 10 Pryor 7en VH-4150 (manufactured by Dainippon Ink Co., Ltd., OH equivalent: 118, softening point 86° C.) is a novolak type resin of bisphenol A, and the above Pryor 7 as a polyfunctional Evokiku resin of bisphenol novolak En V
It is a resin obtained by glycidyl etherification of H-4150,
Epiclon N-880 (manufactured by Dainippon Ink Co., Ltd., epoxy equivalent: 213, softening point: 77°C) and a glycidyl etherified resin of trifluoromethyl-type bisphenol A novolac type resin (epoxy equivalent: 77°C)
Novolac type phenol resin (manufactured by Hitachi Chemical Co., Ltd., softening point 81°C, number average molecular weight 475), poly-p-hydroxy As styrene, M resin (manufactured by Maruzen Oil Co., Ltd., number average molecular weight 4soo), as a polyfunctional N-substituted limide compound, N,N'-4,4'-diphenylmethane simalimide, as a polyfunctional epoxy resin, XD-9053 (manufactured by Dow Chemical Company, epoxy equivalent: 220) was used to blend the predetermined amounts shown in Table 1.

These formulations were supplemented with 2 parts by weight of triphenylphosphine and epoxysilane KB as a coupling agent.
M303 (Shin-Etsu Chemical Co., Ltd. ff) 2 parts by weight, as a mold release agent,
1 part by weight of calcium stearate, 1 part by weight of Hoechst Wax K (manufactured by Hoechst Japan), as a flame retardant,
5 parts by weight of addition-type imide coated red phosphorus, as a filler,
A total of 75% by weight and t% of fused silica glass powder, 9 coloring materials, and 2 parts by weight of carbon black (manufactured by Cabot) were added and blended.

Next, the above-mentioned mixture was heated and kneaded using two 8-inch diameter rolls at 75 to 85°C, cooled, and coarsely ground to obtain a resin composition.

Table 1 shows the properties of each resin composition obtained.

Example 11.12 and Comparative Reli 1 As a novolac type epoxy resin of bisphenol A, 100 weight tt part of Evicron N-880 (manufactured by Dainippon Ink Co., Ltd., epoxy contact, 213, softening point 77 ° C.) was used,
In addition, novolac type phenolic resin Hp is used as a curing agent.
-6oyN (manufactured by Hitachi Chemical Co., Ltd.) 55-layer upper part and Ply-O7enV as a novolac type resin of bisphenol A.
H-4150 (softening point, 86°C: manufactured by Dainippon Ink Co., Ltd.) 5
Two formulations were made by adding 5 parts by weight separately.

To these, 2.5 parts by weight of triphenylphosphine as a curing accelerator, 2 parts by weight of epoxysilane xBn3os (manufactured by Shin-Etsu Chemical Co., Ltd.) as a coupling agent, and 4 parts by weight of addition-type imide coated red phosphorus as a flame retardant. 0 parts by weight,
As a mold release agent, 1 part by weight of calcium stearate, 81.0 parts by weight of Bexto wax, 480 parts by weight of fused silica glass powder as a filler, and 2 parts by weight of carbon black (Cabot Exhibition) as a coloring agent. was added.

Next, the two types of blends were heated and kneaded for about 7 minutes using two 8-inch diameter rolls heated to 75-85°C. Thereafter, the mixture was cooled and coarsely pulverized to obtain two types of LSI sealing resin compositions.

Then, using the resin composition, DR
AM memory LSI, each 100 (hard, 175℃,
70197cm'' for 1.5 minutes to obtain a resin-sealed LSI.The resin-sealed LSI was placed in supersaturated steam (PCT) at 121°C and 2 atm for a predetermined period of time. , I took it out and checked whether the electrical operation of the LSI was normal.

The abnormal LSI was destroyed and it was confirmed that the AT wiring on the element had corroded, leading to a disconnection failure. Table 2 shows the results of the moisture resistance reliability of this LSI.

Note to Table 2 [Yes] In this example, the epoxy resin is the conventionally known novolak type epoxy resin y1! ! 0N1273(
(manufactured by Ciba) was used.

As is clear from Table 2, the moisture resistance reliability of the semiconductor device according to the present invention is superior to that of the conventional device.

Example 13 As a bisphenol novolak type resin, 100 parts by weight of Pryophen VH-4150 and 10 parts by weight of chlorocyan
A novolac-type bisphenol resin having a cyanate group (Y in the formula! is a cyano group) obtained by reacting 1 part by weight with 1 part by weight of triethylamine was used.

60 parts by weight of N,N'-4,4'-diphenylmethane bismaleimide and 5 parts by weight of dicyandiamide were added to 100 parts by weight of this resin, and after heating and mixing, 200C
A cured product was obtained by press molding at 200 kgf/cm for 12 hours. The glass transition point of this cured product was 250C and 160℃.
The electrical insulation resistance (volume resistivity) is 1.8X101
It was 4Ω/Confucian.

〔Effect of the invention〕

As explained above, the resin composition of the present invention has heat resistance,
It is capable of imparting temperature resistance and low stress, and the semiconductor device of the present invention, which is resin-sealed using the composition, is especially popular in terms of moisture resistance and reliability! It has a remarkable effect.

4. Simple Explanation of Figure 1 Figure 1 is a sectional view of a resin molded semiconductor device F7 according to an embodiment of the present invention.

1: L8 element, 2: Lead wire, 3: Wire bond line,
4: Sealing resin composition

Claims (1)

[Claims] 1. The following general formula I: ▲There are mathematical formulas, chemical formulas, tables, etc.▼... [I] (In the formula, R_1 and R_2 are the same or different, and are hydrogen, a methyl group, or a trifluoromethyl group. , X represents hydrogen or a glycidyl group, Y represents hydrogen, a glycidyl group, or a cyano group, and n represents a number greater than 0). A heat-resistant resin composition. 2. The heat-resistant resin composition according to claim 1, wherein the composition contains a resin in which X and Y are hydrogen in the general formula I, and a resin in which X and Y are groups other than hydrogen. thing. 3. The heat-resistant resin composition according to claim 1 or 2, wherein the composition contains an epoxy resin of formula I and a curing agent thereof. 4. At least a part of the semiconductor element and lead wire is expressed by the following general formula I: ▲There are mathematical formulas, chemical formulas, tables, etc.▼...
[I] (In the formula, R_1 and R_2 are the same or different and represent hydrogen, a methyl group or a trifluoromethyl group, X represents hydrogen or a glycidyl group, Y represents hydrogen, a glycidyl group or a cyano group, and n is 1. A resin-sealed semiconductor device characterized in that it is molded with a heat-resistant resin composition containing a bisphenol novolac type resin containing a unit represented by the formula (indicating a number greater than 0).