JPH044218A - Semiconductor sealant composition - Google Patents

Abstract

PURPOSE:To provide the subject composition having excellent thermal impact resistance by compounding a phenol novolak resin to which a silane coupling agent-reacted polysiloxane polymer is dispersed and bonded, an epoxy resin containing a curing agent, etc., and an inorganic filler in a specific ratio. CONSTITUTION:The objective composition reduced in the generation of cracks and employed as a sealing agent comprises 1-50 pts.wt. of a product prepared by dispersing and bonding a silane coupling agent-reacted polysiloxane polymer to a phenol novolak resin, the silane coupling agent-reacted polysiloxane polymer being prepared by reacting an epoxy group-containing polysiloxane compound [e.g. a compound of the formula (n is an positive integer)] with an amino group- containing silane coupling agent (e.g. gamma-aminopropyltriethoxysilane), (B) 100 pts.wt. of an epoxy resin (e.g. bisphenol A type resin) containing a curing agent (e.g. phthalic anhydride) and a curing accelerating agent [e.g. 2,4,6-tris(dimethylaminomethyl) phenol] and (C) 200-700 pts.wt. of an inorganic filler (e.g. molten silica).

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to an encapsulant composition for semiconductors.

[Prior art and its problems] Epoxy resins are widely used as encapsulating materials for semiconductors. Epoxy resin has excellent moldability, adhesiveness, mechanical strength, electrical properties, heat resistance, moisture resistance, etc., but it can cause internal stress due to temperature changes during molding of semiconductor elements and handling after molding. There are problems such as the occurrence of cracks in elements and sealing resin, which significantly reduces the reliability of semiconductor products.As a solution to this problem, organic silicone compounds such as silicone oil and silicone rubber are used as low stress modifiers. have been proposed (for example, Japanese Patent Application Laid-Open No. 6
3-248822).

Silicone oil and silicone rubber have the problem of poor thermal shock resistance because it is difficult to uniformly disperse and bond with epoxy resin.Also, for the same reason, silicone oil and silicone rubber tend to bleed during molding, resulting in molds getting dirty and poor workability. There are also the problems mentioned above.

[Means for Solving the Problems] In order to solve the above-mentioned problems, the present invention involves polymerizing (A) a silane coupling agent in which one of the functional groups is an amino group into a polysiloxane compound having an epoxy group. Products 1 to 1 in which a silane-coupled polysiloxane polymer is bonded to a phenol novolak resin in a dispersed state.
50 parts by weight, (B) 100 parts by weight of an epoxy resin containing a curing agent and a curing accelerator, and (C) 200 to 7 parts by weight of an inorganic filler.
00 parts by weight of the semiconductor encapsulant composition.

First, the starting material for product A will be explained.

As the polysiloxane compound having an epoxy group, for example, compounds represented by the following two types of structural formulas can be used.

[1 line margin] However, n and I indicate positive integers.

The molecular weight of the polysiloxane compound having an epoxy group represented by these structural formulas is preferably within the range of about 500 to 20,000.0 If the molecular weight is less than 500, it is poor in reducing stress, and if it is more than 20,000, it may react with the amino group. The properties of the product decrease, making it difficult to obtain the desired product A.

As a silane coupling agent in which one of the functional groups is an amino group, for example, γ-aminopropyltriethoxysilane, N-β(aminoethyl)γ-aminopropyltrimethoxysilane, N-β(aminoethyl)γ-amino Propylmethyldimethoxysilane or the like can be used.

Examples of phenol novolak resins include, for example, the trade names [TD-2106, TD-2131 (manufactured by Dainippon Ink and Chemicals), Tamanol 758. Tamanol 759 (manufactured by Arayo Kagaku Kogyo)].

The starting material for product A is such that the molar ratio a+/a2 of the polysiloxane compound (a1) having an epoxy group and the silane coupling agent (a2) having an amino group is 0.
．． It is preferable that the weight ratio a1/as of the polysiloxane compound (at) having an epoxy group and the phenol novolac resin (a3) is selected to be in the range of 0.5 to 2.

Moreover, if the molar ratio at/az is less than 0.5, it will be inferior in terms of stress reduction, and if it is more than 10, it will be inferior in terms of immobilization of the polysiloxane compound having an epoxy group in the resin component, and the desired product will not be obtained. You won't be able to get it. Weight ratio a□/a3
If it is less than 0.1, it will be inferior in terms of stress reduction, and if it is more than 2, the dispersibility in the resin component will be poor, making it impossible to obtain the desired product.

Next, epoxy resin B containing a curing agent and a curing accelerator will be explained. As the epoxy resin, for example, bisphenol A type, novolak type, alicyclic type, linear fatty acid type, or halogenated type epoxy resin can be used. As curing agents for these epoxy resins, for example, acid anhydrides such as phthalic anhydride, amines such as diaminodiphenylsulfone, phenol novolac resins, cresol novolac resins, etc. can be used, and as curing accelerators, for example, 2,4.6-)lith(dimethylaminomethyl)phenol, tertiary amines such as benzyldimethylamine, imidazoles such as 2-methylimidazole, organic phosphines such as triphenylphosphine,
1.8-Diazabicyclo(5,4,O)undecene-7
(DBU) and its derivatives, etc. can be used.

Next, the inorganic filler C will be explained. As the inorganic filler, for example, fused silica, crystalline silica, alumina, magnesia, calcium carbonate, glass fiber, etc. can be used.

Each composition for such a semiconductor encapsulant includes 100 parts by weight of epoxy resin B containing a curing agent and a curing accelerator;
Product A is 1 to 50 parts by weight, and inorganic filler C is 200 to 50 parts by weight.
It is blended in a proportion of 700 parts by weight.

If the product A is less than 1 part by weight, the modification effect of reducing stress cannot be obtained, and if it is more than 50 parts by weight, it causes a decrease in mechanical strength.

If the inorganic filler C is less than 200 parts by weight, the coefficient of linear expansion α1 becomes large and the thermal shock resistance decreases. If it exceeds 700 parts by weight, fluidity decreases and molding workability deteriorates.

In the present invention, colorants, flame retardants, etc. may be added as appropriate.

[Operation] Product A is a silane coupling agent-containing polysiloxane polymer obtained by polymerizing a silane coupling agent having an amino group as one of the functional groups to a polysiloxane compound having an epoxy group, dispersed in a phenol novolak resin. Since the polysiloxane compound is bonded to the polysiloxane compound, dispersion and bonding to the epoxy resin B containing the curing agent and curing accelerator are improved, and bleeding of the polysiloxane compound is extremely reduced.

Product A is a silane coupling agent-containing polysiloxane polymer obtained by polymerizing a silane coupling agent in which one of the functional groups is an amino group to a polysiloxane compound having an epoxy group, which is bonded in a dispersed state in a phenol novolac resin. It functions as an appropriate stress relaxation material for semiconductor sealing materials using epoxy resin.

Since the inorganic filler has a higher thermal conductivity than the synthetic resin component, it contributes to efficiently dissipating heat to the outside without accumulating the amount of heat generated by the semiconductor element inside.

[Example 1] First, 25 parts of a phenol novolac resin (Tamanol 758 manufactured by Arakawa Chemical Industries) and 100 parts of a polysiloxane compound having an epoxy group (KF 105 manufactured by Shin-Etsu Chemical Industries) were melted at 120°C and stirred for 60 minutes. do. At this time, the phenol novolac resin (Tamanol 758) hardly reacts with the epoxy group of the polysiloxane compound (KF105) having an epoxy group at a temperature of 120°C, so it is uniformly dispersed by stirring for 60 minutes. It turns out.

After that, while the temperature was maintained at 120°C, an aminosilane coupling agent (KBM602 manufactured by Shin-Etsu Chemical Co., Ltd.) was added.
25 parts of the epoxy group-containing polysiloxane compound (KF105) and the aminosilane coupling agent (KBM602) were added and stirred for 10 minutes.
) reacts well with the amino group at a temperature of 120°C, so an aminosilane coupling agent (KBM602
) is the amino group of phenol novolak resin (Tamanol 7).
58) A polymerization reaction occurs with the epoxy groups of the polysiloxane compound (KF105) having epoxy groups dispersed therein.

After that, aminosilane coupling agent (KBM602)
amino groups and phenolic novolac resin (Tamanol 75)
8) A polysiloxane compound (KF105) having an epoxy group dispersed therein was subjected to a polymerization reaction with the epoxy group, which was left to cool and was pulverized to obtain a product A1.

11 parts of this product A1, 100 parts of 0-cresol novolac type epoxy resin, 50 parts of phenol novolak resin as an epoxy resin hardener, 1.5 parts of triphenylphosphine as a hardening accelerator, and melting of the inorganic filler. 400 parts of silica (manufactured by FS-74 Denki Kagaku Kogyo), mold release agent (
After thoroughly mixing 4.5 parts of WAXOP (manufactured by Hequist Java) in a mixer, kneading with a heated roll (100°C),
After cooling, it was pulverized to obtain a semiconductor encapsulant composition.

[Example 2] First, 25 parts of a phenol novolak resin (KP-757B manufactured by Arakawa Chemical Industries) and 100 parts of a polysiloxane compound having an epoxy group (KF 102 manufactured by Shin-Etsu Chemical Industries) are stirred at 120° C. for 60 minutes. At this time, the phenol novolac resin (KP-757B) hardly reacts with the epoxy group of the polysiloxane compound (KF102) having an epoxy group at a temperature of 120°C, so 6
Stirring for 0 minutes will result in uniform dispersion.

After that, while the temperature was maintained at 120°C, an aminosilane coupling agent (KBM602 manufactured by Shin-Etsu Chemical Co., Ltd.) was added.
25 parts of the epoxy group-containing polysiloxane compound (KF102) and the aminosilane coupling agent (KBM602) are added and stirred for 10 minutes.
) reacts well with the amino group at a temperature of 120°C, so an aminosilane coupling agent (KBM602
) is the amino group of phenol novolak resin (KP-75
A polymerization reaction occurs with the epoxy groups of the polysiloxane compound (KF102>) having epoxy groups dispersed in 7B).

After that, aminosilane coupling agent (KBM602)
amino group and phenolic novolac resin (KP~757
A polysiloxane compound (KF102) having epoxy groups dispersed in B) was subjected to a polymerization reaction with the epoxy groups, which was left to cool and was pulverized to obtain product A2.

11 parts of this product A2, 100 parts of O-cresol novolak type epoxy resin, 50 parts of phenol novolac resin as an epoxy resin hardener, 1.5 parts of triphenylphosphine as a hardening accelerator, and melting of the inorganic filler. 400 parts of silica (manufactured by FS-74 Denki Kagaku Kogyo), mold release agent (
After thoroughly mixing 4.5 parts of WAXOP (manufactured by Hequist Japan) in a mixer, kneading with a heated roll (100°C),
After cooling, it was pulverized to obtain a semiconductor encapsulant composition.

[Comparative Example 1 Polysiloxane compound having coepoxy group (KF105
Shin-Etsu Chemical Co., Ltd.) 7 parts, 100 parts of 0-cresol novolak type epoxy resin, 50 parts of phenol novolac resin as an epoxy resin hardener, 1.5 parts of triphenylphosphine as a hardening accelerator, melting of inorganic filler. 400 parts of silica (manufactured by FS-74 Denki Kagaku Kogyo), mold release agent (W
4.5 parts of AXOP (manufactured by Hoechst Japan) were thoroughly mixed in a mixer, kneaded with a heating roll (100°C), cooled and pulverized to obtain an encapsulant composition for semiconductors.

[Comparative Example 2] 14 parts of epoxy-modified polysiloxane compound (KF105) was added to 100 parts of phenol novolak resin at 120°C.
The mixture was stirred for 60 minutes, 0.5 part of DBU was added, and the mixture was further stirred at 120° C. for 30 minutes, left to cool, and pulverized to obtain a semiconductor encapsulant composition.

The bending strength (according to JIS K6911) and bending modulus (JI
S K6911 compliant) Glass transition temperature Tg (TMA
), coefficient of linear expansion α1 (TMA), and mold contamination.
Table 2 shows the results of the resin crack generation test.

[7 lines below] Table 1 Measurement of bending strength and bending modulus is based on JIS K6911.

The glass transition temperature Tg and linear expansion coefficient α were measured by TMA.

Table 2 Sample shape: 16pin DIP Pretreatment conditions = 85°C/85%RH By using Product A, in which a reaction product with a ring agent is combined in a dispersed state in a phenol novolac resin, in an epoxy resin composition, the compatibility between the organosilicone compound and other resin components is improved. Thermal shock resistance is improved without deterioration of properties such as mechanical strength and heat resistance, and as a result,
This has the effect of reducing cracks in semiconductor elements and sealing resin.

In addition, since the polysiloxane compound having an epoxy group dispersed in the phenol novolak resin is combined with the silane coupling agent whose functional group is an amino group, there is no bleeding to the surface of the molded product and the mold It has the effect of improving stains.

Patent applicant: Rikyo Kogyo Co., Ltd. hand Continued Supplementary Positive book (spontaneous) June 1990 I5 1.Display of the incident 1990 Patent Application No. 105689 2. Name of the invention 3. Person who corrects Relationship to the case Patent applicant Postal code　〒530 4. Date of amendment order spontaneous 5. Subject of correction Detailed description of the invention in the specification 6. Contents of amendment However, n, ■, and 1 indicate positive integers.

The molecular weight of the polysiloxane compound having an epoxy group represented by these structural formulas is preferably within the range of about 500 to 20,000. If the molecular weight is less than 500, it will be poor in reducing stress, and if it is more than 20,000, it will not react with the amino group. The properties of the product decrease, making it difficult to obtain the desired product A.

As a silane coupling agent in which one of the functional groups is an amino group, for example, γ-aminopropyltriethoxysilane, N-β(aminoethyl)γ-aminopropyltrimethoxysilane, N-β(aminoethyl)γ-amino Propylmethyldimethoxysilane or the like can be used.

Claims (2)

[Claims] (1) (A) A silane coupling agent-containing polysiloxane polymer obtained by polymerizing a silane coupling agent whose functional group is an amino group to a polysiloxane compound having an epoxy group is bonded in a dispersed state in a phenol novolak resin. 1 to 50 parts by weight of the prepared product; and (B) 10 epoxy resins containing a curing agent and a curing accelerator.
0 parts by weight, and (C) 200 to 700 parts by weight of an inorganic filler. (2) Product A has a molar ratio (=a_1/
a_2) is selected in the range of 0.5 to 10, and the polysiloxane compound (a_1) and the phenol novolak resin (
a_3) weight ratio (=a_1/a_3) of 0.1 to 2
2. The semiconductor encapsulant composition according to claim 1, wherein the semiconductor encapsulant composition is selected within the range of .