JPH0586138A - Heat-resistant resin composition - Google Patents

Abstract

PURPOSE:To obtain the title composition excellent in heat resistance, low-stress properties, adhesion, etc., by mixing a specified modified maleimide compound with a specified bismaleimide compound and a specified aromatic diamine in a specified mixing ratio. CONSTITUTION:The title composition is prepared by mixing a polysiloxane- modified maleimide compound (A) of formula I [wherein R<1> to R<4> are each H or a (halo)hydrocarbon group; X<1> and X<2> are each alkylene or alkenylene; Ar<1> and Ar<2> are each a bivalent group having one benzene ring; D<1> and D<2> are each a bivalent group containing a C-C double bond as a main chain; n is 2-30; and u and v are each 0 or 1] with a bismaleimide compound (B) of formula II[wherein X<3> is-CH2-, -C(CH3)2-, -SO2-, -SO-, -S-or-O-; Ar<3> and Ar<4> are each Ar<1>; D<3> and D<4> are each D<1>; and m is u] and an aromatic diamine (C) of the general formula: H2N-Ar<5>-NH2 (wherein Ar<5> is Ar<1>) in such a mixing ratio that A/B = 10/90-100/0 (molar ratio) and C/(A+B) = 50/100-100/100 (molar ratio).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a heat-resistant resin composition which is excellent in heat resistance, moisture resistance, low stress and adhesion and is useful as a sealing material or coating material for electronic parts such as semiconductors and electronic equipment. Is.

[0002]

2. Description of the Related Art In recent years, encapsulating materials composed of thermosetting resin, mainly epoxy resin, have been widely used for semiconductor elements such as IC and LSI. Epoxy resin type encapsulant
It is excellent in terms of cost and productivity, and is used in large quantities, but it has reached the limit in terms of heat resistance.Recent reliability after solder immersion due to high integration and high density mounting etc. However, the heat resistance requirement is not being satisfied.

On the other hand, polyimide has been conventionally known as a heat-resistant resin, and a dehydration condensation type polyimide is used for a passivation film and an α-ray protective film of a semiconductor element, and a part of heat-resistant sealing. Addition-type maleimide-based polyimide is used as the material resin.

However, although these polyimides have a sufficiently satisfactory heat resistance, they have the drawback that they are hard and brittle and cracks easily occur, and the internal stress after curing is large, resulting in poor adhesion to the device. It was

In order to solve the drawbacks of these polyimides,
Although some methods have been proposed for adding a silicone compound or using diaminopolysiloxane as a diamine which is a raw material for polyimide, these silicone-modified polyimides have been improved in adhesion and stress reduction. However, there is a problem that the heat resistance, which is a characteristic of polyimide, is also reduced.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to solve the conventional problems of cracking and adhesion of polyimide, or deterioration of heat resistance due to silicone modification, and to maintain high heat resistance. And to provide a heat resistant resin composition having excellent adhesion and low stress.

[0007]

The present invention provides a polysiloxane-modified maleimide compound represented by the general formula (1), a bismaleimide compound represented by the general formula (2), and an aromatic compound represented by the general formula (3). It is a heat resistant resin composition obtained by mixing diamine in the following ratio. (1) / (2) = 10/90 to 100/0 (molar ratio) (3) / {(1) + (2)} = 50/100 to 100 /
100 (molar ratio)

The present invention will be described in detail below. Among the polysiloxane-modified maleimide compounds represented by the general formula (1), those having u and v = 1 can be obtained by the following synthetic route. Alkenyl halides such as allyl chloride, methallyl chloride or butenyl chloride,
Alternatively, reacting an alkynyl halide such as butynyl chloride having a triple bond in the molecule with an aminophenol,
Alkenyloxyphenylamine or alkynyloxyphenylamine is synthesized as an intermediate. The intermediate is reacted with maleic anhydride to obtain an alkenyloxyphenylmaleimide or alkynyloxyphenylmaleimide, which is hydrosilylated with a siloxane oligomer having a hydrogen terminal (for example, formula A).

[0009]

[Chemical 4]

The polysiloxane-modified maleimide compound of u, v = 0 can be obtained by the following synthetic route.
Alkenylphenylamine such as aminostyrene or allylaniline or alkynylphenylamine such as ethynylaniline is reacted with maleic anhydride to obtain alkenylphenylmaleimide or alkynylphenylmaleimide, which is hydrosilylated with a siloxane oligomer. (Eg Formula B).

[0011]

[Chemical 5]

The number of repeating siloxanes (n in the general formula (1)) of the polysiloxane-modified maleimide compound used in the present invention is 2 to 30, preferably 4 to 10.
Is. When n is larger, the stress relaxation effect of the resin composition is larger, but when it is too large, the molecular weight becomes large, so that the crosslink density in the reaction with the aromatic diamine decreases and the heat resistance decreases, which is not preferable.

Further, for the same reason, in the general formula (1),
The alkylene or alkenylene of X ¹ and X ² preferably has a short chain length, and propylene or butylene, or propenylene or butenylene is suitable. Furthermore, R ^{1 to} R ⁴ bonded to Si are preferably methyl or phenyl from the viewpoint of easy synthesis of the raw material, and for the purpose of lowering the dielectric constant of the resin composition and increasing transparency, trifluoromethyl group —CF is used. _{3 is} also preferred.

As D ¹ and D ² in the general formula (1) and D ³ and D ⁴ in the general formula (2), a vinylene group or one in which one hydrogen of the vinylene group is replaced with a methyl group is used. Among them, vinylene group is preferable from the viewpoint of easy synthesis of raw materials. Ar ¹ and Ar ² in the general formula (1) and Ar ³ and Ar ⁴ in the general formula (2) are phenylene groups or
One in which one or more hydrogen atoms in the same group are replaced with halogen is included. X ³ in the general formula (2) is —CH ₂ —,
-C (CH ₃ ) _2- , -SO _2- , -SO-, -S- or -O- may be mentioned, but -CH ₂ -is preferable because of easy availability, and m = 1 for the same reason. Is preferred.

In the present invention, the molar ratio (1) / (2) of the polysiloxane-modified maleimide compound to the unmodified maleimide compound is 10: 1.
Although it is / 90 to 100/0, the range of 20/80 to 50/50 is the most preferable in terms of the balance between the stress relaxation effect and the heat resistance.

The molar ratio (3) / {(1) + (2)} of all maleimide compounds and aromatic diamine is 50/100.
It is necessary to be 100 to 100/100, preferably 70/100 to 90/100. Aromatic diamine reacts only with maleimide compound, but maleimide compound not only reacts with diamine but also with maleimide mutual reaction, so if diamine is in excess of the above molar ratio, unreacted diamine will remain. Heat-resistant,
It is not preferable because mechanical properties are deteriorated. On the other hand, when the maleimide compound is in excess of the above molar ratio, the reactivity of curing is lowered, which is also not preferable.

Examples of Ar ⁵ in the general formula (3) include a phenylene group and a group in which the benzene ring of the group is replaced with biphenyl or benzophenone. Examples of the aromatic diamine preferably usable in the present invention include diaminodiphenyl ether, diaminodiphenylmethane, diaminodiphenylsulfone, 4,4′diamino / 3,3′diethyldiphenylmethane, phenylenediamine and diaminobenzophenone.

[0018]

The resin composition obtained by the present invention is easily cured by heating, and the cured product obtained has good adhesion and low stress and high heat resistance. The reason is that the polysiloxane skeleton that imparts adhesion and low stress is
It is presumed that the modified maleimide compound introduced into the heat-resistant maleimide compound was used, while the diamine component, which was conventionally the cause of the decrease in heat resistance, was replaced with a highly heat-resistant aromatic diamine.

[0019]

【Example】

Example 1 The following 1. ~ 4. The above raw materials were mixed and dissolved to obtain a varnish of the heat resistant resin composition. The varnish was treated at the temperature and time shown in Table 1 while stirring in an oil bath. Then, the obtained composition was heat-treated at the temperature and time shown in Table 1 to prepare a test piece having a width of 4 mm, a length of 30 mm and a thickness of 2 mm.
The test described in Table 1 was performed. The evaluation results are shown in Table 1.

1. Polysiloxane-modified maleimide compound:

[0021]

[Chemical 6]

2. Bismaleimide compound: 4,4'diaminodiphenylmethane bismaleimide

[0023]

[Chemical 7]

3. Aromatic diamine: 4,4'diaminodiphenylmethane

[0025]

[Chemical 8]

4. Solvent: N-methylpyrrolidone

Examples 2 and 3 and Comparative Example 1 Using the same raw materials as in Example 1, test pieces of the resin composition were prepared under the compounding ratio and conditions shown in Table 1, and the test shown in Table 1 was conducted. Is shown in Table 1.

[0028]

[Table 1]

[0029]

The resin composition obtained according to the present invention has high heat resistance, low stress and excellent adhesion. This resin is a useful material having high adhesion and reliability as a passivation film, an insulating film, an α-ray protective film for semiconductor elements, or as a heat resistant coating material or a molding material.

Claims (1)

[Claims] 1. A polysiloxane-modified maleimide compound represented by the following general formula (1), a bismaleimide compound represented by the general formula (2) and an aromatic diamine represented by the general formula (3) are mixed in the following ratios. A heat resistant resin composition comprising: [Chemical 1] [Chemical 2] [Chemical 3] (1) / (2) = 10/90 to 100/0 (molar ratio) (3) / {(1) + (2)} = 50/100 to 100 /
100 (molar ratio)