JP3255706B2 - Silicone compound - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel silicone compound, and more particularly to a novel silicone compound which can be used as a flexibility imparting agent for thermosetting resins such as electronic materials and adhesives, and a method for producing the same. The invention further relates to a flexibility-imparting agent for thermosetting resins such as epoxy resins, maleimide resins, and polyimide resins.

[0002]

2. Description of the Related Art In recent years, the size, weight, and performance of electronic, electric, and transportation equipment have been reduced, and accordingly, materials having excellent heat resistance have been desired. As the heat-resistant resin, a maleimide resin and a polyimide resin are generally known, but the cured product is hard and brittle, and the application field is limited. Similarly, the cured product of the epoxy resin is hard, and problems such as peeling and cracking of the adhesive surface due to shrinkage stress during curing are caused.

[0003] Conventionally, in order to solve such a problem, for example, an epoxy resin composition for semiconductor encapsulation containing a reaction product of a polybutadiene having two or more carboxy groups and a silicone resin having one or more hydroxyl groups or alkoxy groups (particularly, Japanese Patent Application Laid-Open No. Sho 63-11621, or a pre-reaction product of a modified silicone oil having an epoxy group and a phenol novolak resin.
6) and the like are disclosed. However, the performance of these resin compositions or plasticizers is still insufficient, and the applicable resins are limited.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned drawbacks of the prior art, and is intended to be used in various fields. Another object of the present invention is to provide a silicone compound for providing a resin composition having excellent flexibility, crack resistance, adhesion and hydrophobicity, and a flexibility imparting agent comprising the compound.

[0005]

The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, a novel silicone compound, namely, a silphenylene disiloxane-siloxane copolymer, has a particularly high heat resistance. The knowledge that it contributes to imparting flexibility was obtained. That is, the siloxane having a skeletal structure and the alkyl group and vinyl group in the side chain in one copolymer component contribute to stress relaxation and improvement in hydrophobicity due to shrinkage during curing, and the aromatic ring in the other copolymer component serves as a heat-resistant component of the composition. The present invention was completed based on the knowledge of preventing a decrease in the properties.

It has also been found that the thermosetting resin to which the compound of the present invention is added is effective for all thermosetting resins such as epoxy resin, maleimide resin, polyimide resin, melamine resin, urea resin and phenol resin. Was. Thus, the silicone compounds of the present invention have the formula I:

[0007]

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Wherein R ₁ represents a lower alkyl group;
R ₂ and R ₃ are independent of each other and
Which represents a vinyl group or a lower alkyl group or a phenyl group, and n: m represents a ratio of 0.2: 1 to 2: 1), and is characterized by being a silicone compound having a molecular weight of 500 to 100,000.

The method for producing the silicone compound is represented by the following formula II:

[0010]

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(Wherein R ₁ represents a lower alkyl group;
R ₄ represents a lower alkoxy group or a halogen atom), and a silphenylene compound represented by the following formula III:

[0012]

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[0013] (wherein, R ₂ and R ₃ independently of one another are
OriKatsu, respectively, a vinyl group or a lower alkyl group, or a phenyl group, R ₅ is Table Wa lower alkoxy group or a halogen atom, provided that the reaction of a silicon compound represented by different) from R ₄ Features. Furthermore, the flexibility-imparting agent of the present invention is characterized by comprising the silicone compound of the formula I.

In the present invention, the defined lower alkyl group means an alkyl group having 1 to 4 carbon atoms, preferably an alkyl group having 1 to 2 carbon atoms. The lower alkoxy group means an alkoxy group having 1 to 4 carbon atoms, preferably an alkoxy group having 1 to 2 carbon atoms. Further, the halogen atom means a chlorine, bromine, iodine or fluorine atom, preferably a chlorine atom.

The silicone compound of the present invention has a molecular weight of 50
0 to 100000 is preferred. This is because if it is less than 500, the heat resistance and flexibility of the composition will be degraded, and if it exceeds 100,000, bleed out to the surface of the cured product due to reduced compatibility with the composition and heat resistance will be degraded. The silicone compound of the present invention can be obtained by copolymerizing the silphenylene compound of the formula II and the silicon compound of the formula III as described above.

The copolymerization reaction is preferably carried out in a solvent using a polymerization reaction catalyst. As the solvent, toluene, methyl isobutyl ketone, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, butyl cellosolve, N-
Methyl-2-pyrrolidone, dimethylacetamide, dimethylformamide, dimethylsulfoxide and the like can be mentioned, and all of them are those subjected to a dehydration treatment. In some cases, a mixture of two or more solvents may be used.

In the present invention, polymerization is carried out by performing a dehydration condensation reaction after hydrolyzing a functional group of a monomer to form a silanol. As a catalyst for promoting the dehydration condensation reaction, an acid catalyst such as hydrochloric acid, sulfuric acid, and nitric acid can be preferably used. Further, in the present invention, a hydroxyl group as a terminal group may be silylated in order to stabilize use and storage. Examples of the silylating agent include trimethylchlorosilane, triphenylchlorosilane, trivinylchlorosilane, divinylmethylchlorosilane, dimethylvinylchlorosilane, divinylphenylchlorosilane, diphenylvinylchlorosilane, and methylphenylvinylchlorosilane. Chlorsilane can be used. In order to promote silylation, a basic catalyst such as pyridine or triethylamine may be used.

Further, the reaction temperature is in a temperature range of 60 ° C. to 150 ° C.
It can be preferably carried out in a box. Siliconization of the present invention
The compound is, as shown above, the monomer (1) formula and the monomer
(2) Production by copolymerization with the formula
The point to do is R_Four, R_FiveHave the same functional group and
Hydrolysis can lead to differences in conjugated, non-conjugated and linear
This would inhibit the copolymerization reaction. Therefore,
R as a feature of Ming _Four, R_FiveWith different functional groups (eg
For example, R_FourIs a methoxy group, R_FiveUses chloro group etc.)
Thus, these problems can be solved.
That is, a silicone compound having a high copolymerization ratio is produced.
be able to.

[0019]

The silicone compound according to the present invention has the above-mentioned property improvements, but the heat resistance, hydrophobicity, flexibility, crack resistance, and adhesion of the cured thermosetting resin are improved. Works effectively against Therefore, it is possible to simultaneously improve heat resistance, hydrophobicity, flexibility, crack resistance, mold release, and adhesion.

Hereinafter, the present invention will be further described with reference to examples, but it is needless to say that the present invention is not limited to these examples.

[0021]

EXAMPLE 1 1,4-bis (dimethylmethoxysilyl) benzene 9
1.6 g (0.4 mol), divinyldichlorosilane 3
2.26 g (0.2 mol) of methyl isobutyl ketone 2
The reaction mixture was dissolved in 00 g and charged in a 1-liter reaction vessel. Pure water 2
5.2 g (1.4 mol) was added dropwise and left for 30 minutes. 1.5 g of hydrochloric acid was added, and the mixture was heated at 118 ° C. for 5 hours. On this occasion,
N ₂ gas was bubbled to remove water remaining during hydrolysis and water of reaction condensation. The obtained reaction solution was washed five times with a separating funnel and then concentrated under the condition of 10 mmHg. Next, the obtained product was dissolved in benzene and freeze-dried to obtain 78 g of a silicone compound. The obtained silicone compound was found to have a weight average molecular weight of 22,000 (FIG. 1) from a gel permeation chromatogram. Also, from the ¹ H-NMR spectrum (FIG. 2), 6
The presence of a vinyl group could be confirmed at around ppm, and the content was about 0.25 with respect to the silphenylene monomer 1. Example 2 1,4-bis (dimethylmethoxysilyl) benzene 9
1.6 g (0.4 mol), divinyldichlorosilane 6
0.52 g (0.4 mol) of methyl isobutyl ketone 2
The reaction mixture was dissolved in 00 g and charged in a 1-liter reaction vessel. Pure water 2
8.8 g (1.6 mol) was added dropwise and left for 30 minutes. 1.5 g of hydrochloric acid was added, and the mixture was heated at 118 ° C. for 5 hours. On this occasion,
N ₂ gas was bubbled to remove water remaining during hydrolysis and water of reaction condensation. The obtained reaction solution was washed five times with a separating funnel and then concentrated under the condition of 10 mmHg. Next, the obtained product was dissolved in benzene and freeze-dried to obtain 89 g of a silicone compound. The obtained silicone compound was found to have a weight average molecular weight of 18,000 from a gel permeation chromatogram. Application Example 1 Cresol novolak type epoxy resin (epoxy equivalent 2
00) 100 parts, 55 parts of a phenol novolak resin (hydroxyl equivalent 105), 1 part of triphenylphosphine, and 5 parts of the silicone compound obtained in Example 1 were heated and mixed, and cured at 150 ° C. for 10 hours. The elastic modulus, water absorption, and adhesion to the aluminum plate were evaluated.

The evaluation of physical properties in all the applied examples was based on the following test standards and methods. Glass transition temperature Thermomechanical analyzer (943TMA, Du
pont) Elastic modulus Dynamic viscoelasticity measuring device (983DM)
A, Dupont) Water absorption JIS K6911 Adhesion Cure resin on aluminum plate (180
C. for 1 hour) and the peeled state was observed using an ultrasonic flaw detector.

The results are shown in Tables 1 and 2 below. In the table, the evaluation criteria for the adhesion are as follows: 無 し No peeling ○ Small peeling △ Half-face peeling
× Full peel application example 2 Cresol novolak type epoxy resin (epoxy equivalent 2
00) 100 parts, 55 parts of a phenol novolak resin (hydroxyl equivalent: 105), 1 part of triphenylphosphine, and 10 parts of the silicone compound obtained in Example 1 were heated and mixed, and cured at 150 ° C. for 10 hours. The elastic modulus, water absorption, and adhesion to the aluminum plate were evaluated. The results are shown in Tables 1 and 2 below. Application Example 3 Cresol novolak type epoxy resin (epoxy equivalent 2
00) 100 parts, 55 parts of a phenol novolak resin (hydroxyl equivalent 105), 1 part of triphenylphosphine, and 20 parts of the silicone compound obtained in Example 1 were heated and mixed, and cured at 150 ° C. for 10 hours. The elastic modulus, water absorption, and adhesion to the aluminum plate were evaluated. The results are shown in Tables 1 and 2 below. Application Example 4 Cresol novolak type epoxy resin (epoxy equivalent 2
00) 100 parts, 55 parts of a phenol novolak resin (hydroxyl equivalent 105), 1 part of triphenylphosphine, and 5 parts of the silicone compound obtained in Example 2 were heated and mixed, and cured at 150 ° C. for 10 hours. The elastic modulus, water absorption, and adhesion to the aluminum plate were evaluated. The results are shown in Tables 1 and 2 below. Application Example 5 Cresol novolak type epoxy resin (epoxy equivalent 2
00) 100 parts, 55 parts of a phenol novolak resin (hydroxyl equivalent 105), 1 part of triphenylphosphine, and 10 parts of the silicone compound obtained in Example 2 were heated and mixed, and cured at 150 ° C. for 10 hours. The elastic modulus, water absorption, and adhesion to the aluminum plate were evaluated. The results are shown in Tables 1 and 2 below. Application Example 6 Cresol novolak type epoxy resin (epoxy equivalent 2
00) 100 parts, 55 parts of a phenol novolak resin (hydroxyl equivalent 105), 1 part of triphenylphosphine, and 20 parts of the silicone compound obtained in Example 2 were mixed by heating and cured at 150 ° C. for 10 hours. The elastic modulus, water absorption, and adhesion to the aluminum plate were evaluated. The results are shown in Tables 1 and 2 below. Application Example 7 100 parts of bismaleimide, diaminodiphenylmethane 5
0 parts and 5 parts of the silicone compound obtained in Example 1 were mixed by heating and cured at 200 ° C. for 10 hours, and the glass transition temperature, elastic modulus, water absorption, and adhesion to an aluminum plate were evaluated. The results are shown in Tables 1 and 2 below. Application Example 8 100 parts of bismaleimide, diaminodiphenylmethane 5
0 parts and 10 parts of the silicone compound obtained in Example 1 were mixed by heating and cured at 200 ° C. for 10 hours, and the glass transition temperature, elastic modulus, water absorption, and adhesion to the aluminum plate were evaluated. The results are shown in Tables 1 and 2 below. Application Example 9 100 parts of bismaleimide, diaminodiphenylmethane 5
0 parts and 20 parts of the silicone compound obtained in Example 1 were mixed by heating and cured at 200 ° C. for 10 hours, and the glass transition temperature, elastic modulus, water absorption, and adhesion to an aluminum plate were evaluated. The results are shown in Tables 1 and 2 below. Application Example 10 100 parts of bismaleimide, diaminodiphenylmethane 5
0 parts and 5 parts of the silicone compound obtained in Example 2 were mixed by heating and cured at 200 ° C. for 10 hours, and the glass transition temperature, elastic modulus, water absorption, and adhesion to an aluminum plate were evaluated. The results are shown in Tables 1 and 2 below. Application Example 11 100 parts of bismaleimide, diaminodiphenylmethane 5
0 parts and 10 parts of the silicone compound obtained in Example 2 were mixed by heating and cured at 200 ° C. for 10 hours, and the glass transition temperature, elastic modulus, water absorption, and adhesion to the aluminum plate were evaluated. The results are shown in Tables 1 and 2 below. Application Example 12 100 parts of bismaleimide, diaminodiphenylmethane 5
0 parts and 20 parts of the silicone compound obtained in Example 2 were mixed by heating and cured at 200 ° C. for 10 hours, and the glass transition temperature, elastic modulus, water absorption, and adhesion to an aluminum plate were evaluated. The results are shown in Tables 1 and 2 below. Comparative Example 1 Cresol novolak type epoxy resin (epoxy equivalent 2
00) 100 parts, 55 parts of phenol novolak resin (hydroxyl equivalent: 105) and 1 part of triphenylphosphine were mixed under heating and cured at 150 ° C. for 10 hours, and the glass transition temperature, elastic modulus, water absorption, and adhesion to aluminum plate were obtained. Was evaluated.
The results are shown in Tables 1 and 2 below. Comparative Example 2 100 parts of bismaleimide, diaminodiphenylmethane 5
0 parts were mixed by heating and cured at 200 ° C. for 10 hours, and the glass transition temperature, elastic modulus, water absorption, and adhesion to the aluminum plate were evaluated. The results are shown in Tables 1 and 2 below.

[0024]

[Table 1]

[0025]

[Table 2]

[0026]

As described above, the present invention is constructed as described above. Therefore, the thermosetting resin composition such as an epoxy resin or a maleimide resin has a heat resistance, a hydrophobic property, a flexibility, and an adhesion property. This has the effect of effectively improving the characteristics.

[Brief description of the drawings]

FIG. 1 is a graph showing the weight-average molecular weight of a silicone compound according to one embodiment of the present invention.

FIG. 2 shows ¹ H- of the silicone compound of one embodiment of the present invention.
It is a chart of an NMR spectrum.

Continuation of the front page (72) Inventor Norio Saruwatari 1015 Uedanaka, Nakahara-ku, Kawasaki-shi, Kanagawa Prefecture Inside Fujitsu Limited (56) References Japanese Patent Publication No. Sho 41-14111 (JP, B1) (58) Fields surveyed (Int. Cl. ^7, DB name) C08G 77/52

Claims (4)

(57) [Claims] 1. The following formula I: (Wherein, R ₁ represents a lower alkyl group, and R ₂ and R
₃ are independent of each other and each represents a vinyl group, a lower alkyl group, or a phenyl group;
Represents a ratio of 0.2: 1 to 2: 1). A silicone compound having a molecular weight of 500 to 100,000. 2. The method for producing a silicone compound according to claim 1, comprising the following formula II: (Wherein R ₁ represents a lower alkyl group, R ₄ represents a lower alkoxy group or a halogen atom), and a silphenylene compound represented by the following formula III: (Wherein R ₂ and R ₃ are independent of each other and
Respectively, represents a vinyl group or a lower alkyl group, or a phenyl group, wherein R ₅ is Table Wa lower alkoxy group or a halogen atom, provided that the reaction of a silicon compound represented by different) from R ₄ The manufacturing method described above. 3. The process according to claim 2, wherein the reaction is carried out in a reaction solvent at a temperature of 60 ° C. to 150 ° C. 4. A flexible agent for a thermosetting resin, comprising the silicone compound according to claim 1.