JP3506398B2 - Resin composition - Google Patents

Description

Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition having improved adhesion to metal. 2. Description of the Related Art In recent years, the production of electronic components such as integrated circuits such as ICs, LSIs, and LEDs and diodes has increased due to the progress of electronics. These electronic components are sealed with a resin such as an epoxy resin, which greatly contributes to cost reduction, improvement in productivity, and the like. Further, a frame made of copper, iron, nickel, chromium or the like or an alloy thereof is generally used for a frame of an electronic component. In electronic components, reliability with respect to moisture resistance is important, and adhesion between a sealing resin and a metal surface such as a frame is an important factor influencing reliability. [0003] Conventionally, silane-based, titanium-based coupling agents and the like have been known for improving the adhesion between an inorganic filler and a resin. It is known that a mercaptan-based silane coupling agent is effective. However, in the case of a mercaptan-based silane coupling agent, there is a disadvantage that the effect of adhesiveness to a metal gradually decreases when the silane coupling agent is blended with a resin and stored for a long time. The present invention has been made to solve the above-mentioned disadvantages, and an object of the present invention is to provide a highly reliable resin composition having excellent adhesion to metal even after long-term storage. The inventors of the present invention have made intensive studies to achieve the above-mentioned object, and as a result, by blending a resin with a thermally decomposable sulfur compound, the resin can be stored for a long time. The inventors have found that a resin composition having excellent adhesion to metal can be obtained later, and have completed the present invention. That is, the present invention provides a resin composition comprising a synthetic resin and a sulfur compound which generates an SH group by heating and has a trialkoxysilyl group as essential components. A resin composition comprising a compound in an amount of 0.01 to 10% by weight. Hereinafter, the present invention will be described in detail. [0008] The synthetic resin used in the present invention is not particularly limited, and may be an epoxy resin, an unsaturated polyester resin, a polyimide resin, a polyamideimide resin, a polyetherimide resin, a polyphenylene oxide resin, a polyetherketone resin, a polyetherketone resin, or the like. Ether sulfide resin, polyphenylene sulfide resin, phenolic resin, thermosetting resin such as silicone resin, also polystyrene resin, polyethylene resin, polypropylene resin, polyvinyl chloride resin, acrylic resin, thermoplastic resin such as polycarbonate resin, and the like, These can be used alone or in combination of two or more. The sulfur compound used in the present invention is a compound containing sulfur which generates an SH group by thermal decomposition and also having a trialkoxysilane structure in the molecule.
These compounds include thiazole compounds, sulfenamide compounds, and tyrium compounds. Specific compounds include, for example, the following compounds, which can be decomposed by heating to, for example, 140 ° C. [0010] Chemical name: N, N, N'-trimethyl-N '-(trimethoxysilylpropyl) thiuram monosulfide Chemical name: 2- (4-morpholinodithio) -6- (trimethoxysilylpropyl) benzothiazole Chemical name: N- (cyclohexyl) -6- (trimethoxysilylpropyl) -2-benzothiazolylsulfenamide Chemical name: N, N-dicyclohexyl-6- (trimethoxysilylpropyl) -2-benzothiazolylsulfenamide In addition to these compounds, it has a trimethoxysilyl group and a triethoxysilyl group, and is thermally decomposed into SH. Any sulfur compound capable of forming a group can be used. The compounding ratio of this sulfur compound is 0.01 to 10 with respect to the resin composition.
It is desirable to contain it in a proportion of weight%. 0.0
If the amount is less than 1% by weight, the effect of adhesion is not sufficient, and
Exceeding the weight percentage is undesirable because it degrades various properties inherent to the resin. The sulfur compound can be added to the resin as it is, but it can be used as a primer by diluting the sulfur compound in a solvent such as ethanol and applying it to the metal to be adhered. The sulfur compound does not improve the adhesion when it is simply added to the resin, but decomposes when heated and cured to exhibit the effect of the adhesion. Therefore, unlike the prior art, the present invention is excellent in long-term storage properties and adhesion after long-term storage as compared with conventional resin compositions. The resin composition of the present invention contains a synthetic resin and a specific sulfur compound as essential components, but within a range not inconsistent with the object of the present invention, silica powder, inorganic fillers such as aluminum hydroxide, silver and copper. And various components such as a metal powder such as nickel, a coloring agent, a thixotropic agent, a solvent, and a curing agent. When a metal powder is blended, the adhesion of the sulfur compound to the metal powder added to the synthetic resin is improved in addition to the improvement of the adhesion to the adherend. The resin composition of the present invention can be easily produced by blending a synthetic resin, a specific sulfur compound and other additives, mixing and stirring. And this resin composition,
Widely used for electronic components as casting materials, sealing materials, adhesives, etc. The resin composition of the present invention has an adhesion to a metal even after being stored for a long period of time, because it contains a sulfur compound which generates an SH group upon heating and has a trialkoxysilyl group. Excellent adhesion can be maintained without deterioration. EXAMPLES Next, the present invention will be described specifically with reference to examples, but the present invention is not limited to these examples. Example 1 100 g of epoxy resin Epon 828 (trade name, manufactured by Yuka Shell Epoxy), 100 g of hexahydrophthalic anhydride,
1-cyanoethyl-2-ethyl-4-methylimidazole 1.0
0 g and 3.0 g of the sulfur compound of Chemical Formula 1 were mixed and stirred to produce a uniform resin composition. Example 2 100 g of epoxy resin Epon 828 (trade name, manufactured by Yuka Shell Epoxy), 100 g of hexahydrophthalic anhydride,
1-cyanoethyl-2-ethyl-4-methylimidazole 1.0
0 g and the sulfur compound of Formula 2 (3.0 g) were mixed and stirred to produce a uniform resin composition. Example 3 100 g of epoxy resin Epon 807 (trade name, manufactured by Yuka Shell Epoxy Co.), 110 g of hexahydrophthalic anhydride,
1-cyanoethyl-2-ethyl-4-methylimidazole 1.0
0 g and the sulfur compound of Formula 3 (3.0 g) were mixed and stirred to produce a uniform resin composition. Example 4 Epoxy resin celloxide 2021 (manufactured by Daicel Chemical Industries, trade name) 100 g, hexahydrophthalic anhydride 120 g,
1-cyanoethyl-2-ethyl-4-methylimidazole 1.0
0 g and 3.0 g of the sulfur compound of Chemical Formula 4 were mixed and stirred to produce a uniform resin composition. Example 5 100 g of epoxy resin EPON 828 (trade name, manufactured by Yuka Shell Epoxy), 100 g of hexahydrophthalic anhydride,
1-cyanoethyl-2-ethyl-4-methylimidazole 1.0
0 g and the sulfur compound of Formula 3 (3.0 g) were mixed and stirred to produce a uniform resin composition. Comparative Example 1 100 g of epoxy resin Epon 828 (trade name, manufactured by Yuka Shell Epoxy), 100 g of hexahydrophthalic anhydride,
And 1.00 g of 1-cyanoethyl-2-ethyl-4-methylimidazole were mixed and stirred to produce a uniform resin composition. Comparative Example 2 100 g of epoxy resin Epon 807 (trade name, manufactured by Yuka Shell Epoxy), 110 g of hexahydrophthalic anhydride,
And 1.00 g of 1-cyanoethyl-2-ethyl-4-methylimidazole were mixed and stirred to produce a uniform resin composition. Comparative Example 3 100 g of epoxy resin celloxide 2021 (trade name, manufactured by Daicel Chemical Industries, Ltd.), 120 g of hexahydrophthalic anhydride,
And 1.00 g of 1-cyanoethyl-2-ethyl-4-methylimidazole were mixed and stirred to produce a uniform resin composition. After injecting the resin compositions produced in Examples 1 to 5 and Comparative Examples 1 to 3 into a mold having a 10 mm square cube, a 5 mm × 20 mm × 1 mm thick iron plate, copper plate, silver plated copper plate Three kinds of metal plates were fixed inside and cured at 140 ° C. for 5 hours. After curing, the molded product was taken out of the mold, boiled in red ink for 30 minutes, and visually evaluated whether or not the red ink had entered the interface between the metal plate and the resin composition. The results are shown in Table 1. The resin composition of the present invention was excellent, and the remarkable effect of the present invention could be confirmed. The method of the present invention is effective not only for casting but also for transfer molding, and can be applied to various applications where adhesion to metal is important. [Table 1] * 1: Evaluation criteria, ○: no coloring, Δ: very slight coloring at the interface, ×: 10 to 50% of the whole. As is clear from the above description and Table 1, the resin composition of the present invention has excellent adhesion to metal even after long-term storage, and is suitable for casting materials such as electronic parts. Widely used as sealing materials, adhesives, etc.

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Claims (1)

(57) Claims 1. A resin composition comprising a synthetic resin and a sulfur compound which generates an SH group by heating and has a trialkoxysilyl group as essential components, the resin composition comprising: A resin composition comprising the sulfur compound in an amount of 0.01 to 10% by weight based on the weight of the resin composition.