JPH0651784B2 - Thermosetting resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a composition containing a phenol resin having excellent moisture resistance, which is characterized by using a phenol resin synthesized by using a highly hydrophobic hydrocarbon-substituted monoaldehyde.

Conventionally, it has been considered that the phenol resin composition is inferior to the polyester resin composition and the epoxy resin composition in insulation and moisture resistance. This is because it has a hydrophilic phenolic hydroxyl group and has a property of attracting water.
Many attempts have been made so far to improve the hydrophilicity and make it hydrophobic, but it has not succeeded until it bears fruit. For example, a method of increasing the hydrophobicity by using alkylphenol (cresol, xylenol, butylphenol, etc.) as a raw material was also examined, but in this case, the hydrophobicity is certainly increased but the curability is decreased, which is not suitable for molding material applications. there were.

In addition, xylene-modified phenolic resins and zylogous resins were also examined, but these had a large OH equivalent and the distance between the phenol nuclei and the phenol nuclei became too long, resulting in a marked decrease in rigidity and curability, which could not be put to practical use. .

However, since the phenolic resin has excellent moisture resistance, it is possible to substitute for the polyester resin if the insulating property and the moisture resistance can be improved. Therefore, there is a strong demand for improving the insulating property and the moisture resistance.

Further, recently, phenol resin has been used as a curing agent for epoxy resin composition (molding material / laminated board), and improvement of hydrophobicity of phenol resin has been required more than ever before. This is because the epoxy resin composition is increasingly used for semiconductor encapsulation applications and electric circuit substrate applications, that is, in the electric / electronic-related fields, and thus the insulation and moisture resistance are more strictly required.

The present invention provides a phenol resin composition and an epoxy resin composition that satisfy these requirements, and a phenol resin is a co-condensed phenol resin of phenol and a hydrocarbon-substituted monoaldehyde (butyraldehyde, benzaldehyde, acrolein, etc.). By using it as the main resin of the composition and as the curing agent of the epoxy resin composition, the improvement of the insulating property and the moisture resistance is achieved.

It does not hydrophobize the phenol itself like alkylphenol, and carbonizes the hydrogen in one bonding group between the phenol nuclei without increasing the distance between the phenol nuclei as in xylene-modified phenol resin or Zylog resin. It has been found that the hydrophobicity can be enhanced by hydrogen substitution to enhance the water repellency without lowering the curability. Since the curability does not decrease, it can be cured for a short time, and it can now be applied to molding material applications. Further, since the crosslink density does not decrease, it is possible to prevent an increase in water absorption due to the decrease in crosslink density. In the alkylphenol resin, although the resin itself was hydrophobized, a phenomenon in which the water absorption amount was increased due to a decrease in crosslink density and the hydrophobizing effect was offset was also recognized, but in the present invention, such a problem is completely solved. did it. Co-condensation of phenol and hydrocarbon-substituted monoaldehyde with a conventional phenol resin or alkylphenol resin and the like can also be used to obtain a hydrophobic effect, but in this case the effect fades as the combined ratio of conventional resins increases, Generally, in order to make a significant difference, the combined ratio of the conventional resins is preferably 50% or less. Further, when used as a curing agent for an epoxy resin composition, impurities (unreacted phenol, unreacted aldehyde,
It is preferable to reduce the amount of the catalyst) as much as possible. For example, when 5 g of resin is extracted with 45 ml of pure water at 125 ° C. for 20 hours, the electric conductivity of the extracted water is preferably 15 μ / cm or less.

A description will be given below based on an embodiment. All parts used in the examples are parts by weight.

The phenolic resins used in the examples are as follows.

The softening points of all novolac resins are 100 ° C. or,
The electric conductivity of the extracted water was 10 μ / cm.

Example 1 20 parts of hexamethylenetetramine, 2 parts of calcium hydroxide, 60 parts of wood powder, 30 parts of calcium carbonate and 3 parts of stearic acid were mixed with 100 parts of a phenol resin, and the mixture was kneaded for 5 minutes on a hot roll at 100 ° C. to be molded. Made into the material. At this time, as the phenolic resin, 5 levels of, / = 4/6, / = 7/3 were taken to obtain 5 kinds of molding materials.

As a result of examining the curability, insulating property, strength, and water absorption of this molding material, as shown in Table 1, the three types containing the phenolic resin were excellent. Among them, those using 1/2 or more are particularly excellent.

Example 2 70 parts of wood powder, 40 parts of calcium carbonate, 5 parts of magnesium hydroxide and 3 parts of stearic acid were mixed with 100 parts of a phenol resin, and the mixture was kneaded with a hot roll at 100 ° C. for 5 minutes to obtain a molding material. At this time, two types were selected as the phenol resin and two types of molding materials were obtained.

As a result of examining the curability, insulating property, strength, and water absorption of this molding material, it is remarkably excellent to use the phenol resin as shown in Table 1.

Example 3 Epoxy resin [ESCN-200S manufactured by Sumitomo Chemical Co., Ltd.] 20
Parts, 10 parts phenol resin, 70 parts fused silica, 1 part antimony trioxide, flame-retardant epoxy resin [ESB-4, Sumitomo Chemical Co., Ltd.]
00] 3 parts, silane coupling agent [Chesso EES-
M] 0.5 part, catalyst [Fukudihara Chemical Co., Ltd. PP-360]
0.2 parts of release agent 0.5 parts of Hoechst wax S are mixed,
The mixture was kneaded with a hot roll of 80 ° C. for 5 minutes to obtain a molding material. At this time, 3 kinds of phenol resin were selected and 3 kinds of molding materials were obtained.

As a result of investigating the curability, insulating property, strength, water absorbency of this molding material and reliability of the IC encapsulation product, the use as a phenol resin as shown in Table 2 is significantly superior.

Claims (1)

[Claims] 1. A thermosetting resin composition containing an epoxy resin and a co-condensation phenol resin curing agent of phenol and a hydrocarbon-substituted monoaldehyde as an essential component.