JPS6099117A - Thermosetting resin composition - Google Patents

Abstract

PURPOSE:The titled composition having improved water resistance and insulating properties free from reduction in curing characteristics, comprising a polycondensation phenolic resin of phenol and a hydrocarbon-substituted aldehyde. CONSTITUTION:The desired composition comprising preferably >=50wt% polycondensation phenolic resin of phenol and a hydrocarbon-substituted aldehyde (e.g., butylaldehyde, etc.). USE:Useful as a curing agent for epoxy composition.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a phenolic resin-blended composition (=
One of its characteristics is that it uses a phenolic resin synthesized using a highly hydrophobic hydrocarbon-substituted aldehyde (there are two types).

Conventionally, phenolic resin compositions have been considered to be inferior to polyester resin compositions and epoxy resin compositions in terms of insulation and moisture resistance. This is because it has a hydrophilic phenolic hydroxyl group and has the property of attracting water.

Until now, attempts have been made to improve this hydrophilicity and make it hydrophobic (=
Numerous attempts have been made, but none have borne fruit. For example, using alkylphenols (cresol, xylenol, butylphenol, etc.) as raw materials (
A method of increasing hydrophobicity from 2 was also considered, but in this case, the hydrophobicity increased but the curability decreased, making it unsuitable for use as a molding material.

In addition, Kinlen-modified phenolic resin and Zylog resin were considered, but these were too large and the distance between the phenol nuclei was too long, resulting in a significant decrease in rigidity and hardenability, making it impossible to put them into practical use. .

However, since phenolic resin has excellent moisture resistance, it is possible to replace polyester resin (2) if its insulation and moisture resistance can be improved, so there is a strong demand for improved insulation and moisture resistance. There is.

In addition, recently, phenolic resins have been used as curing agents for epoxy resin compositions (molding materials, laminates), and there has been a demand for improved hydrophobicity of phenolic resins. As products are increasingly being used for semiconductor encapsulation and electrical circuit board applications, that is, for electrical and electronic related fields, stricter requirements for insulation and moisture resistance have arisen (-).

The present invention provides a phenol resin composition or an epoxy resin composition that satisfies these requirements. As the main resin for products,
By using it as a curing agent for epoxy resin compositions, improvements in insulation and moisture resistance have been achieved.

Like alkylphenol (= instead of making the phenol itself hydrophobic, and without increasing the distance between phenol nuclei like xylene-modified phenol resin or Zylog resin), one bonding group between phenol nuclei: carbon It has been discovered that hydrophobicization through hydrocarbon substitution can improve water repellency without reducing curability.

It can be cured in a short time because the curability does not decrease, so it can be used as a molding material (2).In addition, since there is no decrease in crosslink density, it can also prevent a slight increase in water absorption due to a decrease in crosslink density. With alkylphenol resins, even though the resin itself was made hydrophobic, there was a phenomenon in which the crosslinking density decreased (which resulted in a slight increase in water absorption due to the second effect), canceling out the hydrophobization effect, but the present invention eliminates this phenomenon. This problem has been completely solved.It is possible to obtain a hydrophobic effect even if a co-condensed phenol resin of phenol and a hydrocarbon-substituted aldehyde is used in combination with a conventional phenol resin or alkylphenol resin, but in this case, the conventional resin The effect weakens as the combined ratio of resin increases, and generally there is a significant difference (Secondly, the combined ratio of conventional resins is preferably 50% or less 6) Also, when used as a curing agent in an epoxy resin composition (
Second, impurities (unreacted phenol, unreacted aldehyde,
It is preferable to reduce the amount of catalyst (catalyst, etc.) as much as possible. For example, when resin 5I is extracted with 45 ml of pure water at 125° C. for 20 hours, the electrical conductivity of the extracted water is preferably 15 μ2P′σ or less.

The following description will be made based on Example 2. All parts used in Example fA1 are parts by weight.

The phenolic resins used in the examples are as follows.

Phenolic resin ■ Novolak "10" made by Mitsui Toatsu UcD
00 (regular phenol, formaldehyde novolac) Phenolic resin ■ Novolac P manufactured by Mitsubishi Gas (Higaku)
-100 (Phenol Novolac) Phenolic Resin ■ Resol made by Resident Dales ■ (regular resol) Phenolic Resin ■ Nippon Kakyo 61 PN-100 (Phenol Novolac, curing agent for epoxy resin) Phenol Resin ■ Nippon Kakyo ■ 0CN- 100 (Hard Dunkresol Novolak for epoxy resin) Resole resin (Power to hydroxylate phenol and butyraldehyde Lucium novolac resin (Phenol and benzaldehyde are reacted with oxalic acid and washed with water (high purity novolak purified from second stage) The softening point of novolac resin is The temperature in both cases was 100°C.

In addition, the electrical conductivity of the extracted water in ■, ■, and ■ are all lOμτ
It was μ.

Example 1 100 parts of phenol resin was mixed with 20 parts of hexamethylenetetramine, 2 parts of calcium hydroxide, 6 parts of wood flour, 30 parts of calcium carbonate, and 3 parts of stearic acid and heated at 100°C.
The mixture was kneaded for 5 minutes using hot rolls to form a molding material. At this time, as phenolic resin, ■, ■, (seasonal).

Five levels were taken: σ [Yes] -4/6, (N -7/3), and a molding material with a sum of 5 and 1 was obtained.

As a result of examining the curability, insulation, strength, and water absorption properties of this molding material, three types containing ■ as a phenol resin were superior as shown in Table 1. Also, among these, those containing 1 part 2 or more of ■ are particularly excellent.

Example 2 70 parts of wood flour, 40 parts of calcium carbonate, 5 parts of magnesium hydroxide, and 3 parts of stearic acid were mixed with 100 parts of phenol resin and kneaded for 5 minutes with heated rolls at 100°C to obtain a molding material. At this time, two types of phenolic resins, ■ and ■, were selected, and two types of molding materials were also obtained.

As a result of investigating the curability, insulation, strength, and water absorption properties of this molding material, Table 1 shows that (-) using phenol resin is significantly better.

Example 3 Epoxy resin [ESCN-2008 manufactured by Juju Chemical Industry Co., Ltd.]
20 parts, 10 parts of phenolic resin, 0 parts of fused silica, 1 part of antimony trioxide, flame-retardant epoxy resin
33 parts of SB-400, 0.5 parts of a silane coupling agent (Chisso EES-M), 0.2 parts of a catalyst (Fukudi Ihara Chemical PP-360), and 0.5 parts of a mold release agent (Hoechst Wax S). , 5 with a hot roll at 80℃
The mixture was kneaded for a minute to obtain a molding material (:l). At this time, three types of phenol-1 resin, ①, ②, and ① were added to obtain three types of molding material.

Curability, insulation, strength, water absorption and IC of this molding material
As a result of investigating the reliability of the encapsulated product, as shown in Table 2 (= excellent using ■ as the phenolic resin).

Table-2 Reliability of IC products; ■C products at 125℃, 100%,
1000hrs Defective products when stored/judged by total number Crackability of IC products;
50℃ bath (= soaked for 2 minutes each, product (= judged by number of cycles where cracks appear)

Claims (1)

[Claims] A thermosetting resin composition comprising a co-condensed phenol resin of phenol and a hydrocarbon-substituted aldehyde.