JPH06112606A - Epoxy resin composite for printed wiring board - Google Patents

Abstract

PURPOSE:To acquire a resin composition excellent in discoloration heating treatment without lowering other characteristics of an epoxy resin- multifunctional phenol resin setting printed wiring board. CONSTITUTION:The title epoxy resin composition for a printed wiring board is formed by mixing a compound having (a) epoxy resin, (b) multifunctional phenol resin and (c) alkoxyl group as an essential element.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an epoxy resin composition used for printed wiring boards and the like.

[0002]

2. Description of the Related Art As electronic devices have become smaller and have higher performance, printed wiring boards mounted therein have higher densities due to higher multi-layers, thinner products, smaller through-hole diameters and smaller hole intervals. Is in progress. For this reason, the requirements for heat resistance and electrical insulation properties of printed wiring boards are becoming more and more stringent.
Epoxy resin, which has been widely used as an insulating material for printed wiring boards, has been widely studied mainly for curing with dicyandiamide.However, in the dicyandiamide curing system, it is deposited or obtained when a prepreg is produced. There are drawbacks such as high hygroscopicity of the plate. On the other hand, in a system using a polyfunctional phenol resin as a curing agent, a cured resin product having a low water absorption rate and good properties as a laminate can be obtained. However, a laminated board using such a polyfunctional phenol resin may cause a problem of discoloration during heat treatment depending on the type of the phenol resin. Japanese Patent Publication No. 61-5933 proposes a system in which a high orthophenol formaldehyde resin is blended for the purpose of improving the heat discoloration property. However, an ordinary phenol formaldehyde resin produced industrially at low cost was used. In this case, heat discoloration was inevitable.

[0003]

SUMMARY OF THE INVENTION The present invention has been made in view of the above situation, and it is possible to obtain another printed wiring board by adding a compound having an alkoxyl group to a polyfunctional phenol resin curing system. An object of the present invention is to provide an epoxy resin composition which is excellent in discoloration during heat treatment without deteriorating the characteristics.

[0004]

That is, the epoxy resin composition of the present invention is characterized in that (a) an epoxy resin, (b) a polyfunctional phenol resin, and (c) a compound having an alkoxyl group are added as essential components. And Hereinafter, the present invention will be described in detail.

The epoxy resin (a) may be any compound as long as it is a compound having two or more epoxy groups in the molecule, for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S. Type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A novolac type epoxy resin, bisphenol F novolac type epoxy resin, alicyclic epoxy resin, aliphatic chain epoxy resin, glycidyl ester type epoxy resin, glycidyl Amine type epoxy resin, hydantoin type epoxy resin, isocyanurate type epoxy resin, other diglycidyl ether compound of bifunctional phenols,
There are diglycidyl ether compounds of difunctional alcohols, and their halides and hydrogenated products. The molecular weight of these compounds may be any. Several kinds of these compounds can be used in combination.

The polyfunctional phenolic resin (b) is not particularly limited as long as it has two or more phenolic hydroxyl groups in one molecule and reacts with an epoxy resin. For example, bisphenol A, bisphenol F, Examples include polyvinylphenol, novolac resins such as phenol, cresol, alkylphenol, catechol, bisphenol A and bisphenol F, and halides of these phenol resins. These phenol resins may be used in combination of several kinds. The amount of the phenolic aquatic group is 0.5 to 1.5 with respect to the epoxy group.
It is preferably within the equivalent range.

The compound (c) having an alkoxyl group is not particularly limited as long as it is a compound having an alkoxyl group such as a methoxyl group, an ethoxyl group, a propoxyl group and a butoxyl group, and for example, 2-methoxyethanol, Methoxybutanol, 2-methoxy-2-methylpropane, methoxybenzene, 2-methoxyphenol, 2-methoxynaphthalene, o-, p-methoxyaniline and the like, compounds having these ethoxyl groups and the like, alkoxy-substituted organosilanes and the like is there. Typical compounds having a methoxyl group, an ethoxyl group, etc. are coupling agents such as silane coupling agents and titanate coupling agents. Since these coupling agents generally have about 3 alkoxy groups, they are effective in improving the heat discoloration property. Several kinds of these compounds having an alkoxyl group can be used in combination. The compounding amount is preferably within the range of 0.1 to 50 parts by weight with respect to 100 parts by weight of the epoxy resin. If the amount is less than 0.1 parts by weight, the characteristics are hardly improved, and if it is more than 50 parts by weight, the heat resistance and the like are likely to be lowered.

The effect of the epoxy resin composition of the present invention can be further increased by further adding a reducing agent. As the reducing agent, a reducing agent such as a phenol-based, sulfur-based, or phosphorus-based reducing agent can be used, but a phenol-based reducing agent is preferable because it can improve electrical insulation characteristics without degrading characteristics such as drill workability. . As the phenol-based reducing agent, 1,2,3-trihydroxybenzene, butylated hydroxyanisole, 2,4-di-
Monophenol compounds such as t-butyl-4-ethylphenol and 2,2'-methylene-bis- (4-methyl-6-t)
Butylphenol, 4,4'-thiobis- (3methyl-
6-t-butylphenol) and 1,3,5-trimethyl-2,4,6-tris-
(3,5-di-t-butyl-4-hydroxybenzyl)
Benzene, tetrakis- [methylene-3- (3'5'-
Di-t-butyl-4'-hydroxyphenyl) propionate] methane, triethylene glycol-bis-3-
There are polymeric phenolic systems such as (3-t-butyl-4-hydroxy-5-methyl-phenyl) propionate. Examples of the sulfur-based reducing agent include dilauryl thiodipropionate and distearyl thiodipropionate. Examples of phosphorus-based reducing agents include triphenyl phosphite and diphenyl isodecyl phosphite.
These reducing agents may be used in combination of several kinds, and the compounding amount is preferably 0.1 to 20 parts by weight with respect to 100 parts by weight of the epoxy resin. If the amount is less than 0.1 parts by weight, the insulating property is not improved, and if it exceeds 20 parts by weight, the insulating property and the heat resistance are deteriorated.

In the present invention, it is possible to further mix an inorganic filler. There is no particular limitation as the inorganic filler, for example, calcium carbonate, alumina, titanium oxide, mica, aluminum carbonate, aluminum hydroxide,
Magnesium silicate, aluminum silicate, silica, short glass fibers and the like are used. Further, several kinds of these may be used together, and the compounding amount is not particularly limited.

The epoxy resin composition according to the present invention is used in various forms, but a solvent is often used when coating and impregnating the base. As the solvent, acetone, methyl ethyl ketone, toluene, xylene, methyl isobutyl ketone, ethyl acetate, ethylene glycol,
Monomethyl ether, N, N-dimethylacetamide,
There are methanol, ethanol, etc., and these may be mixed in several kinds.

The varnish obtained by blending the above-mentioned respective components is impregnated into a base material such as glass cloth, non-woven glass cloth or paper, cloth containing components other than glass, and dried at 80 to 200 ° C. in a drying oven. By doing so, a prepreg for a printed wiring board is obtained. The prepreg is 150 to 190 ° C., 2.0 to 8.
It is used for producing a printed wiring board or a metal-clad laminate by heating and pressing in the range of 0 MPa. The drying here means removing the solvent when the solvent is used, and making the fluidity disappear at room temperature when the solvent is not used.

[0012]

EXAMPLES The present invention will be described below based on examples, but the present invention is not limited thereto.

Example 1 100 parts by weight of brominated bisphenol A type epoxy resin (Dow-Chemical: DER-518 epoxy equivalent 481) Phenol novolac resin 22 parts by weight (Hitachi Chemical: HP-800N hydroxyl equivalent 106) A-187 2 0.5 parts by weight (manufactured by Nippon Unica-γ-glycidoxypropyltrimethoxysilane) 2-ethyl-4-methylimidazole 0.5 parts by weight A varnish was prepared by blending the above composition in a solvent.

Example 2 The blending amount of A-187 in Example 1 was set to 10 parts by weight. Example 3 A-187 in Example 1 was used as A-163 (manufactured by Nippon Unica: methyltrimethoxysilane). Example 4 A-187 in Example 1 was methoxybenzene. Example 5 A-187 in Example 1 was changed to 2-methoxyphenol. Example 6 In Example 1, aluminum hydroxide was added as an inorganic filler in an amount of 5
0 parts by weight was compounded.

Comparative Example 1 A-187 in Example 1 was not blended. Comparative Example 2 A-187 in Example 6 was not blended.

Example 7 The composition of Example 1 was supplemented with a phenol-based reducing agent 1,
0.5 parts by weight of 2,3-trihydroxybenzene was blended. Example 8 The blending amount of A-187 in Example 7 was set to 10 parts by weight. Example 9 A-187 in Example 7 was used as A-163 (manufactured by Nippon Unica: methyltrimethoxysilane). Example 10 A-187 in Example 7 was methoxybenzene. Example 11 A-187 in Example 7 was 2-methoxyphenol. Example 12 In place of 1,2,3-trihydroxybenzene of Example 7, 0.5 parts by weight of 4,4′-butylidene bis (3-methyl-6-t-butylphenol) was added. Example 13 50 parts by weight of aluminum hydroxide was added as an inorganic filler to the composition of Example 7. Example 14 50 parts by weight of aluminum hydroxide was added as an inorganic filler to the compound of Example 12.

Comparative Example 3 A-187 in Example 7 was not blended. Comparative Example 4 The 1,2,3-trihydroxybenzene in Example 7 was not added. Comparative Example 5 A-187 and 1,2,3-trihydroxybenzene in Example 7 were not blended. Comparative Example 6 A-187 in Example 13 was not blended. Comparative Example 7 1,2,3-trihydroxybenzene in Example 13 was not added. Comparative Example 8 A-187 and 1,2,3-trihydroxybenzene in Example 13 were not blended.

A glass cloth having a thickness of 0.2 mm was impregnated with the varnishes obtained in Examples 1 to 5 and 7 to 12 and Comparative Examples 1 and 3 to 5 and then heated at 140 ° C. for 5 to 10 minutes to prepare a prepreg. Got In addition, Examples 6, 13, 14 and Comparative Examples 2, 6
The varnish of ~ 8 is a glass non-woven fabric (weight 75 g /
m ² ) was used. A copper foil with a thickness of 18 μm is arranged on both sides of the predetermined number of prepregs thus obtained, and 170
A double-sided copper-clad laminate was produced under the press conditions of 90 ° C. and 90 MPa for 4.0 minutes.

Various tests were carried out using this laminated plate. Solder heat resistance test, after etching the entire surface of the copper foil,
A sample cut into a 50 mm × 50 mm square was treated with a pressure cooker for 2 hours, immersed in solder at 260 ° C. for 20 seconds, and visually evaluated for appearance. Those without blisters were OK and those with blisters were NG. .

To evaluate the peeling strength of the copper foil, a 10 mm wide line was formed on the outer layer copper foil, and the peeling strength of the line in the 90 ° direction was measured. Peeling speed is 5
It was set to 0 mm / min.

The heat discoloration test was carried out using a sample obtained by cutting a copper foil on its entire surface and then cutting it into 50 mm × 50 mm squares. Discoloration of the substrate is caused by each temperature condition (140
(° C, 160 ° C) for 1 to 3 hours, the surface of the substrate after the treatment was visually evaluated, and those with no discoloration were OK and those with discoloration were NG.

The migration test was carried out by using a test pattern in which the hole wall spacing of through holes was 350 μm.
The insulation resistance of 400 holes was measured with time for each sample. The test conditions are 85 ° C, 100V in 90% RH atmosphere.
It was applied and applied, and the time until the conduction breakdown occurred was measured.

The measurement results of each resin system are shown in Tables 1 and 2. The systems containing compounds having an alkoxyl group (Examples 1 to 6) had good heat discoloration without lowering of solder heat resistance and copper foil peeling strength. Further, the systems (Examples 7 to 14) in which a reducing agent was further added exhibited further improved heat discoloration and showed excellent electrolytic corrosion resistance.

[0024]

[Table 1]

[0025]

[Table 2]

[0026]

As is apparent from the above description, by using the epoxy resin composition of the present invention, it is possible to obtain a laminated plate excellent in heat discoloration even with a phenol-curing material without deteriorating other general properties. It has become possible to obtain.

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Claims (5)

[Claims] 1. An epoxy resin composition for a printed wiring board, which comprises (a) an epoxy resin, (b) a polyfunctional phenol resin, and (c) a compound having an alkoxyl group as essential components. 2. The epoxy resin composition for a printed wiring board according to claim 1, which further comprises a reducing agent. 3. The epoxy resin for a printed wiring board according to claim 1, wherein the compounding amount of the compound having an alkoxyl group is 0.1 part by weight or more and 50 parts by weight or less with respect to 100 parts by weight of the resin solid content. Composition. 4. The epoxy resin composition for printed wiring boards according to claim 1, which is a compound having a methoxyl group or an ethoxyl group as an alkoxyl group. 5. The epoxy resin composition for a printed wiring board according to claim 1 or 2, which further comprises an inorganic filler.