JPH04356521A - Epoxy resin composition - Google Patents

Abstract

PURPOSE:To obtain an epoxy resin composition excelling in storage stability and giving a cured product having good humidity resistance and heat resistance, a high Tg and excellent drillability by mixing a specified polyepoxy resin or its brominated derivative with dicyandiamide, a specified polyamine and a cure accelerator. CONSTITUTION:This composition comprises a polyepoxy resin having at least three glycidyl ether groups in the molecule or a brominated polyepoxy resin prepared by reacting the above resin with tetrabromobisphenol A, a tetraglycidyl-etherified resin of diaminodiphenyl ether or a brominated resin prepared by reacting the above epoxy resin with tetrabromobisphenol A, dicyandiamide, a diamine of formula I (wherein R1 and R2 are each CH3, C2H5 or the like) or a polyamine of formula II (wherein (n) is 1-3) and a cure accelerator.

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 manufacturing laminates used as printed wiring boards.

0002

2. Description of the Related Art Hitherto, dicyandiamide has been widely used as a curing agent for epoxy resins. However, dicyandiamide has poor solubility, and it has been strongly desired to improve the heat resistance and moisture resistance of its cured product. For this reason, JP-A-54-64599 discloses that the heat resistance can be improved by using aromatic diamines such as diaminodiphenylsulfone and diaminodiphenylmethane. However, in these cases, the storage stability of the resin composition and adhesive sheet called prepreg is significantly shortened. In order to ensure storage stability, the Tg and heat resistance of the cured product are still not sufficient, and something even better has been expected, as well as something with better drill workability.

0003

[Problems to be Solved by the Invention] Therefore, the present invention provides an epoxy resin that has excellent storage stability, good moisture resistance of its cured product, high Tg, further excellent heat resistance, and excellent drill workability. An object of the present invention is to provide a composition.

0004

[Means for Solving the Problems] As a result of studies in view of the above-mentioned problems, the present invention has been made based on the following results: - A brominated polyfunctional epoxy resin reacted with alcohol A, and (1) a tetraglycidyl etherified resin of diaminodiphenyther or a brominated resin obtained by reacting the epoxy resin with tetrabromo bisphenol A, and (2) dicyandiamide. An object of the present invention is to provide an epoxy resin composition comprising: (1) a diamine represented by chemical formula 3 or a polyamine represented by chemical formula 4; and (2) a curing accelerator. In addition, chemical formula 1 and chemical formula 2 in the claims are described as chemical formula 3 and chemical formula 4, respectively.

[0005]

[Chemical formula 3]

[0006]

[Chemical formula 4]

As the epoxy resin used in the present invention, polyfunctional epoxy resins represented by (a), (b), and (c) of chemical formula 5 at the end of the specification, and the above resins are combined with tetrabromobisphenol. Examples include brominated polyfunctional epoxy resins obtained by the reaction with ole A, tetraglycidyl etherified resins of diaminodiphenyther, and brominated resins obtained by reacting the epoxy resins with tetrabromo bisphenol A. It will be done.

Examples of the diamine include dicyandiamide and functional groups represented by R1 and R2 in chemical formula 3, such as bis(4-amino-3ethyl-5methylphenyl).
Methane, bis(4-amino-3,5-diethylphenyl)methane, bis(4-amino-3,5-diisopropylphenyl)methane, 4,4'-diaminodiphenylmethane, 4,
Examples include 4'-diaminodiphenyl ether.

[0009] The polyamine has the chemical formula 4, and it is preferable to use it in an amount of 0.3 to 1.3 equivalents per equivalent of the epoxy resin, and the number of n in the chemical formula is as follows:
If n = 0 bodies, n = 2 and n = 3 bodies are out of these ranges, that is, if n = 0 bodies is less than 50 and n = 2 and n = 3 bodies are in the range of over 20, the cured product The hardness becomes too high, and the abrasion of the drill becomes significant, resulting in poor workability. When n = 0 body exceeds 90 and n = 2 and n = 3 bodies are less than 3, impregnation into the base material becomes poor, moisture resistance decreases, drilling workability is poor and smear occurs. do.

As the curing accelerator, tertiary amines, imidazoles, organic peroxides, etc. can be used.

[0011] In addition, in order to make a varnish by blending the above materials, dimethylacetamide (DM) is used as a diluting solvent.
Ac), N-methylpyrrolidone (NMP), methyl ethyl ketone (MEK), dimethylformamide (DMF)
, methyl cellosolve (MC), dioxane, propylene glycol monomethyl ether (PC), etc., may be used alone or in combination.

0012

[Examples] The present invention will be specifically explained below with reference to Examples.

Example 1 As an epoxy resin, 658 g of a methyl ethyl ketone solution (solid content 75%) of Tecmore VF-2801 manufactured by Mitsui Petrochemicals, which is a trifunctional brominated epoxy resin, and a tetraglycidyl etherified brominated epoxy of diaminodiphenyl ether were used. XJ-8 manufactured by Ciba Geigy, which is a resin
004 dissolved in methyl ethyl ketone (solid content 80%)
To 625 g, 13.5 g of dicyandiamide and bis(4
100 g of amino-3,5-diethylphenyl)methane was mixed in advance with a mixed solvent of dimethylformamide (DMF) and propylene glycol monomethyl ether (PC) 2
The mixture was dissolved in 50 g and mixed, and 0.5 g of 2-ethyl-4-methylimidazole (hereinafter referred to as 2E4MZ) was added as a hardening accelerator to prepare a varnish.

[0014] This varnish was impregnated into a glass cloth of specification 7628 type (7628W manufactured by Asahi Shavel Co., Ltd.) for 160 min.
The prepreg was obtained by drying at ℃ for 5 minutes. The resin content of this prepreg was 43%, and the curing time at 170°C was 120 seconds.

[0015] Eight sheets of the above prepreg were stacked, 18 μm copper foil was placed on both sides, and the temperature was 170° C. and the pressure was 30 kg/c.
m2, and laminated for 90 minutes to obtain a copper-clad laminate with a thickness of 1.6 mm.

[0016] Also, 3 sheets of prepreg, 3 sheets of 0.5 mm
After forming an inner layer board with 5μm copper foil arranged on the top and bottom, and after blackening the copper foil on the surface, two sheets of prepreg were arranged on the top and bottom, and the outermost layer of 18μm copper foil was arranged and laminated.
℃, pressure 30 kg/cm2, 90 minutes lamination molding 4
A layered copper-clad laminate was obtained.

Example 2 In place of 100 g of bis(4amino-3,5-diethylphenyl)methane in Example 1, 1 of the polyamine represented by the chemical formula 4 (Anilix A-110 manufactured by Mitsui Toatsu Chemical Co., Ltd.) was used.
A copper-clad laminate and a four-layer copper-clad laminate were obtained in the same manner as in Example 1 except that 02g was used.

Comparative Example 1 In place of 625 g of XJ-8004 in Example 1, Y of bisphenol A type brominated epoxy resin manufactured by Toto Kasei Co., Ltd.
DB-500 dissolved in methyl ethyl ketone (solid content 8
A copper-clad laminate and a 4-layer copper-clad laminate were obtained in the same manner as in Example 1 except that 625 g of 0%) was used.

Comparative Example 2 A methyl ethyl ketone solution of bisphenol A type brominated epoxy resin DER-514 manufactured by Dow Chemical Company (solid content 80%) 1125 and a methyl ethyl ketone solution of cresol novolac type epoxy resin YDCN-701 manufactured by Toto Kasei Co., Ltd. 133 g of product (solid content 75%), 280 g of a mixture of DMF and PC (1:1), and 21 g of dicyandiamide.
The dissolved material was mixed and stirred, and 1.0 g of 2E4MZ was added as a hardening accelerator, and then everything was mixed to form a varnish. The gel time of this product was measured in the same manner as in Example 1 and was 6 minutes. Thereafter, a copper-clad laminate and a four-layer copper-clad laminate were obtained in the same manner as in Example 1.

Comparative Example 3 Copper cladding was produced in the same manner as in Example 1, except that 100 g of bis(4-amino-3,5-diethylphenyl)methane, the hardening agent in Example 1, was not mixed and 27 g of dicyandiamide was used alone. A laminate, a four-layer copper-clad laminate, was obtained.

[0021] The above copper-clad laminate was used to evaluate Tg and air oven heat resistance, and the 4-layer copper-clad laminate was used to evaluate moisture absorption rate, moisture absorption after solder dipping, drilling, and pre-preg to evaluate its preservability. did. The test methods for these evaluation items were conducted under the following conditions. Tg is determined by TMA method. Air oven heat resistance means that when exposed to that temperature for 30 minutes, it will swell,
This was the highest temperature at which no abnormalities in appearance such as peeling or cracking occurred. The moisture absorption rate is 96% at a temperature of 40°C and a relative humidity of 90% after removing the outermost 18μm copper foil by etching.
It is expressed as the weight increase rate of the four-layer copper-clad laminate test piece before and after the time treatment. Moisture absorption after solder immersion involves removing the outermost 18 μm copper foil by etching, treating it under the same conditions as the moisture absorption rate above, and then immersing it in a 260°C solder bath for 20 seconds to remove any appearance such as blistering, peeling, or cracking. The extent to which an abnormality occurred in the test piece is ○ if no abnormality was observed, △ if a slight abnormality occurred, or × if a significant abnormality occurred.
It was expressed as Drilling was performed by stacking two 4-layer copper-clad laminates and placing a paper phenol laminate underneath. Drill diameter is φ0.9 mm, rotation speed is 60,000 rpm,
50μ/Rev. This was done at a feed rate of Up to 5,000 holes were drilled and cross-sectional observation was performed to observe and evaluate the occurrence of smear. A case where no smear occurred was indicated by ◯, and a case where a slight occurrence of smear occurred was indicated by △.

[0022] Prepreg storage stability was evaluated by whether or not the prepreg could be molded without abnormalities such as smudges and voids when molded under the same conditions after being stored for 30 days at 23°C and 50% relative humidity. ○ indicates that the molding was possible without any abnormality.
× indicates that abnormalities such as scratches and voids have occurred.

From Table 1, the resin compositions of the examples ensured the storage stability of the prepreg compared to those of the comparative examples, and the Tg
It was confirmed that the material has high heat resistance, excellent moisture resistance, and excellent drilling workability.

[0024]

[Effect of the invention] The epoxy resin composition of the present invention provides
It is possible to obtain a resin varnish or prepreg with excellent storage stability, and a laminate with good moisture resistance, high Tg, further excellent heat resistance, and excellent drill workability.

[0025]

[Table 1]

[0026]

[Chemical formula 5]

[0027]

[0028]

Claims (1)

[Claims] [Claim 1] ■ Three or more glycidyl ethers in the molecule
A polyfunctional epoxy resin having a ester group, or a brominated polyfunctional epoxy resin obtained by reacting the epoxy resin with tetrabromobisphenol A, and a tetraglycidyl etherified resin of diaminodiphenyther, or the epoxy resin. A brominated resin reacted with tetrabromobisphenol A, ■dicyandiamide, and ■chemical formula 1
An epoxy resin composition characterized by containing a diamine represented by the following formula or a polyamine represented by the chemical formula 2, and (1) a curing accelerator. [Chemical formula 1] (Left below) [Chemical formula 2]