JPH07732B2 - Epoxy resin composition for laminated board - Google Patents

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 for laminates which has excellent adhesiveness to metals, heat resistance and flexibility.

[0002]

2. Description of the Related Art Conventionally, as a flexibility-imparting agent for an epoxy resin for flexible laminates, a composition obtained by reacting a polybutadiene-acrylonitrile copolymer having a terminal carboxyl group with a bifunctional or higher functional epoxy resin ( For example, JP-A-1-139630), or epoxy group-containing 1,4-polybutadiene (for example, JP-A-57).
-180626) is known.

[0003]

However, the laminate using these flexibility-imparting agents has insufficient solder heat resistance, bending property, or adhesiveness with copper foil.

[0004]

The present inventors have arrived at the present invention as a result of extensive studies to solve the above problems. That is, the present invention provides an epoxy resin composition comprising a flexibility-imparting agent (A), an aromatic epoxy resin (B) and an epoxy curing agent (C), wherein the (A) is 1,2-polybutadiene glycol or a compound thereof. It is an epoxy resin composition for laminated boards, characterized in that it contains glycidyl ether of hydride as a main component.

The flexibility-imparting agent (A) in the present invention is a glycidyl ether derived from polybutadiene glycol or a hydride thereof, and further contains a 1,2-polybutadiene skeleton in the total polybutadiene skeleton of the polybutadiene glycol. The rate is usually 50% or more,
It is preferably 70% or more. If the content of the 1,2-polybutadiene skeleton is less than 50%, the solder heat resistance and the adhesion with the copper foil will be insufficient.

The epoxy equivalent of the flexibility-imparting agent (A) is usually
It is 250 to 2500 g / eq, preferably 500 to 2000 g / eq. If the epoxy equivalent is less than 250 g / eq, the bendability is insufficient, and if it exceeds 2500 g / eq, the solder heat resistance and the adhesiveness to the copper foil are insufficient. The number average molecular weight of (A) is usually 500.
-10000, preferably 1000-5000. Below 500,
The flexibility effect decreases, and when it exceeds 10,000, the viscosity of the resin composition increases and the workability during resin molding decreases.

The flexibility-imparting agent (A) may be produced by either of the conventionally known one-step method and two-step method. For example, in the one-step method, 1,2-polybutadiene glycol can be synthesized by reacting it with epichlorohydrin usually in the presence of caustic soda at 30 to 70 ° C. In the two-step method, 1,2-polybutadiene glycol and epichlorohydrin are subjected to an addition reaction in the presence of a catalyst, and then caustic alkali is added to carry out a dehydrochlorination reaction to synthesize the compound. Of the two methods, the one-step method is preferable because the total chlorine content of (A) produced is small.

Further, the conversion rate (glycidylation rate) of the polybutadiene constituting the flexibility-imparting agent (A) from hydroxyl groups to glycidyl groups is usually 65% or more, preferably 80% or more. When the glycidylation rate is low, the solder heat resistance of the cured epoxy resin product of the present invention becomes insufficient.

Examples of the aromatic epoxy resin (B) in the present invention include bisphenol type epoxy resin (for example, diglycidyl ether of bisphenol A); phenol novolac type epoxy resin (for example, polyglycidyl ether of phenol novolac, alkylbenzene modified). Phenol novolac polyglycidyl ether, etc.); Cresol novolac type epoxy resin (eg ortho-cresol novolac polyglycidyl ether); Phenol type epoxy resin (eg resorcin diglycidyl ether, phloroglysin diglycidyl ether), etc., or these Brominated compounds are mentioned. These may be used alone or in combination of two or more.

The epoxy equivalent of the aromatic epoxy resin (B) is usually 50 to 1000 g / eq, preferably 100 to 600 g / eq.

The amount of the flexibility-imparting agent (A) used in the present invention is usually 1 to 70% by weight, preferably 2 to 50% by weight, based on the weight of the aromatic epoxy resin (B). If it is less than 1% by weight, the effect of imparting flexibility is lowered, and if it exceeds 70% by weight, the solder heat resistance is lowered.

Examples of the epoxy curing agent (C) in the present invention include polyamines (chain aliphatic polyamines such as diethylenetriamine: alicyclic polyamines such as N-aminoethylpiperazine: xylenediamine, xylenediamine formalin polycondensate, etc.). Aliphatic aromatic polyamines:
Aromatic polyamines such as metaphenylenediamine: Dicyandiamide: Adipic acid dihydrazide: Polyamide polyamine obtained by polycondensation of dimer acid and polyamine), polybasic acid (phthalic acid, trimellitic acid, etc.), polybasic acid anhydride (anhydrous) Phthalic acid, hexahydrophthalic anhydride, etc., polyphenols (phenol novolac resin,
Cresol novolac resins, various novolac resins synthesized from bisphenol A and resorcin), polymercaptans, imidazoles, BF ₃ complexes and the like. These may be used alone or in combination of two or more.

The amount of the epoxy curing agent (C) used is (C)
In the equivalent ratio of the active hydrogen equivalent of 1 to the total epoxy equivalent of the flexibility-imparting agent (A) and the aromatic epoxy resin (B) (total epoxy equivalent), usually (0.4 to 1.4): 1, preferably Is (0.5 to 1.2): 1.

If desired, a known curing accelerator can be added to the resin composition of the present invention. As the curing accelerator, phosphorus compounds such as triphenylphosphine, 2-
Examples thereof include imidazoles such as methylimidazole and tertiary amines such as benzyldimethylamine.

When a curing accelerator is used, the amount added is usually 0.1 to 5.0% by weight, preferably 0.2 to 3.0, based on the total weight of the flexibility-imparting agent (A) and the aromatic epoxy resin (B).
% By weight.

[0016]

EXAMPLES The present invention will be further described below with reference to examples, but the present invention is not limited thereto. Parts in Examples and Production Examples are parts by weight.

(Synthesis of glycidyl ether) Production Example 1 Polybutadiene glycol [NISSO PB G-1000, average molecular weight 1450, 1,2-butadiene skeleton / 1,4-butadiene skeleton = 90/10, manufactured by Nippon Soda Co., Ltd.] 100 parts, epichlorohydrin 35 parts, granular sodium hydroxide 16 parts, and toluene 50
5 parts at 50 ° C under a nitrogen atmosphere with vigorous stirring.
Reacted for hours. After the reaction, 100 parts of water was added and the mixture was stirred for 10 minutes and washed with water. After standing, the upper layer was separated and filtered, and then excess epichlorohydrin and toluene were removed under reduced pressure to obtain a residue of 1,
2-Polybutadiene glycol glycidyl ether (A-
1) I got 90 copies. The epoxy equivalent of this glycidyl ether was 920 g / eq.

Production Example 2 Polybutadiene glycol [NISSO-PB G-2000, average molecular weight 2500, 1,2-butadiene skeleton / 1,4-butadiene skeleton =
90/10, manufactured by Nippon Soda Co., Ltd.] 100 parts, epichlorohydrin 35 parts, granular sodium hydroxide 16 parts and toluene 50 parts were charged and reacted for 5 hours at 50 ° C. under a nitrogen atmosphere with vigorous stirring. The rest of the procedure was the same as in Production Example 1 to obtain 90 parts of glycidyl ether of polybutadiene glycol (A-2). The epoxy equivalent of this glycidyl ether is 15
It was 90 g / eq.

Production Example 3 Polybutadiene glycol [NISSO-PB G-2000, average molecular weight 2500, 1,2-butadiene skeleton / 1,4-butadiene skeleton =
90/10, manufactured by Nippon Soda Co., Ltd.] 100 parts, epichlorohydrin 9 parts, boron trifluoride diethyl ether complex 0.15 parts and toluene 50 parts were charged, and the reaction was carried out at 55 ° C. for 5 hours under a nitrogen atmosphere with vigorous stirring. . Then, 9.5 parts of 48% sodium hydroxide aqueous solution was added, and the ring-closing reaction was carried out at 65 ° C. for 5 hours. After the reaction, 100 parts of water was added, and the remaining operations were performed in the same manner as in Production Example 1 to obtain 95 parts of glycidyl ether (A-3) of polybutadiene glycol. The epoxy equivalent of this glycidyl ether was 1430 g / eq.

Production Example 4 Hydrogenated polybutadiene glycol [NISSO PB GI-1000,
Average molecular weight 1450, manufactured by Nippon Soda Co., Ltd.] 100 parts, epichlorohydrin 35 parts, granular sodium hydroxide 16 parts, and toluene 50 parts were charged, and under vigorous stirring under a nitrogen atmosphere 50
The reaction was carried out at ℃ for 5 hours. The rest of the procedure was the same as in Production Example 1 to obtain 90 parts of hydrogenated polybutadiene glycol glycidyl ether (A-4). The epoxy equivalent of this glycidyl ether was 1030 g / eq.

Production Example 5 Hydrogenated polybutadiene glycol [NISSO PB GI-2000,
An average molecular weight of 2500, manufactured by Nippon Soda Co., Ltd.] 100 parts, epichlorohydrin 35 parts, granular sodium hydroxide 16 parts, and toluene 50 parts were charged, and under vigorous stirring under a nitrogen atmosphere 50
The reaction was carried out at ℃ for 5 hours. The rest of the procedure was the same as in Production Example 1 to obtain 85 parts of hydrogenated polybutadiene glycol glycidyl ether (A-5). The epoxy equivalent of this glycidyl ether was 1800 g / eq.

Examples 1 to 5 and Comparative Examples 1 to 2 Based on the formulations of Examples 1 to 5 and Comparative Examples 1 and 2 shown in Table 1 below, all components were mixed and dissolved to obtain resin varnishes. A glass non-woven fabric was impregnated with this varnish according to a conventional method to obtain a prepreg. A certain number of these are stacked and copper foil (thickness;
35 μm) and then 180 ° C., 30 Kg / cm ² , 60
It was subjected to press working to obtain a laminated plate having a thickness of 0.6 mm. Table 2 shows the physical properties of this laminate.

[0023]

[Table 1] Note) (S-1): 1,4-polybutadiene containing terminal epoxy group (Poly b
d R-45EPT, Idemitsu Petrochemical Co., Ltd., average molecular weight 2800,
Epoxy equivalent 1500 g / eq) (S-2): Polybutadiene-acrylonitrile copolymer containing terminal carboxyl group [CTBN 1300X8 Ube Industries, Ltd.] and Epicoat 828 (weight ratio 1: 1) using triphenylphosphine as a catalyst. Reaction product obtained by reacting at 180 ° C. for 4 hours a: ESB-500 [brominated bisphenol A epoxy resin, epoxy equivalent 470 g / eq, manufactured by Sumitomo Chemical Co., Ltd.] b: dicyandiamide c: benzyldimethylamine

[0024]

[Table 2]

Measuring method (1) Copper foil peeling strength: conforming to JIS-C-6481 (2) Insulation resistance: conforming to JIS-C-6481 (3) Soldering heat resistance: conforming to JIS-C-6481 (4) ) Bending property: Bending the laminated plate along the circumference of a cylinder rod with a sufficiently small diameter that is suitable for bending without causing cracks, and the radius that can hold the bent state after releasing the bending force. Indicated.

[0026]

The epoxy resin composition of the present invention has excellent features such as excellent adhesion to metals, heat resistance and flexibility, and good moldability and good appearance of molded articles. . From this, the resin composition of the present invention is suitable for laminated boards.

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Claims (4)

[Claims] 1. An epoxy resin composition comprising a flexibility-imparting agent (A), an aromatic epoxy resin (B) and an epoxy curing agent (C), wherein the (A) is 1,2-polybutadiene glycol or a compound thereof. An epoxy resin composition for a laminate, which comprises a glycidyl ether of a hydride as a main component. 2. The epoxy resin composition for a laminate according to claim 1, wherein the content of the 1,2-polybutadiene skeleton in the entire polybutadiene skeleton in the flexibility-imparting agent (A) is 50% or more. 3. The flexibility-imparting agent (A) has an epoxy equivalent of 2
The epoxy resin composition for laminated boards according to claim 1 or 2, which has an amount of 50 to 2500 g / eq. 4. The laminate according to claim 1, wherein the content of the flexibility-imparting agent (A) is 1 to 70% by weight based on the weight of the aromatic epoxy resin (B). Epoxy resin composition.