JP3440365B2 - 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 FRP, which has excellent heat resistance and a small water absorption rate, and more particularly to an epoxy resin composition having properties suitable for copper-clad laminates.

[0002]

2. Description of the Related Art Epoxy resins are widely used in electronic parts, electric devices, automobile parts, FRP, sports equipment and the like because they are excellent in adhesiveness, electric characteristics, mechanical characteristics and heat resistance. However, the FRP, in particular, the copper-clad laminate used for electronic circuit boards is made thinner and thinner, and the epoxy resin used for this purpose is required to have improved heat resistance.

As an epoxy resin for a conventional laminated board, an epoxy equivalent of 300 to 800 g / eq and a bromine content of 18 produced from tetrabromobisphenol A and epichlorohydrin or bisphenol A diglycidyl ether are used.
~ 26% of brominated epoxy resin is mainly used, and dicyandiamide is used alone as the curing agent, or the compound is used in combination with a polyamine compound, or a tertiary amine or imidazole is used in combination as a curing accelerator. ing.

Further, in order to impart further heat resistance to the epoxy resin, a phenol novolac epoxy resin which is a multifunctional epoxy resin or an epoxy resin containing 5 to 25% by weight of a cresol novolac epoxy resin is used.

However, even if the heat resistance of the cured epoxy resin, that is, the glass transition temperature (Tg) is usually increased, the recent thin and multi-layered laminate absorbs moisture when left indoors and is immersed in solder. Since problems such as blistering and peeling occur and deterioration of physical properties are occurring, epoxy resins for laminated boards are required to have improved heat resistance and reduced water absorption.

[0006]

The inventors of the present invention completed the present invention as a result of various studies to improve Tg and reduce the water absorption rate in order to suppress the problems caused by moisture absorption as described above. Then, an object of the present invention is to provide an epoxy resin composition which is suitable as a matrix resin for a laminate having heat resistance and a small water absorption.

[0007]

Means and operation for solving the problems] The present invention is represented by the following formula (I) [Formula 1] 2,5 Sita - Chari - butyl hydroquinone diglycidyl ether and Te
Reaction product with trabromobisphenol A or
2,5-Ditertiary-butyl hydroquinone diglycy
Zyl ether, tetrabromobisphenol A and bisulfite
Enol A is a reaction product with diglycidyl ether.
Bromine-containing 2,5-di-tert-butylhydroquinone
Epoxy resin mainly composed of epoxy resin
Ri product layer plate epoxy resin composition der, characterized in that blended with accelerator is low in water absorption.

[In the formula, n represents an integer of 0 to 10.] ]

The reaction component of the present invention, 2,5-di-tert-butyl-hydroquinone diglycidyl ether, has a hydrophobic tert-butyl group on the heat-resistant benzene ring, so that when it is used as a laminate. It can be expected that the moisture absorption rate will decrease. Furthermore, since it has a low viscosity, it has good permeability to the glass cloth fiber which is a base material during the production of a laminated plate, and is considered to be effective in preventing blistering that occurs during soldering.

[0009] The present invention is of this 2,5-Sita - Shari - tetrabromo butyl hydroquinone diglycidyl ether
React with bisphenol A (hereinafter referred to as TBA)
Alternatively, 2,5-di-tert-butyl hydroxy
Non-diglycidyl ether, TBA and bisphenol A
Flame-retardant bromine as a reaction product with diglycidyl ether
Containing 2,5-ditertiary-butyl hydroquinone
Epoxy resin mainly composed of poxy resin, curing agent and curing accelerator
It is a blend of a progressing agent.

As a means for adding 2,5-ditertiary butyl hydroquinone diglycidyl ether, when it is reacted with TBA which is a raw material of a flame-retardant epoxy resin for laminates, there is no difference from the known epoxy resin production. For example, a commonly used catalyst such as a metal oxide, an inorganic base, an organic base and salts thereof, an onium compound or a phosphine may be used. The epoxy equivalent of the obtained reaction product is in the range of 300 to 800 g / eq, preferably 350 to 750 g / eq.

Thereafter, a conventional compounding agent such as a curing agent, a curing accelerator and a filler is added to the reaction product and the mixture is cured to obtain the desired product. Next, when 2,5-ditertiary butyl hydroquinone diglycidyl ether is added as a compounding agent, it is cured by adding it to an epoxy resin raw material together with a conventional compounding agent such as a curing agent, a curing accelerator and a filler.

The amount of 2,5-ditertiary butyl hydroquinone diglycidyl ether added is about 5 to 30% by weight. If this compound is added more than this, crystals may precipitate during storage after being dissolved in a solvent. There is a nature. Of course, if it is heated and dissolved again before use, it can be used without problems, but it will be troublesome. Therefore, it is more preferable to use it in a form reacted with TBA rather than simply adding it.

As the curing agent in the present invention, an ordinary curing agent for epoxy resin can be used, but in view of storage stability, adhesiveness and heat resistance, dicyandiamide (hereinafter referred to as DI
It is preferable to use CY) alone or in combination with polyamines, or in combination with a tertiary amine or imidazole as a curing accelerator.

[0014]

EXAMPLES AND COMPARATIVE EXAMPLES The present invention will be described in detail with reference to production examples, examples and comparative examples.

Production Example 1 A four-necked flask equipped with a stirrer, a thermometer, a cooling pipe, and a nitrogen gas introducing device was placed in an Epotote ZX-1312 (2,5-ditertiarybutylhydroquinone diglycidyl manufactured by Toto Kasei Co., Ltd.). Ether, epoxy equivalent 175g / e
q) 635 parts and TBA 365 parts were charged and melted by heating while flowing nitrogen gas, 0.5 part of benzyltrimethylammonium chloride was added and reacted at 160 ° C. for 4 hours to obtain an epoxy equivalent of 442 g / eq and a bromine content of 21.5%. A brominated epoxy resin was obtained and dissolved in 250 parts of methyl ethyl ketone. The viscosity of the obtained resin solution is 850 mPa · s
/ 25 ° C (international unit, SI unit).

Production Example 2 Epotote ZX-1312 300 parts, Epotote YD
-128 (manufactured by Tohto Kasei Co., Ltd., bisphenol A diglycidyl ether, epoxy equivalent 187 g / eq) 335
And TBA (365 parts) were charged and reacted in the same manner as in Production Example 1 to obtain a brominated epoxy resin having an epoxy equivalent of 468 g / eq and a bromine content of 21.5%, which was dissolved in 250 parts of methyl ethyl ketone. The viscosity of the obtained resin solution is 1550 mPa.
-It was s / 25 ° C.

Next, a curing agent and a curing accelerator were added to each epoxy resin in a weight ratio shown in Table 1 to prepare a laminated plate, and its physical properties are also shown in Table 1.

The manufacturing conditions of the laminated plate were as follows. For each epoxy resin dissolved in methyl ethyl ketone, a curing agent DICY (manufactured by Nippon Carbide Industry Co., Ltd.), a curing accelerator 2 ethyl 4-methyl imidazole (Shikoku Chemicals Co., Ltd.)
(Made by Nitto Boseki Co., Ltd.), WEA-1
8K-105BZ2) and impregnated with 150 ° C. × 6 min.
Was dried to B-stage to prepare a prepreg.

A 35 μ copper foil (3EC manufactured by Mitsui Mining & Smelting Co., Ltd.) was laminated on the upper and lower sides of the prepreg 4 ply to give 170
Approximately 4 resin components under curing conditions of ℃ × 20kg / cm ² × 2hr
A laminated plate having a thickness of 2% and a thickness of 0.8 mm was produced.

The physical properties of the laminate were measured by the following methods. The glass transition point (Tg) as the heat resistance of the laminate was measured at 2 ° C./min using a viscoelasticity spectrometer DMA982 manufactured by DuPont. It was measured at the temperature rising rate of and was shown by the value of tan δ. The water absorption rate was measured by removing the copper foil by etching, drying at 50 ° C. × 24 hr, and performing a moisture absorption treatment at 40 ° C. × 90% humidity × 96 hr. Flame resistance is JI
The measurement was performed according to S C 6481. The copper foil peel strength was measured according to JIS C 6486 7.7.

[0021]

[Table 1] (*) Epototo YDB-500EK80: Toto Kasei Co., Ltd. trade name, brominated epoxy resin, epoxy equivalent 50
0 g / eq, bromine content 21.5%, methyl ethyl ketone solution, solid content 80%, viscosity 2500 mPa · s / 25 ° C. (* 2) Epotote YDCN-704EK75: Toto Kasei Co., Ltd. trade name, orthocresol novolac epoxy resin, epoxy Equivalent weight 215 g / eq, number of epoxy groups in one molecule is about 11, methyl ethyl ketone solution, solid content 75
%, Viscosity 2000 mPa · s / 25 ° C.

[0022]

As described above, 2,5-ditertiary-butylhydroquinone diglycidyl ether is used as a starting material.
By using the error epoxy resin which is a reaction product, than conventional laminates epoxy resin composition with improved heat resistance, and increase the effect of providing a low water absorption laminate epoxy resin composition It is a thing.

─────────────────────────────────────────────────── ─── Continuation of the front page (56) Reference JP-A-6-298902 (JP, A) JP-A-6-145293 (JP, A) JP-A-7-196770 (JP, A) JP-A-2- 88622 (JP, A) JP 5-140269 (JP, A) JP 5-140263 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) C08G 59/00-59 / 72 B32B 15/08 H05K 1/03-1/05

Claims (2)

(57) [Claims] 1. 2,5 represented by the following formula (I)
- Sita - Chari - butylhydroquinone diglycidyl et <br/> over Te le and the reaction product of tetrabromobisphenol A
Alternatively, 2,5-ditertiary-butyl hydroquinone
Diglycidyl ether and tetrabromobisphenol A
Reaction of bisphenol A with diglycidyl ether
Bromine-containing 2,5-di-tertiary-butyl hydrate
Hard to epoxy resin mainly composed of roquinone type epoxy resin
Agent, product layer plate epoxy resin composition characterized in that a curing accelerator. [Chemical 1] [In formula, n shows the integer of 0-10. ] 2. The epoxy resin composition for a laminate according to claim 1, wherein the curing agent is dicyandiamide and the curing accelerator is 2-ethyl-4-methylimidazole.