JPH0662736B2 - Epoxy resin composition for laminated board - Google Patents

Description

Description: <Industrial field of application> The present invention relates to an epoxy resin composition for laminates, which has excellent heat resistance and drill workability.

<Prior Art> In recent years, the development of the electronic device industry centering on ICs, LSIs, etc. has been remarkable, and a large amount of these electronic devices have been incorporated not only in computers but also in home electric appliances, automobiles and the like.

Epoxy resin laminates are mainly used as substrates for mounting these electronic devices.

Physical properties required for this type of laminated plate include not only heat resistance but also drill workability, dimensional stability, chemical resistance and the like.

Particularly, in recent years, high-density wiring has been performed, and demands for drill workability have become strict.

That is, it is required that the heat resistance be high enough to withstand the frictional heat during drilling and that less peeling and cracking occur during drilling.

At present, a mixture of bisphenol A type glycidyl ether and 0-cresol novolac glycidyl ether or phenol novolac glycidyl ether is used for an epoxy resin composition for laminates in order to improve heat resistance.

<Problems to be solved by the invention> However, by adding glycidyl ether of 0-cresol novolac or phenol novolac for improving the heat resistance, the glass transition temperature is increased, the heat resistance is increased, but the elastic modulus is also increased, so that the drill is used. Cracks are likely to occur during processing.

Therefore, there is a demand for a composition having a high glass transition temperature and an appropriate elastic modulus.

<Means for Solving the Problem> The present invention relates to bisphenol A type glycidyl ether 50-
99 parts by weight General formula (1) (In the formula, R ^{1 to} R ⁴ are groups selected from hydrogen, an alkyl group having 1 to 10 carbon atoms, and halogen, and n is an average of 2 to 50.) Poly (isopropenylphenyl) An epoxy resin composition for a laminate, which is formed by impregnating a base material (excluding carbon fiber) consisting of 1 to 50 parts by weight of glycidyl ethers and a curing agent with the resin composition.

The bisphenol A type glycidyl ether used in the present invention means a glycidyl ether of bisphenol A obtained from bisphenol A and epichlorohydrin, and a halogen-substituted bisphenol A such as bisphenol A or tetrabromobisphenol A added to the obtained glycidyl ether of bisphenol A. And the glycidyl ether of mixed bisphenol A obtained from epichlorohydrin and bisphenol A and halogen-substituted bisphenol A.

For applications where flame retardancy is required, the adduct obtained by using this tetrabromobisphenol A and the glycidyl ether of the above mixed bisphenol A are desirable.

Examples of poly (isopropenylphenyl glycidyl ether) represented by the general formula (1) include O-, m-,
P-, three types of poly (isopropenylphenylglycidyl ether), poly (2,6-dimethyl-4-isopropenylphenylglycidyl ether), poly (2,6-dibromo-4-isopropenylphenylglycidyl ether), and These are copolymers and the like.

These production methods can be obtained by cationically polymerizing the isopropenylphenol into a polymer of the isopropenylphenol, which is further reacted with epichlorohydrin to form a glycidyl ether.

It can also be obtained by reacting the isopropenylphenol with epichlorohydrin to form a glycidyl ether, which is then subjected to cationic polymerization with a specific catalyst such as hydrogen iodide or a mixed catalyst of hydrogen iodide and halogen.

Mixture of bisphenol A type glycidyl ether and said poly (isopropenylphenyl glycidyl ether) 10
The amount of the poly (isopropenylphenyl glycidyl ether) is 1 to 50 parts by weight, preferably 5 to 30 parts by weight, based on 0 parts by weight.

A small amount of another type of glycidyl ether may be mixed with the glycidyl ether mixture in this proportion.

The curing agent in the present invention is not particularly limited,
Various conventionally known hardeners can be used in a stoichiometric amount approximately equal to the epoxy equivalent of glycidyl ether or about half thereof.

Examples of the curing agent include dicyandiamide, diphenyldiaminomethane, diphenyldiaminosulfone, etc., as described in "Printed wiring materials and processing technology" CMC Technical Report No. 17 (publishing office, CMC Co., Ltd.) and the like. Is used.

The epoxy resin composition of the present invention, if necessary, further
A curing accelerator, a filler, a surface treatment agent, etc. may be added.

The curing accelerator can be appropriately selected from known ones depending on the type of curing agent used.

For example, when the curing agent is dicyandiamide, 2-ethyl-4-methylimidazole, benzyldimethylamine, etc. are exemplified.

As the filler, silica, alumina, aluminum hydroxide, talc, mica, etc. are used.

Surface treatment agents include γ-glycidoxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl)
Examples thereof include ethyltrimethoxysilane and γ-aminopropyltrimethoxysilane.

The laminated board can be manufactured, for example, by the method described in the above-mentioned "Materials and Processing Technology for Printed Wiring", and the base material for the laminated board is made of organic or inorganic natural fiber, glass fiber, or synthetic fiber. Cloth, non-woven cloth, mat, etc., and specific examples thereof include glass cloth, polyester cloth, paper, and Tetoron cloth.

<Effects of the Invention> The epoxy resin used for the laminate is used by mixing conventional bisphenol A type glycidyl ether with conventional 0-cresol novolac glycidyl ether or phenol novolac glycidyl ether in order to improve heat resistance. There is.

However, with these novolac glycidyl ethers,
Heat resistance can be increased, but on the other hand, elastic modulus is also increased,
It becomes brittle and easily cracked, and the drill workability deteriorates.

The composition of the present invention comprises a mixture of poly (isopropenylphenyl glycidyl ether) s and bisphenol A type glycidyl ether.

With this composition, the heat resistance is higher, but the elastic modulus is moderately suppressed, it is hard to crack, and the drilling workability is excellent.

<Example> Epoxy equivalent is defined as gram equivalent per mole of glycidyl ether group.

Further, the number average degree of polymerization is a vapor pressure osmotic pressure method (Corona,
It is calculated from the number average molecular weight measured by a molecular weight measuring device 117 type).

Further, the glass transition temperature and the elastic modulus were measured with Rheolograph Solid (manufactured by Toyo Seiki Co., Ltd.).

Reference Example 1 (1) Synthesis of isopropenylphenyl glycidyl ether Bisphenol A was thermally decomposed as described in Example 1 of Japanese Examined Patent Publication No. 38-1368, and the resulting mixture was purified to obtain p-isopropenylphenol.

1 equipped with a thermometer, separation tube, dropping funnel and stirrer
In a flask, 135 g of the p-isopropenylphenol was dissolved in 7.0 mol of epichlorohydrin, and the temperature was 73 ° C and the pressure was 250 mm.
Keeping at Hg, 48% NaOH aqueous solution was continuously added in 8 hours.

During this time, epichlorohydrin and water were azeotropically liquefied to be liquefied and separated into an organic layer and an aqueous layer by a separation tube, the aqueous layer was removed outside the system, and the organic layer was circulated inside the system.

After completion of the reaction, the temperature was kept for 1 hour to evaporate and remove unreacted epichlorohydrin, and the reaction product was dissolved in methyl isobutyl ketone.

Next, after removing the by-product salt, methyl isobutyl ketone was evaporated and removed to obtain p-isopropenylphenyl glycidyl ether.

(2) Synthesis of poly (isopropenyl phenyl glycidyl ether) 19 g of p-isopropenyl phenyl glycidyl ether obtained in (1) was dissolved in 181 g of methylene chloride dehydrated with Molecular Sieves 4A and cooled to -20 ° C. Hydrogen iodide
0.128 g and toluene 2.5 g were added, and the mixture was kept warm for 15 minutes.

After 100 g of methanol was added to stop the reaction, the reaction mixture was washed with 100 g of a 10 wt% sodium thiosulfate aqueous solution, and then the solvent and residual monomers were removed by distillation to obtain poly (p-isopropenylphenylglycidyl ether).

The epoxy equivalent was 209 and the number average degree of polymerization was 9.1.

Reference Example 2 Hydrogen iodide instead of 0.128 g hydrogen iodide and 2.5 g toluene
Polymerization was performed in the same manner as in Reference Example 1 except that 0.128 g, toluene 2.5 g, iodine 0.254 g, and toluene 2.5 g were used to obtain poly (p-isopropenylphenylglycidyl ether).

The epoxy equivalent was 213 and the number average degree of polymerization was 37.

Examples 1 to 4 Sumipoxy ESB-500 which is an adduct of glycidyl ether of bisphenol A and tetrabromobisphenol A
(Sumitomo Chemical Co., Ltd., epoxy equivalent 489, bromine content 2
0% by weight) and the poly (isopropenylphenyl glycidyl ether) obtained in Reference Examples 1 and 2 were dissolved in 25 g of methyl ethyl ketone in the amounts shown in Table 1 to obtain an epoxy resin varnish.

To this varnish, 4.0 g of dicyandiamide, 2-ethyl-4
-Methylimidazole 0.1 g and methylcellosolve 40 g were added and mixed homogeneously.

Subsequently, the mixture was poured into a mold, the solvent was dried and removed, and then press molding was performed at 160 ° C. under the condition of 100 kg / cm ² for 10 minutes.

Further, it was cured at 180 ° C. for 1 hour to obtain a molded product.

The glass transition temperature and the elastic modulus at 20 ° C. of the molded product were measured.

The results are shown in Table 1.

Comparative Example 1 Example 1 was repeated except that poly (isopropenylphenyl glycidyl ether) was not used.

The results are shown in Table 1.

Comparative Examples 2-3 Other than using poly (isopropenylphenyl glycidyl ether) in place of 0-cresol novolac glycidyl ether Sumiepoxy ESCN-220 (Sumitomo Chemical Co., Ltd., epoxy equivalent 215, number average degree of polymerization 4.8). The same procedure as in Examples 1 and 2 was performed.

The results are shown in Table 1.

Front page continuation (72) Inventor Tadashi Ikushima 5-1 Sokai-cho, Niihama-shi, Ehime Sumitomo Chemical Co., Ltd. (56) References JP-A-52-123488 (JP, A) JP-A-62-84114 ( JP, A)

Claims (1)

[Claims] 1. A bisphenol A type glycidyl ether 50.
~ 99 parts by weight, general formula (1) (In the formula, R ^{1 to} R ⁴ are groups selected from hydrogen, an alkyl group having 1 to 10 carbon atoms, and halogen, and n is an average of 2 to 50.) Poly (isopropenylphenyl) An epoxy resin composition for a laminate, which is made by impregnating a base material (excluding carbon fibers) with a resin composition, which comprises 1 to 50 parts by weight of a glycidyl ether) and a curing agent.