JPH0749466B2 - Epoxy resin composition for laminated board - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION <Field of Industrial Application> The present invention relates to an epoxy resin composition which is particularly useful as a laminate material.

<Prior Art> Conventionally, a combination of a bisphenol epoxy resin and dicyandiamide has been mainly used as a material for an industrial printed wiring board. In recent years, with high-density mounting and multilayered printed wiring boards, improvement in heat resistance of the boards has been required. Conventionally, for such purpose, a method has been adopted in which a polyfunctional novolac type epoxy resin is used in combination with a bisphenol type epoxy resin as a heat resistance imparting component.

A heat-resistant epoxy resin containing another polyfunctional epoxy resin as a component has also been used.

<Problems to be Solved by the Invention> When a novolac type epoxy resin is added to a bisphenol type epoxy resin for the purpose of improving heat resistance, heat resistance is improved by increasing the addition amount, but it cannot be said to be sufficient. On the contrary, since the toughness of the cured product is reduced and becomes brittle, the adhesion with the metal foil forming the circuit is deteriorated, the moisture resistance is deteriorated, and the formability is deteriorated. Especially when using a bisphenol type epoxy resin brominated for the purpose of imparting flame retardancy, it is necessary to maintain the minimum Br content necessary for flame retardancy, and the addition amount of the novolac type epoxy resin is Due to the limitation, insufficient heat resistance has been a problem. Further, when a heat-resistant epoxy resin containing another polyfunctional epoxy resin as a component is used, there is a problem in terms of adhesiveness and moisture resistance even though heat resistance is sufficient. Therefore, there has been a demand for a well-balanced resin composition that is excellent not only in heat resistance but also in adhesiveness and moisture resistance, and is flame retardant.

<Means for Solving the Problem> From such a background, the present inventors have diligently studied an epoxy resin composition for laminates which is excellent in heat resistance and balanced with other physical properties, and as a result, bisphenols and bisphenols. It has been found that an epoxy resin for laminates comprising an epoxy resin and an epoxy curing agent and an adduct obtained by previously reacting a glycidyl ether compound of a condensate of a specific aromatic carbonyl compound and phenols is suitable for the above purpose. The present invention has been completed.

That is, the present invention relates to (A) at least one bisphenol selected from the group consisting of bisphenol A, bisphenol F and tetrabromobisphenol A, and (B) bisphenols belonging to the group consisting of bisphenol A, bisphenol F and tetrabromobisphenol A At least one epoxy resin selected from the group of epoxy resins diglycidyl etherified with (C) an epoxy resin represented by the general formula (I) and an epoxy curing agent are essential. The present invention provides an epoxy resin composition as a component for laminated boards.

(In the formula, the substituents R ¹ to R ⁶ are saturated alkyl groups having 1 to 6 carbon atoms, and the substituents R ⁷ to R ¹² are hydrogen atoms, saturated alkyl groups having 1 to 4 carbon atoms, or 1 to 4 carbon atoms. X is a chlorine or bromine atom, GE is a glycidyl ether, a, b, c, d, e are 0 or 1, and the average number of repeating units l and m is 0 or more. And 1 + m is a number from 5 to 0.5.) Further detailed description of each component in the present invention is added below.

In the general formula (I), specific examples of R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ include a methyl group, an ethyl group, a propyl group, a butyl group, an amyl group and a hexyl group. Preferred examples include:

Further, specific examples of R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , and R ¹² are a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, and a methoxy group, but preferably a hydrogen atom. Or
Methyl group is particularly preferred as hydrogen atom.

A larger n is more preferable from the viewpoint of heat resistance, but if it exceeds too much and becomes too large, the melt viscosity becomes high and the operability, moldability and the like are deteriorated.

The epoxy resin represented by the general formula (I) of the present invention is, for example, the general formula (II) (In the formula, R corresponds to R ¹¹ and R ¹² in the general formula (I), and R ′,
R ″ corresponds to R ⁷ , R ⁸ , R ⁹ and R ¹⁰ of the general formula (I), and Y
Corresponds to Xb and Xd in the general formula (I). ) Is obtained by glycidyl etherification of a condensate of an aromatic carbonyl compound represented by

Specific examples of the aromatic carbonyl compound include hydroxybenzaldehyde, methylhydroxybenzaldehyde, dimethylhydroxybenzaldehyde, methoxyhydroxybenzaldehyde, chlorohydroxybenzaldehyde, bromobenzaldehyde, hydroxyacetophenone, hydroxyphenylethylketone and hydroxyphenylbutylketone. , Hydroxybenzaldehydes, particularly p-hydroxybenzaldehyde are preferred.

A small amount of another carbonyl compound may be used in combination with the aromatic carbonyl compound. For example, formaldehyde, acetaldehyde, crotonaldehyde, acrolein, glyoxal, benzaldehyde and the like.

Further, when exemplifying phenols, phenol, cresol, ethylphenol, propylphenol, butylphenol, amylphenol, hexylphenol, methylpropylphenol, methylbutylphenol, methylhexylphenol, methylphenylphenol,
Chlorophenol, bromophenol, chlorocresol, bromocresol, etc. are preferred, with methylbutylphenol being preferred.

Condensation of aromatic carbonyl compounds with phenols requires 0.5-1 phenols per mole of aromatic carbonyl compound.
Well-known acidic catalysts for synthesizing novolac, for example, mineral acids such as hydrochloric acid, sulfuric acid and phosphoric acid; organic acids such as oxalic acid and toluenesulfonic acid;
It is carried out in the presence of a salt such as zinc acetate.

At this time, an aromatic solvent such as toluene or chlorobenzene may be used.

In order to increase the number of repeating units as an oligomer, the ratio of phenols may be decreased, the temperature may be increased, and the catalyst may be increased.

The polyhydric phenols thus obtained can be halogenated with chlorine or bromine by a known method.

The glycidyl etherification can be obtained by a well-known method of converting phenols into glycidyl ether.

That is, it is a method of reacting the condensate with epichlorohydrin in the presence of an alkali such as caustic soda. In particular, the reaction in an aprotic polar solvent as described in JP-A-60-31517 previously filed by the present inventors is preferable. Further, the preliminary reaction of the (A) bisphenol, the (B) bisphenol type epoxy resin of the present invention and the (C) epoxy resin represented by the general formula (I) may be carried out by a known method. For example, there is a method in which the above components are reacted in the presence of a basic catalyst such as triphenylphosphine. Regarding the blending ratio of each of the above components, it is possible to select any ratio, but it is preferable that the component (C) is 20 to 60%, the epoxy equivalent after the preliminary reaction is 400 to 1000 g / eq, and the brominated component. When using, the weight ratio of bromine to the total is 18 wt%
The above is desirable.

Further, other known epoxy resins may be mixed with the epoxy resin adduct after the preliminary reaction of the present invention to such an extent that the effect of the present invention is not impaired. Other known epoxy resins include hydroquinone, resorcin, phloroglycine, tris- (4-hydroxyphenyl) methane, 1,1,2,2-
Glycidyl ether compounds derived from dihydric or trihydric or higher phenols such as tetrakis (4-hydroxyphenyl) ethane or halogenated bisphenols, and novolaks which are reaction products of phenol and phenols such as o-cresol and formaldehyde. Novolak epoxy resin derived from resin, aniline, p-
Aminophenol, m-aminophenol, 4-amino-m-cresol, 6-amino-m-cresol, 4,
4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether,
3,4'-diaminodiphenyl ether, 1,4-bis (4-
Aminophenoxy) benzene, 1,4-bis (3-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy)
Benzene, 2,2-bis (4-aminophenoxyphenyl) propane, p-phenylenediamine, m-phenylenediamine, 2,4-toluenediamine, 2,6-toluenediamine, p-xylylenediamine, m-xylylenediamine Amine, 1,4-cyclohexane-bis (methylamine),
1,3-Cyclohexane-bis (methylamine), 5-amino-1- (4'-aminophenyl) -1,3,3-trimethylindane, 6-amino-1- (4'-aminophenyl) -1 Amine-based epoxy resins derived from 3,3,3-trimethylindane and the like, glycidyl ester-based compounds derived from aromatic carboxylic acids such as p-oxybenzoic acid, m-oxybenzoic acid, terephthalic acid and isophthalic acid, 5 ,
Hydantoin-based epoxy resin derived from 5-dimethylhydantoin, etc., 2,2'-bis (3,4-epoxycyclohexyl) propane, 2,2-bis [4- (2,3-epoxypropyl) cyclohexyl] propane Alicyclic epoxy resins such as vinylcyclohexenedioxide and 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, triglycidyl isocyanurate, and 2,4,6-triglycidoxy-S-triazine 1 type (s) or 2 or more types can be mentioned.

Further, the epoxy resin curing agent of the present invention is a known epoxy resin curing agent, for example, phenol novolac,
Examples include polyphenols such as cresol novolac, amine-based curing agents such as aromatic amines and aliphatic amines, acid anhydrides, dicyandiamide, and hydrazine compounds. The mixing ratio is 0.5 to 1.2 with respect to the epoxy group.
Equivalent weights are preferred.

Particularly when a curing agent for polyhydric phenols is used, short circuits between circuits caused by migration of copper during moisture absorption when dicyandiamide is used are eliminated, which is advantageous for applications requiring this property. .

In the present invention, a curing accelerator, a flame retardant, and
Known additives such as a release agent, a surface treatment agent and a filler may be added.

Imidazoles, tertiary amines, etc. as curing accelerators, antimony trioxide, red phosphorus, etc. as flame retardants, waxes, zinc stearate, etc. as release agents, and silane cups as surface treatment agents. A ring agent can be mentioned. Examples of the filler include silica, alumina, talc, clay, glass fiber and the like.

When the resin composition of the present invention is used for a laminated board, the resin composition is uniformly dissolved in a solvent such as methyl ethyl ketone or toluene, ethylene glycol monomethyl ether, dimethylformamide, etc. alone or in combination, and glass fiber, polyester fiber, polyamide A prepreg obtained by impregnating a base material made of woven fabric, mat, paper or a combination thereof made of organic or inorganic fiber such as fiber or alumina fiber and heating and drying may be hot press molded.

<Effects of the Invention> The resin composition of the present invention thus obtained provides a laminated molded product having excellent heat resistance and a good balance with other properties.

Therefore, it is particularly useful as a basic material for printed wiring.

Hereinafter, the present invention will be described in more detail with reference to Examples.
The present invention is not limited to these.

Reference Example-1 In a reactor equipped with a thermometer, a stirrer, and a condenser, 3
657 g of -methyl-6-t-butylphenol, 48.8 g of p-hydroxybenzaldehyde and 0.38 g of sodium p-toluenesulfonate (monohydrate) were reacted at 95 to 105 ° C for 6 hours under reflux with stirring. Then, after neutralizing with a 10% aqueous sodium hydroxide solution, dissolving in toluene 1 and washing twice with water, toluene and unreacted monomers are removed by distillation,
Reddish brown triphenolmethanes were obtained.

Furthermore, the amount of triphenolmethanes per one phenolic hydroxyl group was charged into a reaction vessel equipped with a thermometer, a stirrer, a dropping funnel, and a condenser with a separating tube, and dissolved in 462.6 g of epichlorohydrin and 231.3 g of dimethyl sulfoxide. While maintaining the reaction system at 45 Torr, 40% NaOH aqueous solution 10
0 g was continuously added dropwise over 5 hours.

During this time, while keeping the temperature at about 45 ° C., the azeotropic epichlorophudrine and water were cooled and liquefied, and the reaction was performed while returning the organic layer into the reaction system.

After completion of the reaction, unreacted epichlorohydrin was removed by distillation under reduced pressure, glycidyl ether of triphenolmethanes containing by-product salt and dimethylsulfoxide was dissolved in methyl isobutyl ketone, and by-product salt and dimethylsulfoxide were removed by washing with water. .

Further, methyl isobutyl ketone was removed by vacuum distillation.

The epoxy equivalent of the glycidyl ether thus obtained was measured and found to be 209 g / eq.

Reference Example-2 3-methyl-6-t-butylphenol 657g in Reference Example-1 was replaced with 3-methyl-6-t-butylphenol 492g.
Then, the same operation was performed except that m-cresol was changed to 108 g to obtain an epoxy resin having an epoxy equivalent of 204 g / eq.

Reference Example-3 In a round bottom flask equipped with a stirrer, a condenser, and a thermometer, 40 parts of the epoxy resin of Reference Example 1, Smye epoxy EL
A-128 (bisphenol A type epoxy resin, epoxy equivalent 187g / eq, Sumitomo Chemical Co., Ltd. product) 27.7g, tetrabromobisphenol A 32.3g, 9 parts of methyl ethyl ketone were charged and heated to 110 ° C to be completely dissolved. After that, 0.02 parts of triphenylphosphine was added, and the mixture was reacted at 110 ° C. for 4 hours. The epoxy equivalent of the obtained resin was 467 g / eq and the Br content was 19 wt%.

Reference Example-4 Epoxy resin 50 of Reference Example-1 among the compounding ratios of Reference Example-3
The same operation was performed except that Sumiepoxy ELA-128 was changed to 17.7 parts. The epoxy equivalent of the obtained resin was 472 g / eq, and the Br content was 18.8 wt%.

Reference Example-5 Among the compounding ratios of Reference Example-3, the epoxy resin of Reference Example-1 was used.
The same operation was performed except that 60 parts was changed to 7.7 parts for Sumi Epoxy ELA-128. The epoxy equivalent of the obtained resin was 478 g / eq and the Br content was 19 wt%.

Reference Example-6 Epoxy resin of Reference Example-1 among the charged raw materials of Reference Example-3
The same operation was performed except that 40 parts was changed to 40 parts of the epoxy resin of Reference Example-2, the epoxy equivalent was 454 g / eq, and the Br content was 19 w.
t% resin was obtained.

Comparative Reference Example Epoxy resin of Reference Example-1 among the charged raw materials of Reference Example-3
The same operation was performed except that 40 parts of Sumie Epoxy ESCN-195X (o-cresol novolac type epoxy resin, manufactured by Sumitomo Chemical Co., Ltd.) was changed to 40 parts. The epoxy equivalent of the obtained resin was 412 g / el, and the Br content was 19 wt%.

Examples 1 to 4 The epoxy resins obtained in Reference Examples 3 to 6 and dicyandiamide and 2-ethyl-4-methylimidazole are shown in Table-1.
The respective components were mixed in the proportions shown in Table 1, and a solvent was added so that 15 parts of dimethylformamide and 25 parts of methyl ethyl ketone were added to 60 parts of the resin solid content and dissolved until a uniform solution was obtained. Furthermore, this solution was aged at 80 ° C. for 1 hour to obtain a resin varnish in which dicyandiamide did not precipitate at room temperature.
The varnish was impregnated into glass cloth (KS-1600, manufactured by Kanebo Co., Ltd., treated with epoxysilane) and dried in a hot air dryer at 130 ° C. for 8 to 15 minutes to obtain a prepreg. 6 pieces of prepreg and copper foil (Furukawa Circuit Foil Co., Ltd., TTAI treatment, 35μ
Thickness) were overlapped and press-molded at 160 ° C. under a pressure of 50 kg / cm ² for 90 minutes to obtain a 1 mm-thick copper clad laminate. The physical properties of this laminated plate were measured according to JIS-C-6481, and the results shown in Table 1 were obtained. For the measurement of flame retardancy, a 1.6 mm thick laminated plate obtained by press-molding eight prepregs in the same manner was used.

Comparative Example-1 The epoxy resin obtained in Comparative Reference Example was mixed with dicyandiamide and 2-ethyl-4methylimidazole in the proportions shown in Table-1, and a laminate was obtained in the same manner as in Examples-1 to 4. The physical properties of this laminate were measured by the methods of Examples 1 to 4 and the results are shown in Table-1.

Comparative Example-2 Sumi Epoxy ESB-500 (Brominated Bisphenol A Type Epoxy Resin, Epoxy Equivalent 472g / eq, Sumitomo Chemical Co., Ltd. Product) 90g, Sumi Epoxy ESCN-220F (o-cresol novolac type epoxy resin, epoxy equivalent) 215g
/ eq, Sumitomo Chemical Co., Ltd. product) 10g, diciadiamide 4.
5 g and 0.1 g of 2-ethyl-4-methylimidazole were mixed, and a laminate was obtained by the same method as in Examples-1 to 4. The physical properties of this laminate were measured by the methods of Examples 1 to 4, and the results are shown in Table-1.

Comparative Example-3 Sumy epoxy ESB-500 of Comparative Example-2 in 80 g, Sumi epoxy ESCN-220F in 20 g, dicyandiamide 5.0 g.
The same operation was performed except that the above was changed to obtain the physical properties of the laminated plate. The results are shown in Table-1.

Comparative Example-4 Techmore VF2801 (manufactured by Mitsui Petrochemical Co., Ltd.) 100 g, dicyandiamide 4.85 g, 2-ethyl-4 methylimidazole
0.1 g was added and a laminated plate was obtained in the same manner as in Examples-1 to 4. The physical properties of this laminate were measured by the methods of Application Examples 1 to 4, and the results are shown in Table-1.

From the results shown in Table 1, the laminated plate made of the resin composition according to the present invention has excellent heat resistance and water resistance, and is well balanced with other physical properties, and its usefulness is clear.

Front page continuation (72) Inventor Hide Sakamoto 5-1, Sokai-cho, Niihama-shi, Ehime Sumitomo Chemical Co., Ltd. (72) Inventor Noriaki Saito 5-1, Sokai-cho, Niihama-shi, Ehime Sumitomo Chemical Co., Ltd. (56) References JP-A-1-501800 (JP, A) JP-A-1-271415 (JP, A) JP-A-63-264622 (JP, A) JP-A-57-141419 (JP, A)

Claims (1)

[Claims] 1. At least one bisphenol selected from the group consisting of (A) bisphenol A, bisphenol F and tetrabromobisphenol A, and (B) bisphenol of the group consisting of bisphenol A, bisphenol F and tetrabromobisphenol A. At least one epoxy resin selected from the group of epoxy resins obtained by diglycidyl etherification of compounds with (C) an epoxy resin represented by the general formula (I), and an epoxy curing agent. An epoxy resin composition for laminated boards, which comprises as an essential component. [In the formula, the substituents R ¹ to R ⁶ are saturated alkyl groups having 1 to 6 carbon atoms, and the substituents R ⁷ to R ¹² are hydrogen atoms, saturated alkyl groups having 1 to 4 carbon atoms, or 1 to 4 carbon atoms. Is an alkoxy group, X is a chlorine or bromine atom, and GE is a glycidyl ether. Further, a, b, c, d, e are 0 or 1, the average repeating unit numbers l and m are 0 or more, and l + m is a number from 0.5 to 5. ]