JPH10130365A - Epoxy resin mixture, epoxy resin composition and its hardened material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an epoxy resin mixture excellent in thermal stability, moisture resistance, adhesion, etc., having light weight, further excellent in mechanical properties, and having a low viscosity and an improved operability by mixing two kinds of epoxy resins having specific structures. SOLUTION: This epoxy resin composition is obtained by mixing an epoxy resin of formula I (G is glycidyl) and an epoxy resin of formula II. The amount of the resin of formula II is preferably 10-40wt.% of that of the objective composition. A hardener of 0.6-1.2eq. based on 1eq. of the epoxy resin is preferably used when formulating the hardener to the mixture to form an epoxy resin composition. For example, diethylenetriamine, phthalic anhydride, etc., are used as the hardener. A hardening accelerator such as 2-methylimidazol can be used therewith. An inorganic filler is preferably added to the before composition. The composition is hardened after molding by heating the molded composition at 80-200 deg.C for 2-10hr to obtain a hardened product from the composition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an insulating material for electric and electronic parts such as a high-reliability semiconductor encapsulation, and various kinds of materials such as a laminate (printed wiring board) and CFRP (carbon fiber reinforced plastic). The present invention relates to an epoxy resin mixture, an epoxy resin composition, and a cured product thereof useful for composite materials, adhesives, paints, and the like.

[0002]

2. Description of the Related Art Epoxy resins are used in the fields of electric and electronic parts, structural materials, adhesives, paints, etc. due to their workability and excellent electrical properties, heat resistance, adhesiveness, and moisture resistance (water resistance) of the cured product. Widely used in

[0003]

However, with the recent development in the electric and electronic fields, various properties such as heat resistance, moisture resistance, adhesion, and low viscosity for high filling of the epoxy resin have been developed. Is required to be further improved. In addition, as a structural material, an epoxy resin that is lightweight and has excellent mechanical properties in aerospace materials, leisure and sports equipment applications, and at the same time, has a low viscosity is required to improve workability. Many proposals have been made for epoxy resin compositions to meet these requirements,
Not enough yet.

[0004]

Means for Solving the Problems The present inventors have made intensive studies on an epoxy resin composition having the above-mentioned properties, and as a result, completed the present invention. That is, the present invention

(1) The following equation (1)

[0006]

Embedded image

(Wherein, G represents a glycidyl group)

The epoxy resin (A) represented by the following formula (2)

[0009]

Embedded image

(In the formula, n is an average value and represents a positive number of 1 to 10. G represents a glycidyl group.)

An epoxy resin mixture obtained by mixing the epoxy resin (B) represented by the formula (1), (2) an epoxy resin composition containing the epoxy resin mixture described in the above (1) and a curing agent, and (3) an inorganic resin. The epoxy resin composition according to the above (2), comprising a filler, (4) the above (2) or (3).
And a cured product obtained by curing the epoxy resin composition described above.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION

In the epoxy resin mixture of the present invention, specific examples of the epoxy resin (A) represented by the formula (1) include RE-404S (manufactured by Nippon Kayaku Co., Ltd.).

Next, specific examples of the epoxy resin (B) represented by the formula (2) in the epoxy resin mixture of the present invention include EPPN-501H.

The proportion of the epoxy resin (B) in the epoxy resin mixture described in the above (1) is usually 5 to 50% by weight, preferably 10 to 40% by weight.

Hereinafter, the epoxy resin composition of the present invention will be described. In the epoxy resin composition of the present invention, the epoxy resin mixture of the present invention can be used alone or in combination with another epoxy resin. When used in combination, the proportion of the epoxy resin mixture of the present invention in the total epoxy resin is preferably at least 30% by weight, particularly preferably at least 40% by weight.

Other epoxy resins which can be used in combination with the epoxy mixture of the present invention include bisphenols, phenols (phenol, alkyl-substituted phenol, naphthol,
Polycondensates of alkyl-substituted naphthol, dihydroxybenzene, dihydroxynaphthalene) with various aldehydes,
Polymers of phenols and various diene compounds, polycondensates of phenols and aromatic dimethylol, glycidyl ether-based epoxy resins obtained by glycidylation of biphenols and alcohols, alicyclic epoxy resins, glycidylamine-based epoxy resins, etc. But are not limited to these. These may be used alone or in combination of two or more.

The epoxy resin composition of the present invention contains a curing agent. As the curing agent, amine compounds, acid anhydride compounds, amide compounds, phenol compounds and the like can be used. Specific examples of the curing agent that can be used include diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, dicyandiamide, a polyamide resin synthesized from a dimer of linolenic acid and ethylenediamine,
Phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride,
Polycondensates of hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, bisphenols, phenols (phenol, alkyl-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, dihydroxynaphthalene, etc.) with various aldehydes, phenols And polydiene compounds, polycondensates of phenols and aromatic dimethylol, biphenols and their modified products, imidazole, BF ₃ -amine complex, guanidine derivatives and the like. The amount of curing agent used is
0.5 to 1 with respect to 1 equivalent of epoxy group of epoxy resin.
Five equivalents are preferred, and 0.6-1.2 equivalents are particularly preferred. If the amount is less than 0.5 equivalents or more than 1.5 equivalents with respect to 1 equivalent of the epoxy group, curing may be incomplete and good cured physical properties may not be obtained.

When the above curing agent is used, a curing accelerator may be used in combination. Specific examples of the curing accelerator that can be used include imidazoles such as 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2- (dimethylaminomethyl) phenol,
1,8-diaza-bicyclo (5,4,0) undecene-
Tertiary amines such as 7, phosphines such as triphenylphosphine, and metal compounds such as tin octylate. The hardening accelerator is used in an amount of 0.01 to 15 parts by weight based on 100 parts by weight of the epoxy resin as required. Furthermore, the epoxy resin composition of the present invention can contain various fillers such as an inorganic filler such as silica, alumina, and talc, a silane coupling agent, a release agent, and a pigment, if necessary. Preferably, a material is added. When an inorganic filler is used, it is usually used in an amount of 0 to 95% by weight based on the total weight of the composition including the filler.

The epoxy resin composition of the present invention can be obtained by uniformly mixing the above components. The epoxy resin composition of the present invention can be easily made into a cured product by a method similar to a conventionally known method. For example, the epoxy resin of the present invention and a curing agent, if necessary, a curing accelerator, an inorganic filler, and other compounding materials may be used as necessary in an extruder, a needle,
The epoxy resin composition is sufficiently mixed until it becomes uniform using a die, a roll or the like, and the epoxy resin composition is melted and then molded using a casting or transfer molding machine, and more preferably. The cured product of the present invention can be obtained by heating at 80 to 200 ° C. for 2 to 10 hours.

Further, the epoxy resin composition of the present invention is dissolved in a solvent such as toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, and the like, and is used to prepare glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber, paper, etc. A prepreg obtained by impregnating a substrate and drying by heating may be subjected to hot press molding to obtain a cured product.

In this case, the ratio of the solvent to the total weight of the epoxy resin composition of the present invention and the solvent is usually 1%.
It is used in an amount of 0 to 70% by weight, preferably 15 to 65% by weight.

[0023]

Next, the present invention will be described in more detail with reference to Examples and Comparative Examples. Note that the present invention is not limited to these examples. In the examples, analysis conditions for epoxy equivalent and viscosity are as follows. Epoxy equivalent Measured in accordance with JIS K-7236, unit is g
/ Eq. Viscosity Measured at 25 ° C. using a B-type viscometer, and the unit is centipoise (cps).

Examples 1 to 3 and Comparative Example 1 As the epoxy resin (A), bisphenol F type epoxy resin RE-404S represented by the above formula (1) (manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent: 165 g / eq, (3200 cps at 25 ° C.) and EPPN-501H represented by the formula (2) as an epoxy resin (B) (Nippon Kayaku Co., Ltd., epoxy equivalent 164 g / eq, softening point 53.
6 ° C.) and, as a comparative example, only bisphenol A type liquid epoxy resin Epicoat 828 (manufactured by Yuka Shell Epoxy Co., Ltd., epoxy equivalent: 186 g / eq, viscosity at 25 ° C. 13,000 cps), and a curing agent methylnadic anhydride ( Kayahard MCD, Nippon Kayaku Co., Ltd.) and a curing accelerator (2-ethyl-4-methylimidazole (2E4MZ)) in the amounts shown in the composition column of Table 1 were mixed and mixed. Pour into molds at 80 ° C for 2 hours, 12
Curing was performed at 0 ° C. for 2 hours and at 200 ° C. for 5 hours.

The results of measuring the physical properties of the cured product thus obtained are shown in Table 1 in the column of physical properties of the cured product. The numerical values in the column of the composition of the composition in Table 1 represent parts by weight. The measurement of the physical properties was performed by the following methods. Glass transition temperature (TMA) TM-7000 manufactured by Vacuum Riko Co., Ltd. Temperature rising rate 2 ° C./min.

[0026]

Table 1 Example Comparative Example 1 2 3 1 Formulation Composition RE-404S 90 80 70 0 EPPN-501H 10 20 30 0 Epicoat 828 0 0 0 100 Kayahard MCD 97 97 97 86 2E4MZ 1 11 1 Epoxy Epoxy equivalent (g / eq) 165 165 165 186 Viscosity (cps / 25 ° C.) 6500 13000 26000 13000 Physical properties of cured product Glass transition point (° C.) 179 185 189 175

As apparent from Table 1, the epoxy resin composition of the present invention exhibited a low viscosity in a liquid state while maintaining high heat resistance in the cured product.

[0028]

The epoxy resin composition containing the epoxy resin mixture of the present invention is liquid at room temperature while maintaining high heat resistance, and enables high filling of filler and improvement of workability. Therefore, the epoxy resin of the present invention can be used as an insulating material for electric and electronic parts (such as a highly reliable semiconductor encapsulating material) and various composite materials such as a laminate (such as a printed wiring board) and CFRP, a paint, an adhesive, and a resist. It is very useful for a wide range of applications such as.

Claims (4)

[Claims] (1) The following formula (1): (Wherein G represents a glycidyl group) and an epoxy resin (A) represented by the following formula (2): (Wherein, n represents a positive number of 1 to 10 on average; G represents a glycidyl group.) An epoxy resin mixture obtained by mixing with an epoxy resin (B). 2. An epoxy resin composition comprising the epoxy resin mixture according to claim 1 and a curing agent. 3. The epoxy resin composition according to claim 2, further comprising an inorganic filler. 4. A cured product obtained by curing the epoxy resin composition according to claim 2 or 3.