JPH07173257A - Epoxy resin composition and cured product thereof - Google Patents

Abstract

PURPOSE:To obtain an epoxy resin composition which can give a cured product having low dielectric properties and excellent heat and water resistances and being useful as an electrical or electronic material such as an insulation material, a laminste or a sealing material by mixing a specified epoxy resin with a specified curing agent and optionally a cure accelerator. CONSTITUTION:This composition is obtained by mixing an epoxy resin represented by formula I (where n is 0 or 1-10; R is a group of formula II or III; and M is H or glycidyl, provided that 5-95% of nMs are glycidyl groups) with a curing agent represented by formula IV (wherein n is 2-6; R1 is CH3 or C2H5; and R2 is H or a hydrocarbon group), and optionally a cure accelectator. This composition can give a cured product having low dielectric properties and excellent heat and water resistances as compared with conventional ones and therefore being useful ad an electrical or electronic material such as an insulation material, a laminate or a sealing material.

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 and a cured product thereof. The composition of the present invention can be used for laminating materials, molding materials, casting materials, composite materials, paints, adhesives, resists, etc. Very useful for a wide range of applications.

[0002]

2. Description of the Related Art Epoxy resins, when cured with various curing agents, generally become cured products having excellent mechanical properties, water resistance, chemical resistance, heat resistance, electrical properties, etc. It is used in a wide range of fields such as agents, paints, molding materials, and casting materials.

[0003]

However, in recent years, particularly with the development of the electric and electronic fields, further improvement of various properties such as heat resistance, water resistance, and dielectric property has been demanded, and the improvement of these various properties has been demanded. For this purpose, many proposals have been made on epoxy resins, epoxy curing agents and compositions thereof, but they are still insufficient.

[0004]

Means for Solving the Problems As a result of diligent research on the method for imparting and improving the characteristics as described above, the present inventors have found that
The present invention has been completed by finding a resin composition that can achieve the above object. That is, the present invention provides (1) the following formula (1)

[0005]

[Chemical 4]

(In the formula, n represents an average value and represents a positive number in the range of 0.1 to 10. R represents one of the following formulas (2) and (3) or both. M represents a hydrogen atom or Represents a glycidyl group, n existing M is 5 to 95 as an average value.
% Is a glycidyl group. )

[0007]

[Chemical 5]

An epoxy resin (A) represented by the following formula (4)

[0009]

[Chemical 6]

(In the formula, the value of n represents an average value and represents a positive number in the range of 2 to 6. R ₁ is a methyl group or an ethyl group, and R _{2 is}
Represents hydrogen or a hydrocarbon group. ) A curing agent (B) represented by the formula (1), an epoxy resin composition containing a curing accelerator if necessary, (2) the epoxy resin composition according to the above (1) prepared for a laminate, (3) the above ( A cured product obtained by curing the epoxy resin composition according to 2) or (3).

In the epoxy resin composition of the present invention,
The total amount of the epoxy resin and the curing agent in the resin composition may be the epoxy resin (A) and the curing agent (B) in the present invention, but other epoxy resins and other curing agents may be used in combination.

Specific examples of the epoxy resin that can be used in combination include a bisphenol type epoxy resin and a novolac type epoxy resin, but the epoxy resin is not particularly limited thereto. However, when used in combination with these other epoxy resins,
In order to bring out the features such as high heat resistance and low dielectric constant of the epoxy resin composition of the present invention, at least 30% by weight, preferably 50% by weight or more, of the total resin amount is the epoxy resin (A).
Blend so that

Examples of the curing agent that can be used in combination include amine compounds, acid anhydride compounds, amide compounds, and phenol compounds, but are not limited thereto. Specific examples thereof include diaminodiphenylmethane, diethylenetriamine, triethylenetetramine,
Polyamide resin synthesized from diaminodiphenylsulfone, isophoronediamine, dicyandiamide, linolenic acid dimer and ethylenediamine, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydro Phthalic anhydride, methyl nadic acid anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, pheno-
Lunovolac and modified products thereof, imidazole, B
Examples include F ₃ -amine complexes and guanidine derivatives. However, when used in combination with these other curing agents, at least 30% by weight, preferably 50% by weight or more of the total amount of the curing agent is used in order to bring out the characteristics of the epoxy resin composition of the present invention such as high heat resistance and low dielectric constant. Is the curing agent (B) in the present invention
Blend so that The amount of the curing agent used is 0.7 equivalent of phenolic hydroxyl group to 1 equivalent of epoxy group of epoxy resin.
~ 1.2 equivalents are preferred. If the amount is less than 0.7 equivalent or more than 1.2 equivalent to the epoxy group,
In either case, curing may be incomplete and good cured physical properties may not be obtained.

The epoxy resin composition of the present invention may optionally contain a curing accelerator, and specific examples of the curing accelerator that can be used include imidazole compounds such as 2-methylimidazole and 2-ethylimidazole. Known curing accelerators such as, but not limited to, tertiary amine compounds such as 2- (dimethylaminomethyl) phenol, triphenylphosphine and the like are mentioned. These curing accelerators may be used alone or in combination of two or more. The amount of the curing accelerator used is 0.01 to 15 parts by weight, preferably 0.1 to 5.0 parts by weight, based on 100 parts by weight of the epoxy resin.

With the epoxy resin composition of the present invention, a cured product of the epoxy resin composition can be easily obtained by the same method as a conventionally known method.

For example, an epoxy resin (A), a curing agent (B), and if necessary, an inorganic filler such as silica, alumina or talc, and other additives such as a silane coupling agent, a release agent and a pigment are extruded. The epoxy resin composition obtained by sufficiently mixing it using a machine, a kneader, a roll, etc. until it becomes homogeneous is melted and then molded using a casting machine or a transfer molding machine, and further 80-200. A cured product can be obtained by heating at 1 ° C. for preferably 1 hour or more.

Further, the epoxy resin composition of the present invention is dissolved in a solvent, impregnated into a substrate such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber or paper, heated and semi-dried. The prepreg can be hot-press molded to obtain a cured product.

For example, a glass cloth is impregnated with the epoxy resin composition obtained by heating and stirring the epoxy resin (A), the curing agent (B), the curing accelerator, the solvent for dilution, and the like until they become uniform, and then heating and semi-drying. Then, the required number of the prepregs freed from the solvent are stacked and heated and pressed at 80 to 200 ° C. for 1 hour or more to produce a glass cloth laminate. As specific examples of the diluting solvent used at this time, methyl ethyl ketone, methyl cellosolve and the like are preferable, and the amount thereof is preferably about 30 to 40% by weight in the epoxy resin composition. The resin content of the prepreg is 40-60.
About wt% is good.

The cured product thus obtained has high heat resistance,
Further, since the dielectric constant is low, the epoxy resin composition of the present invention can be used in a wide range of fields in which high heat resistance, low dielectric properties and the like are required. Specifically, it is useful as any electric / electronic material such as an insulating material, a laminated plate, and a sealing material.

[0020]

EXAMPLES Next, the present invention will be specifically described by way of examples. The present invention is not limited to these examples.

Example 1 NER2102 (manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 30) which is an epoxy resin in which R in the formula (1) corresponds to the formula (2)
7 g / eq, softening point 62 ° C.), Nisseki special phenol resin, PP-700-30, which is a curing agent corresponding to formula (4)
0 (Nippon Petrochemical Co., Ltd., hydroxyl equivalent 317 g / e
q, softening point 150 ° C.), 2-ethyl-as a curing accelerator
4-Methylimidazole (2E4MZ), methyl ethyl ketone (MEK) and methyl cellosolve (MCS) as diluents were mixed in the parts by weight shown in Table 1, heated at 80 ° C, stirred, and then aged at 80 ° C for 4 hours to form a varnish. To obtain the epoxy resin composition (EP-1) of the present invention.

Example 2 Nisseki special phenol resin was used in place of the curing agent of Example 1,
PP-1000-180 (manufactured by Nippon Petrochemical Co., Ltd., hydroxyl equivalent 555 g / eq, softening point 112 ° C.) was used and blended in the same weight parts as shown in Table 1, and in the same manner as in Example 1 to give a varnish. An epoxy resin composition (EP-2) of the present invention was obtained.

Comparative Example 1 Instead of the epoxy resin of Example 1, brominated bisphenol A type epoxy (Epomic R-232 (Roblo),
Mitsui Petrochemical Co., Ltd., epoxy equivalent 483g / eq)
In place of the curing agent, phenol novolac resin (manufactured by Nippon Kayaku Co., Ltd., hydroxyl equivalent 105 g / eq, softening point 83
C.) and similarly blended in the weight parts shown in Table 1 and in the same manner as in Example 1 to obtain a varnish-like comparative epoxy resin composition (EP-3).

[0024]

Table 1 Example 1 Example 2 Comparative Example 1 NER2102 100 100 R-232 (Robro) 100 PP-700-300 103 PP-1000-180 180 Phenol novolac 21 Accelerator (2E4MZ) 0.3 0. 3 0.3 Diluted solvent (MEK) 117 162 72 (MCS) 13 18 8

Examples 3 to 4, Comparative Example 2 Varnish-like epoxy resin composition EP-obtained above
1, EP-2, EP-3 with glass cloth (WEA18W
It was impregnated with 105F115N (manufactured by Nitto Boseki Co., Ltd.) and then heat-dried for 7 minutes with a hot air dryer at 120 ° C. to obtain a semi-cured prepreg. 8 pieces of this prepreg and copper foil (Nikko Gould Co., Ltd., JTC foil, 35 μm) were piled up, and 17
A glass cloth laminate was prepared by press molding at 0 ° C. for 60 minutes at 40 kgf / cm ² .

The characteristics of the produced laminated plate were measured by the following items and methods. The measurement results are shown in Table 2. Glass transition temperature Thermomechanical measuring device (TMA): Vacuum Riko TM-7000 Temperature rising rate: 2 ° C / min Copper foil peel strength Tensile tester: Toyo Baldwin Tensilon RTM
-500 Tensile mode (180 ° peeling) Measurement temperature: 30 ° C Crosshead speed: 200mm / min Copper foil: Nikko Gourde Co., Ltd. JTC foil 35μm Water absorption test piece: 5cm × 5cm Boiled in warm water of 100 ° C for 24 hours Weight increase amount (% by weight) Dielectric constant, dielectric loss tangent The measurement was performed according to JIS 6481 (dielectric constant and dielectric loss tangent).

[0027]

Table 2 Example 3 Example 4 Comparative Example 2 Epoxy resin EP-1 EP-2 EP-3 Glass transition temperature (° C) 142 119 125 Copper foil peeling strength (Kg / cm) 2.3 2.1 1.9 Water absorption rate (%) 0.6 0.6 0.8 Dielectric constant 4.2 4.0 4.0 4.8 Dielectric loss tangent 0.014 0.013 0.018

As described above, from Table 2, the cured product obtained by curing the epoxy resin composition of the present invention is superior in heat resistance and water resistance and has a low dielectric property as compared with the conventionally known ones.

[0029]

EFFECT OF THE INVENTION The cured product of the epoxy resin composition of the present invention has excellent heat resistance, water resistance, and low dielectric property, and therefore is useful as any electric / electronic material such as an insulating material, a laminate, or a sealing material. .

Claims (3)

[Claims] 1. The following formula (1): (In the formula, n represents an average value and represents a positive number in the range of 0.1 to 10. R represents one of the following formulas (2) and (3) or both. M represents a hydrogen atom or a glycidyl group. The average value of n existing M is 5 to 95% is a glycidyl group.) And an epoxy resin (A) represented by the following formula (4): (In the formula, the value of n represents an average value and represents a positive number in the range of 2 to 6. R ₁ represents a methyl group or an ethyl group, and R ₂ represents a hydrogen or a hydrocarbon group.) (B), an epoxy resin composition which optionally contains a curing accelerator. 2. The epoxy resin composition according to claim 1, which is prepared for a laminated board. 3. A cured product obtained by curing the epoxy resin composition according to claim 2 or 3.