JPH04122720A - Epoxy resin composition, cured epoxy resin product, copper-clad laminate and production process - Google Patents

Abstract

PURPOSE:To obtain an epoxy resin composition which can give a cured product excellent in heat resistance, adhesiveness, flexibility, chemical resistance and bending strength by mixing a specified resin base with a specified curing agent and a specified additive. CONSTITUTION:This composition comprises a resin base which is a bisphenol A epoxy resin of formula I (wherein (n) is 0-10; R<1> and R<2> are each glycidyl; and A<1> to A<8> are each H or Br), an epoxy resin curing agent which is a novolac resin of a (brominated)bisphenol A or formula I (wherein (n) is 0; R<1> and R<2> are each H, and A<1> to A<4> are each H or Br) or of a (brominated)bisphenol A composed of at least two molecules of the former (brominated)bisphenol A bonded in any of positions A<1> to A<4> through a methylene group and an additive which is an epoxy acrylate resin of formula I (wherein (n) is O-10; R<1> and R<2> are each an acrylic ester group of formula II; and A<1> to A<8> are each H).

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to an epoxy resin composition containing a resin base having a bisphenol A type skeleton, an epoxy resin curing agent, and an additive. Epoxy resin compositions and cured products thereof, which further improve properties such as good adhesion and heat resistance, as well as excellent toughness, flexibility, bending strength, and chemical resistance, and copper products using the same. The present invention relates to a stretched laminate and a method for manufacturing the same.

[Conventional technology]

Epoxy resins have been used in a wide range of industrial fields due to their good adhesion and heat resistance.

Among them, glass epoxy copper-clad laminates used in printed wiring boards are being used not only for industrial purposes, but also for consumer use, where paper phenol copper-clad laminates have been the mainstay until now.

The epoxy resins (compositions) conventionally used for printed wiring boards include: (1) polyfunctional epoxy resins, novolac-type phenolic resins, and brominated polyp-vinyl phenols with improved twist resistance and flame resistance ( Japanese Unexamined Patent Publication 1973-
112924), ■ Epoxy resin blended with phenol novolac resin to improve heat resistance, solvent resistance, etc. (JP-A-57-109642), ■ Epoxy resin and para-secondary butylphenol/phenol co-condensed novolak A product in which heat resistance and solvent resistance are improved by blending a resin (Japanese Patent Application Laid-Open No. 57190025); ■An epoxy resin composition is reacted with a bisphenol A type epoxy resin, a tetrabromo bisphenol A, and a polyfunctional epoxy resin. A product with improved heat resistance by blending the resulting brominated epoxy resin (JP-A No. 62-167044), ■N, N, N', N'-tetraglycidyl-4,4' in the brominated epoxy resin. - Improved flame retardancy by blending diaminophenylmethane (JP-A-62-177014
) etc.

However, as printed wiring boards become more dense and multi-layered, the current situation is that conventional boards using epoxy resins are no longer fully satisfactory.

For example, conventional epoxy resins are fully satisfactory in adhesion strength to copper foil at room temperature, but
When the temperature rises above ℃, its strength decreases rapidly.
In terms of reliability, there is a problem with high-density wiring boards with extremely fine patterns.

In other words, in the reflow process, which is the flow of mounting components on a board, the temperature of the board becomes high in parts due to the use of infrared rays, etc., and the number of reflows tends to increase. In,
There is a problem that problems such as peeling of the patterned copper foil occur. Moreover, some of the parts in the negative part partially raise the temperature of the board to 100 DEG C. or more, and there is also a problem in the board on which such parts are mounted.

In addition, with the spread of IC carts and the reduction in weight of devices, the thickness of circuit boards has become noticeably thinner, and therefore there is a need for strong boards with high strength, especially bending strength, but conventional epoxy resin When using a substrate, there are also problems with the strength of the substrate, such as breakage when subjected to repeated bending loads.

Furthermore, as the pattern spacing and through-hole spacing become narrower, conventional epoxy resins no longer have satisfactory chemical resistance to chemicals used in plating, etching, blackening treatments, and the like.

In this way, as the pattern width becomes narrower due to higher density,
Improvement in the adhesion between the copper foil and the substrate is required from the viewpoint of reliability as well as heat resistance. In addition, as devices become lighter, thinner, shorter, and smaller, substrates become thinner, and improvements in bending strength and flexibility are required. Furthermore, there is a demand for improved chemical resistance to chemicals such as plating, etching, and blackening treatments. Therefore, there is a need for epoxy resin and copper-clad laminates that can fully meet these requirements.

[Problem to be solved by the invention]

In order to meet the above-mentioned needs, the object of the present invention is to provide an object that has excellent heat resistance and adhesive properties, and therefore has high adhesion strength between copper foil and resin at high temperatures, has excellent flexibility and chemical resistance, and has bending strength. An object of the present invention is to provide an epoxy resin composition with high toughness.

Other objects of the present invention are heat resistance, adhesion, flexibility,
An object of the present invention is to provide a strong cured epoxy resin having excellent chemical resistance and high bending strength.

Furthermore, another object of the present invention is that by using the epoxy resin composition, the adhesion strength between the copper foil and the composite material at high temperatures is high, and furthermore, it is excellent in chemical resistance and is strong and has high bending strength. The purpose of this invention is to propose a copper-clad laminate and a method for manufacturing the same.

[Means to solve the problem]

The present invention provides the following epoxy resin composition, cured epoxy resin, copper-clad laminate, and method for producing the same.

(1) (A) As the resin main ingredient, the following general formula [1] (where n is 0 to 10. R1 and R2 are glycidyl groups,
A bisphenol A-based epoxy resin represented by (A1 to A' are hydrogen atoms or bromine atoms); (B) as an epoxy resin curing agent; (b2) the following general formula [1] (where n is 0, R'' and R2 is a hydrogen atom, A1 to A4 are hydrogen atoms or bromine atoms), or (b2) the following general formula [1] (where n is 0, R'' and R2 are hydrogen atoms, A1 ~A4 is a hydrogen atom or a bromine atom) A novolak resin of bisphenol A or its brominated product, in which two or more molecules of bisphenol A or its brominated product are bonded via a methylene group at any position of A1 to A4, and (C ) An epoxy resin composition containing, as an additive, an epoxy acrylate resin represented by the following general formula [1] (where n is an acrylic acid ester group, and A1 to A@ are hydrogen atoms).

... [1] (2) (A) As the resin main ingredient, a compound of the general formula [1] (where n is 0 to 10, R'' and R2 are glycidyl groups, and A1 to AIl are hydrogen atoms or bromine atoms) (B) As an epoxy resin curing agent, (b2) the above general formula [1] (where n is 0, R1 and R2 are hydrogen atoms, and A1 to A4 are hydrogen atoms or bromine atoms); ), or (b2) bisphenol A represented by the above general formula [1] (where n is 0, R1 and R2 are hydrogen atoms, and A1 to A4 are hydrogen atoms or bromine atoms) Or a novolak resin of bisphenol A or its bromide, in which two or more molecules of its bromide are bonded via a methylene group at any of the positions A1 to A4.

(C) As an additive, the general formula [1] (where n is OHO 0 to 10. R1 and R2 are -CH2-CH-CH2
An epoxy resin cured product obtained by curing an epoxy resin composition containing an acrylic acid ester group represented by -0 to C-CH=CH□ and an epoxy acrylate resin represented by A1 to All are hydrogen atoms.

(3) (A) Bisphenol A-based epoxy represented by the general formula [1] (where n is 0 to 10, R' and R2 are glycidyl groups, and A1 to A8 are hydrogen atoms or bromine atoms) as the main resin agent. (B) as an epoxy resin curing agent, (b2) bisphenol A represented by the above general formula [1] (where n is 0, R1 and R2 are hydrogen atoms, and A1 to A4 are hydrogen atoms or bromine atoms); or (b2) bisphenol A represented by the above general formula [1] (where n is 0, R' and R2 are hydrogen atoms, and A1 to A4 are hydrogen atoms or bromine atoms) or its brominated product. , a novolac resin of bisphenol A or its bromide bonded with two or more molecules by methylene groups at any of A1 to A4 positions, and (C) an additive of the above general formula [1] (where n is OHO ll 0 ~10, R1 and R2 are -C)I2-CH-CH2
An epoxy resin composition containing an acrylic acid ester group represented by -0 to C-CH=CH2, and an epoxy acrylate resin represented by A1 to A'' are hydrogen atoms, was irradiated with light to remove the additive (C). A cured epoxy resin product obtained by reacting and then curing the resin base material (A) and the epoxy resin curing agent (B).

(4) A copper-clad laminate in which copper foil is laminated on one or both sides of a composite material obtained by impregnating and curing the epoxy resin composition described in (1) above into a fiber base material.

(5) In a method of manufacturing a copper-clad laminate by impregnating a fiber base material with the epoxy resin composition described in (1) above, laminating copper foil on one or both sides and curing, during curing,
Additive (C) in the epoxy resin composition by light irradiation
A method for producing a copper-clad laminate, which comprises reacting a resin base material (A) with an epoxy resin curing agent (B) and curing the resin.

The resin base material (A) used in the present invention has the general formula [1
] (where n is 0 to 10, R1 and R2 are glycidyl groups, and A1 to A8 are hydrogen atoms or bromine atoms).

This bisphenol-based epoxy resin has the general formula [1
] may be a bisphenol A type epoxy resin in which A1 to A6 are hydrogen atoms, or a brominated epoxy resin in which at least one of A1 to All is a bromine atom and the rest are hydrogen atoms. Brominated epoxy resins are selected when flame retardancy is required. Such bisphenol-based epoxy resin is a bisphenol A-based epoxy resin that is widely used in normal amounts.

As the bisphenol A-based epoxy resin used in the present invention, diglycidyl ether obtained by reacting bisphenol A and/or halogenated bisphenol A with epichlorohydrin can be used. In addition, commercially available products can also be used.
A” is a hydrogen atom), Ebicoat 1001 (the general formula [
1], R1 and R2 are glycidyl groups, n is about 2.0,
A1 to A'' are hydrogen atoms), Epicoat 1004 (R1 and R2 of the above general formula [1] are glycidyl groups, n is about 4
．． 4, A1 to A'' are hydrogen atoms), Epikote 5046 (
R1 and R2 in the general formula [1] are glycidyl groups, n
is about 1.4, A1 to A4 are hydrogen atoms, two of As, p, and @ are bromine atoms and the rest are hydrogen atoms), and Epicoat 5050 (R1 and R2 of the general formula (1) are glycidyl groups). , n is approximately 1.3, and A1 to A8 are bromine atoms) (all trade names, manufactured by Yuka Shell Epoxy Co., Ltd.). These bisphenol A-based epoxy resins may be used alone or in combination.

As the resin base (A), a non-bisphenol A epoxy resin may be mixed with the bisphenol A epoxy resin to the extent that the object of the present invention is not impaired.

The epoxy resin curing agent (B) used in the present invention is bisphenol A represented by the general formula [1] (where n is 0, R1 and R2 are hydrogen atoms, and A1 to A4 are hydrogen atoms or bromine atoms). or its bromide (b2)
, or bisphenol A or its brominated compound represented by the general formula [1] (where n is 0°, R1 and R2 are hydrogen atoms, and A1 to A4 are hydrogen atoms or bromine atoms) is any of A1 to A4. It is a novolak resin (b2) of bisphenol A or its brominated product in which two or more molecules are bonded by methylene groups at positions.

The epoxy resin curing agent (B) has bisphenol A as its skeleton, similar to the epoxy resin as the resin base (A).
It is characterized by having a molded skeleton, which gives it toughness and heat resistance. If further heat resistance is required, bisphenol A or its brominated novolak resin is selected.

The epoxy resin curing agent (B) used in the present invention is 2,2-bis(4-hydroxyphenyl)prono(n) (R1 and R2 of the above general formula [1] are hydrogen atoms, n is 0, 1 to A4 are hydrogen atoms), 2.2-bis(3,5
-dibromo-4-hydroxyphenyl)propane (R1 and R2 in the above general formula (1) are hydrogen atoms, n is O, A
'' to A4 are bromine atoms), and novolac resins containing these as phenolic components (two or more molecules bonded by a methylene group at any position of A1 to A4 in the general formula [1]).

The additive (C) used in the present invention has the above general formula [1]
(However, n is 0 to 10, R1 and R2 are ester groups, and A1 to A' are hydrogen atoms).

In the present invention, the additive (C) is also the resin base material (A).
And, like the epoxy resin curing agent (B), it is characterized by having a bisphenol A type skeleton. In other words, the bisphenol A type skeleton of the additive (C) not only imparts toughness and heat resistance similarly to the bisphenol A-based epoxy resin base resin (A) and the epoxy resin curing agent (B), but also imparts toughness and heat resistance to the epoxy acrylate resin. Adhesive strength, solvent resistance, chemical resistance, and bending strength are greatly improved by the action of .

Since the epoxy acrylate resin used as the additive (C) is a polymer with a high molecular weight, it is very difficult to mix it uniformly with other ordinary resins, curing agents, etc., but in the present invention, Since the basic molecular structures of the resin base (A), epoxy resin curing agent (B), and additive (C) are the same, these three components are sufficiently mixed without causing microscopic layer separation. Therefore, by adding such an additive (C), adhesive strength, bending strength,
Solvent resistance and chemical resistance are significantly improved.

As the additive (C) used in the present invention, commercially available products can also be used, such as RIPOXY VR-60 (where R1 and R2 in the general formula [1] are the acrylic ester groups,
n is approximately 5, A1 to A'' are hydrogen atoms), RIPOXY V
R-90 (R1 and R2 in the general formula [1] are the acrylic acid ester groups, n is about 2, and A1 to 80 are hydrogen atoms) (both manufactured by Showa Kobunshi Co., Ltd., product name), etc. can give.

The greatest feature of the epoxy resin composition of the present invention is that the resin base (A), epoxy resin curing agent (B), and additive (C) all have the same bisphenol A type skeleton. There is. In other words, the epoxy resin base agent (
Since the basic molecular structures of the three components A), epoxy resin curing agent (B), and additive (C) are the same, they mix at the molecular level and do not cause microscopic layer separation. In the case of an epoxy resin composition using components that do not have the same basic molecular structure, a strong epoxy resin composition with high heat resistance and adhesion strength, excellent chemical resistance, and high bending strength can be obtained. It becomes very difficult to mix uniformly, and even if a uniformly dissolved resin composition is achieved by sufficient mechanical stirring, microscopic layer separation will occur during long periods of standing or during prepreg production. As a result, heat resistance may be reduced, or adhesion, chemical resistance, etc. may not be sufficiently improved.

A catalyst can be used in the epoxy resin composition of the present invention in the same manner as in ordinary epoxy resins. Suitably used catalysts include 2-methylimidazole and 2-ethyl-
Imidazole compounds such as 4-methylimidazole, ■-benzy-2-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-heptadecyl imidazole, tetraethylamine, benzyldimethylamine, 2,4゜6-tris(dimethyl Examples include tertiary amine compounds such as (aminomethyl) phenol, dicyandiamide and its derivatives, and BF, -monoethylamine.

Additive (C) as a curing catalyst for epoxy acrylate resins includes catalysts commonly used in vinyl polymerization, such as tertiary-butyl peroxybenzoate, methyl ethyl ketone peroxide, cyclohexanone peroxide, benzoyl peroxide, and cumene hydroperoxide. Peroxides such as , lauryl peroxide, and digmyl peroxide are preferably used. Further, when curing is performed using light such as ultraviolet rays, commonly used sensitizers such as benzoin alkyl ethers, anthraquinones, benzophenones, and xanthones can be used.

Moreover, solvents used for ordinary epoxy resins can be used in the epoxy resin composition of the present invention. For example, alcohols such as ethyl alcohol, propyl alcohol, and butyl alcohol, aromatic hydrocarbons such as benzene, toluene, and xylene, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, ethylene glycol monomethyl ether, and ethylene glycol monomethyl ether. Solvents such as ethers of ethylene glycol and diethylene glycol, such as ethyl ether, diethylene glycol 7-methyl ether, and ethylene glycol monoethyl ether acetate, and their acetate esters are preferably used, but N,N-dimethylformamide, N,N-dimethylacetamide, etc. Polar solvents such as amides such as N-methylpyrrolidone and dimethyl sulfoxide can also be used. These solvents may be used alone or in combination of two or more.

Furthermore, the epoxy resin composition of the present invention may contain other additives such as fillers, dyes, pigments, etc., which are commonly used in epoxy resins.

The resin base (A) in the epoxy resin composition of the present invention.

The respective compounding ratios of the epoxy resin curing agent (B) and the additive (C) are not particularly limited, but the phenol equivalent of (B) is 0.7 to 1.2 with respect to the epoxy equivalent of (A).
A proportion that is equivalent is preferable in view of the properties of the cured product. Also, (C) is 0.1% by weight relative to (A) + (B)
A range of 20% is preferred. That is, if heat resistance is important, the amount of (C) should be small, and if adhesiveness, toughness, and chemical resistance are important, it is preferable to mix a large amount of (C).

The epoxy resin composition of the present invention includes (A), (B) and (
It is manufactured by mixing each component of C) and other added components.

The epoxy resin composition of the present invention thus obtained can be used as it is in the same way as conventional epoxy resins, but the epoxy resin composition of the present invention can also be used as an additive in other epoxy resins. It can also be added to improve the properties of the epoxy resin after addition. However, in that case, the epoxy resin composition of the present invention as an additive needs to be used in an amount of at least 10 parts by weight or more based on the epoxy resin and curing agent components to be added.

If it is less than 10 parts by weight, the desired adhesion strength 1 toughness,
No significant effect was observed in improving chemical resistance, etc.

The epoxy resin composition of the present invention can be used in the same fields as conventional epoxy resins, but it has excellent heat resistance, adhesiveness, flexibility, chemical resistance, bending strength, etc.
It is suitably used in fields where such characteristics are required.

The cured epoxy resin of the present invention is obtained by curing the epoxy resin composition. The cured epoxy resin can be produced by heating in the same way as conventional epoxy resins, or the additive (C) alone can be photocured by reacting in advance by irradiation with ultraviolet rays, etc., and then the main resin can be produced by heating. (A) and epoxy resin curing agent (B)
) can also be produced by a two-step curing method of curing by reacting.

The cured epoxy resin product obtained by the above two-step curing method is an IPN in which the network of the epoxy acrylate resin, which is the additive (C), and the network of the epoxy resin are entangled with each other.
(Interpenetrating Polymer
To form a network (interpenetrating network) structure,
Characteristics improve. Such improvements in properties are achieved through the formation of compatibility and entanglement at the molecular level, and cannot be achieved through a simple blend.

The copper-clad laminate of the present invention includes impregnating the epoxy resin composition into a fiber base material such as glass cloth, glass mat, or aramid cloth.
Copper foil is laminated on one or both sides of a cured composite material.

Such a copper-clad laminate can be manufactured by the same method as a normal epoxy resin copper-clad laminate, or can be manufactured by employing the two-step curing method described above.

That is, the resin composition of the present invention can be directly impregnated into a fiber base material such as glass cloth, glass mat, or aramid cloth without a solvent, or it can be temporarily dissolved in a solvent to form a varnish, and this can be impregnated into the fiber base material. After that, only the solvent is removed to form a so-called prepreg, and then copper foil is laminated on one or both sides of the prepreg, and the resin is cured by heating, pressurizing, etc. to produce the prepreg. In addition, in order to manufacture a copper-clad laminate using the two-step curing method, a prepreg is obtained in the same manner as described above, copper foil is laminated on one or both sides of the prepreg, and additives ( After reacting C), the resin base material (A) and the epoxy resin curing agent (B) are reacted with each other by heating, pressure, etc., and the resin is cured.

The copper-clad laminate thus obtained has high adhesion strength between the copper foil and the composite material at high temperatures, excellent solvent resistance and chemical resistance, and high bending strength and toughness.

Such a copper-clad laminate can be used as a substrate for printed wiring boards and the like.

〔Example〕

Next, the present invention will be specifically explained using examples.

Example 1 Epicoat 828 (manufactured by Yuka Shell Epoxy Co., Ltd., epoxy equivalent: 180-190, trade name) was used as the resin base (A), and 2,
2-bis(4-hydroxyphenyl)propane novolak (phenol equivalent: 150) was converted into a phenol equivalent/epoxy equivalent ratio (hereinafter referred to as PE/EE ratio) of 0.85.
RIPOXY VR-60 (manufactured by Showa Kobunshi Co., Ltd., trade name) was added as an additive (C) to the above-mentioned resin base (A) and an epoxy resin curing agent (B).
Furthermore, 2-ethyl-4-methylimidazole was blended as a catalyst in an amount of 0.1% by weight based on the resin base resin (A) and the epoxy resin curing agent (B), and tert-butyl was further blended as a catalyst. A varnish containing 1.0% by weight of peroxybenzoate based on the additive (C) was dissolved in methyl ethyl ketone to a solid content of 50%.

This was impregnated into a glass woven fabric having a thickness of 0.18 cm and dried to obtain a prepreg with a resin content of 50% by weight. Four sheets of this prepreg were stacked and press-molded with 35-inch copper foil interposed on both sides. The molding conditions are press temperature 180℃, B L/X
The pressure was 40 kg/aJ and the bath time was 90 minutes. Table 1 shows the evaluation results regarding the characteristics of this copper-clad laminate.

Example 2 Copper was prepared in the same manner as in Example 1, except that Epicoat 5046 (manufactured by Yuka Shell Epoxy Co., Ltd., epoxy equivalent: 480, trade name) was used as the resin base (A), and benzyldimethylamine was used as the catalyst. Table 1 shows the evaluation results regarding the properties of the tensioned laminates obtained.

Example 3 Epicoat 1001 (manufactured by Yuka Shell Epoxy Co., Ltd., epoxy equivalent: 450-500, trade name) was used as the resin base (A), the PE/EE ratio was 0.95, and the additive (C)
RIPOXY VR-90 (manufactured by Showa Kobunshi Co., Ltd., trade name) was used in an amount of 5% by weight, and benzoin methyl ether was used as a photosensitizer for the additive at a ratio of 2.
A copper-clad laminate was obtained in the same manner as in Example 1 except that 0% by weight was added. Table 1 shows the evaluation results regarding the characteristics.

Example 4 Non-bisphenol A polyfunctional epoxy resin TACTIX-742 (manufactured by Dow Chemical Company, epoxy equivalent weight 162, trade name) and Epicoat 5046 were used as the resin base (A).
(manufactured by Yuka Shell Epoxy Co., Ltd., epoxy equivalent: 460~
490 (trade name) in a weight ratio of 1:1, and 2,2-bis(4-hydroxyphenyl)propane novolak (phenol equivalent: 180) was used as the epoxy resin curing agent (B). Additive (C) R
IPOXY VR-60 (2) manufactured by Hwa Kobunshi Co., Ltd., trade name) was added to the resin base (A) and the epoxy resin curing agent (B).
), and 0.15% by weight of 2-phenylimidazole as a catalyst was added to the base resin (A) and epoxy resin curing agent (B), and further as a catalyst for the additive (C). A varnish was obtained by dissolving dicumyl peroxide in an amount of 1.0% by weight based on the additive (C) in acetone to a solid content of 55%.

This thickness is 0. A prepreg with a resin content of 48% was obtained by impregnating ILw glass woven fabric and drying it. Four sheets of this prepreg were stacked and press-molded with 35 layers of copper foil interposed on both sides. The molding conditions were a press temperature of 180° C., a press pressure of 40 kg/J, and a press time of 100 minutes. Table 1 shows the evaluation results regarding the characteristics of this copper-clad laminate.

Comparative Example 1 Example except that no bisphenol A-based epoxy resin was used and only non-bisphenol A-based polyfunctional epoxy resin EPPN-502 (manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 160-180, trade name) was used. A copper-clad laminate was obtained in the same manner as in 4. However, this laminate had a cloudy appearance compared to Examples 1 to 4. This is probably due to layer separation of the additive (C) during prepreg production. Table 1 shows the evaluation results regarding the characteristics.

Comparative Example 2 A copper-clad laminate was obtained in the same manner as in Example 4, except that 20 parts by weight of diaminodiphenylsulfone was added as the epoxy resin curing agent (B) to 100 parts by weight of the resin base (A). However, this laminate had a cloudy appearance compared to Examples 1 to 4. Table 1 shows the evaluation results regarding the characteristics.

Comparative Example 3 A copper-clad laminate was obtained in the same manner as in Example 4 except that the additive (C) was omitted. Although the appearance of this laminate was as good as Examples 1 to 4, it was inferior in copper foil adhesive strength and the like. Table 1 shows the evaluation results regarding the characteristics.

As shown in the above examples, the epoxy resin composition of the present invention and the copper-clad laminate obtained therefrom contain a resin base (A), an epoxy resin curing agent (B), and an additive (C).
Because each of these materials has a bisphenol A type skeleton, they are mixed at the molecular level and have heat resistance, adhesion, chemical resistance, and bending strength.

〔Effect of the invention〕

As described above, according to the present invention, the resin base material (A).

Both the epoxy resin curing agent (B) and the additive (C) have a bisphenol A type skeleton, so they have excellent heat resistance and adhesive properties, and are therefore effective against copper at high temperatures. A tough epoxy resin composition with high adhesion strength between the foil and resin, excellent flexibility and chemical resistance, and high bending strength can be obtained.

Further, according to the present invention, a tough epoxy resin cured product having excellent heat resistance, adhesion, flexibility, and chemical resistance and high bending strength can be obtained.

Furthermore, according to the present invention, by using the above-mentioned epoxy resin composition, a strong copper-clad laminate with high adhesion strength between the copper foil and the composite material at high temperatures, excellent chemical resistance, and high bending strength can be produced. is obtained.

Claims (5)

[Claims] (1) (A) As the main resin, the following general formula [1] (where n is 0 to 10, R^1 and R^2 are glycidyl groups, and A^1 to A^8 are hydrogen atoms or bromine atoms) A bisphenol A-based epoxy resin represented by (B) an epoxy resin curing agent, (b1) the following general formula [1] (where n is 0, R^1 and R^2 are hydrogen atoms, A^1~ A^4 is a hydrogen atom or a bromine atom), or (b2) the following general formula [1] (where n is 0, R^1 and R^2 are a hydrogen atom, A^ Bisphenol A or its brominated product, in which two or more molecules of bisphenol A or its brominated product, represented by 1 to A^4 are hydrogen atoms or bromine atoms, are bonded via methylene groups at any of the positions of A^1 to A^4 and (C) as an additive, acrylic acid represented by the following general formula [1] (where n is 0 to 10, and R^1 and R^2 are ▲ mathematical formulas, chemical formulas, tables, etc. ▼ An epoxy acrylate resin represented by an ester group and A^1 to A^8 are hydrogen atoms). ▲There are mathematical formulas, chemical formulas, tables, etc.▼ ・・・[1] (2) (A) As the main resin, the following general formula [1] (where n is 0 to 10, R^1 and R^2 are glycidyl groups, and A^1 to A^8 are hydrogen atoms or bromine atoms) A bisphenol A-based epoxy resin represented by (B) an epoxy resin curing agent, (b1) the following general formula [1] (where n is 0, R^1 and R^2 are hydrogen atoms, A^1~ A^4 is a hydrogen atom or a bromine atom), or (b2) the following general formula [1] (where n is 0, R^1 and R^2 are a hydrogen atom, A^ Bisphenol A or its brominated product, in which two or more molecules of bisphenol A or its brominated product, represented by 1 to A^4 are hydrogen atoms or bromine atoms, are bonded via methylene groups at any of the positions of A^1 to A^4 and (C) as an additive, acrylic acid represented by the following general formula [1] (where n is 0 to 10, and R^1 and R^2 are ▲ mathematical formulas, chemical formulas, tables, etc. ▼ An epoxy resin cured product characterized by curing an epoxy resin composition containing an epoxy acrylate resin represented by an ester group (A^1 to A^8 are hydrogen atoms). ▲There are mathematical formulas, chemical formulas, tables, etc.▼ ・・・[1] (3) (A) As the main resin, the following general formula [1] (where n is 0 to 10, R^1 and R^2 are glycidyl groups, and A^1 to A^8 are hydrogen atoms or bromine atoms) A bisphenol A-based epoxy resin represented by (B) an epoxy resin curing agent, (b1) the following general formula [1] (where n is 0, R^1 and R^2 are hydrogen atoms, A^1~ A^4 is a hydrogen atom or a bromine atom), or (b2) the following general formula [1] (where n is 0, R^1 and R^2 are a hydrogen atom, A^ Bisphenol A or its brominated product, in which two or more molecules of bisphenol A or its brominated product, represented by 1 to A^4 are hydrogen atoms or bromine atoms, are bonded via methylene groups at any of the positions of A^1 to A^4 and (C) as an additive, acrylic acid represented by the following general formula [1] (where n is 0 to 10, and R^1 and R^2 are ▲ mathematical formulas, chemical formulas, tables, etc. ▼ An epoxy resin composition containing an epoxy acrylate resin represented by an ester group (A^1 to A^8 are hydrogen atoms) is reacted with the additive (C) by light irradiation, and then the resin base material (A) An epoxy resin cured product characterized by being cured by reacting with an epoxy resin curing agent (B). ▲There are mathematical formulas, chemical formulas, tables, etc.▼ ・・・[1] (4) A copper-clad laminate, characterized in that copper foil is laminated on one or both sides of a composite material obtained by impregnating and curing the epoxy resin composition according to claim (1) into a fiber base material. (5) A method for manufacturing a copper-clad laminate by impregnating a fiber base material with the epoxy resin composition according to claim (1), laminating copper foil on one or both sides, and curing the epoxy resin composition. , the additive (C) in the epoxy resin composition is removed by light irradiation.
), and then reacting and curing the resin base material (A) and the epoxy resin curing agent (B).