JPH107768A - Epoxy resin composition, prepreg and laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an epoxy resin composition which is a prepreg capable of obtaining a laminate having excellent performance in a short time of molding and capable of obtaining a prepreg having excellent storage stability. . A prepreg manufactured using the epoxy resin composition is provided. A laminate manufactured using the prepreg is provided. SOLUTION: In an epoxy resin composition containing an epoxy resin having two or more epoxy groups in one molecule, an amine-based curing agent, and a curing accelerator, the melting point of the curing accelerator is 145 to 190 ° C. It is characterized by containing an imidazole compound. Further, it is characterized by containing dicyandiamide as an amine-based curing agent. A prepreg obtained by impregnating a base material with the epoxy resin composition and semi-curing. A laminate obtained by laminating and curing the prepreg.

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 used for manufacturing a laminated board, a prepreg using the epoxy resin composition, and a laminated board using the prepreg.

[0002]

2. Description of the Related Art As a material for printed wiring boards, prepregs and laminates using an epoxy resin composition are widely used. Conventionally, an epoxy resin composition used for this purpose generally contains an epoxy resin having two or more epoxy groups in one molecule, an amine-based curing agent, and a curing accelerator. In recent years, in order to meet the demand for cost reduction, even if the molding cycle at the time of molding the prepreg is shortened, the performance such as the heat resistance of the obtained laminate can be secured, and the storage stability of the prepreg is not impaired There is a need for a resin composition. However, the property that the laminate performance can be ensured by short-time molding and the property that the storage stability of the prepreg is excellent are usually contradictory properties. Therefore, it is a satisfactory level to make these two properties compatible. It has not been reached yet.

[0003]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and it is an object of the present invention to provide a laminate having excellent performance in a short period of time. A prepreg, and providing an epoxy resin composition capable of obtaining a prepreg having excellent storage stability, and providing a prepreg manufactured using the epoxy resin composition, and using the prepreg. It is to provide a manufactured laminated board.

[0004]

The epoxy resin composition according to claim 1 of the present invention contains an epoxy resin having two or more epoxy groups in one molecule, an amine-based curing agent, and a curing accelerator. The epoxy resin composition described above is characterized by containing an imidazole compound having a melting point of 145 to 190 ° C. as a curing accelerator.

[0005] The epoxy resin composition of claim 2 according to the present invention is characterized in that, in the epoxy resin composition of claim 1, dicyandiamide is contained as an amine-based curing agent.

The epoxy resin composition according to claim 3 of the present invention is the epoxy resin composition according to claim 1 or 2, wherein the imidazole compound is 2-phenyl-4-methyl represented by the following formula (1): It is characterized by containing imidazole or 2,4-diamino-6- [2-undecylimidazolyl (1)]-ethyl S-triazine represented by the following formula (2).

[0007]

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[0008]

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A prepreg according to a fourth aspect of the present invention is a prepreg obtained by impregnating a substrate with the epoxy resin composition according to any one of the first to third aspects and semi-curing the same.

A laminate according to a fifth aspect of the present invention is a laminate obtained by laminating and curing the prepreg according to the fourth aspect.

In the present invention, the curing accelerator has a melting point of 145.
The use of an imidazole compound having a temperature of up to 190 ° C. has a function of obtaining an epoxy resin composition having low reactivity at room temperature and not impairing the reaction activity at a molding temperature.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The epoxy resin in the present invention comprises:
An epoxy resin having two or more epoxy groups in one molecule, such as a bisphenol A type epoxy resin and a halogenated bisphenol A type epoxy resin. Two or more types may be used in combination. It is preferable to use a brominated epoxy resin such as a tetrabromobisphenol A type epoxy resin as the epoxy resin because the finally obtained laminate has flame retardancy.

The amine curing agent in the present invention includes:
Examples thereof include aromatic diamines such as dicyandiamide and diaminodiphenylmethane, and two or more kinds may be used in combination.
It is preferable to use dicyandiamide as the amine-based curing agent because the storage stability of the prepreg becomes better.

In the present invention, it is important that the epoxy resin composition contains an imidazole compound having a melting point of 145 to 190 ° C. as a curing accelerator. This is because, when an imidazole compound having a melting point of less than 145 ° C. or a melting point of more than 190 ° C. is used, a property that the lamination performance can be ensured in a short period of time and a property that the storage stability of the prepreg is excellent. This is because it is difficult to use an imidazole compound having a melting point within the above range, so that these two properties can be achieved at the same time. The imidazole compound having a melting point of 145 to 190 ° C is not particularly limited,
2-phenyl-4-methylimidazole represented by the formula (1) and 2,4-diamino-6- represented by the formula (2)
[2-Undecylimidazolyl (1)]-ethyl S-triazine and the like can be exemplified. And the melting point is 145
The content ratio of the imidazole compound at 190 ° C. in the epoxy resin composition is not particularly limited, but in order to sufficiently achieve the object of the present invention, an epoxy resin, an amine-based curing agent and a curing accelerator are used. For the total amount,
It is preferably 0.01 to 0.5% by weight. In the epoxy resin composition according to the present invention, if necessary,
It is possible to add solvents, fillers and the like.

The prepreg according to the present invention is a prepreg obtained by impregnating a base material such as a glass cloth or a nonwoven fabric with the epoxy resin composition and semi-curing the prepreg. There is no.

The laminate according to the present invention is a laminate obtained by laminating the above prepreg alone or together with a metal foil such as a copper foil or various films and curing the same. In addition,
A laminate obtained by simply molding only one prepreg may be used. There is no particular limitation on the method for producing the laminate of the present invention, and the laminate can be produced by various methods.

[0017]

The present invention will be described below based on examples and comparative examples.

In each of Examples and Comparative Examples, as shown in Tables 1 and 2, respective raw materials were blended and mixed to prepare a varnish as an epoxy resin composition. The amount of each raw material is parts by weight, and details of each raw material shown in Tables 1 and 2 are shown below. Aromatic diamine: 4,4'-diamino-2,2 ', 3,3'tetrachlorodiphenylmethane (amine value 84) Curing accelerator 1: 2-phenyl-4-methylimidazole Curing accelerator 2: 2,4- Diamino-6- [2-undecylimidazolyl (1)]-ethyl S-triazine curing accelerator 3: trade name of Shikoku Chemicals Co., Ltd. 2E4MZ-C
NS curing accelerator 4: 2-ethyl-4-methylimidazole curing accelerator 5: 2-methylimidazole

The varnish prepared as above has a thickness of 0.2 mm.
Was impregnated, heated and semi-cured to prepare a prepreg. The storage stability of the obtained prepreg was tested by the following test methods, and the obtained results are shown in Tables 1 and 2.

Test method for storage stability of prepreg: The melt viscosity of the resin component which has fallen off from the prepreg and is separated is measured using a constant load extrusion type capillary rheometer (manufactured by Shimadzu Corporation, flow tester). The melt viscosity at the time of preparing the prepreg and the melt viscosity after storing the prepreg at 40 ° C. for 7 days were measured, and the change rate of the melt viscosity (= melt viscosity after storing for 7 days / melt viscosity at the time of preparing the prepreg).
Ask for.

Next, eight prepregs obtained above were stacked, and further, copper foils were arranged on both outer sides of the prepregs.
C. for 40 minutes to obtain a double-sided copper-clad laminate. In addition,
Since the conventional general molding time is about 60 minutes, the condition of molding for 40 minutes is a condition for completing the molding in an extremely short time. The resulting double-sided copper-clad laminate was evaluated for PCT solder heat resistance and glass transition temperature, and the obtained results are shown in Tables 1 and 2. In addition, each test method was performed by the method shown below.

Test method for PCT solder heat resistance: A test piece of 50 mm × 50 mm was prepared by removing a copper foil by etching, and the test piece was treated in saturated steam at 121 ° C. for 2 hours. Immerse for 30 seconds and visually inspect the test piece for any abnormalities such as blisters.
If there is an abnormality, it is displayed as x. This test is performed on five test pieces.

Measurement Method of Glass Transition Temperature A test piece of 5 mm × 50 mm was prepared by removing the copper foil by etching, and the dynamic viscoelasticity of the test piece was measured at a heating rate of 2 ° C./min and a vibration frequency of 10 Hz. The test is performed, and the peak temperature of the obtained tan δ temperature dispersion curve is defined as the glass transition temperature.

[0024]

[Table 1]

[0025]

[Table 2]

From the results shown in Tables 1 and 2, each Example of the present invention has better storage stability of the prepreg than Comparative Example, and the evaluation results of the PCT solder heat resistance and the glass transition temperature are equivalent. Or it was confirmed that it was equivalent or more.

[0027]

According to the epoxy resin composition of the present invention, an imidazole compound having a melting point of 145 to 190 ° C. is used as a curing accelerator. It is possible to obtain a prepreg capable of obtaining a laminated plate having excellent performance and excellent storage stability. Further, since the prepreg of the present invention is produced using the epoxy resin composition of the present invention, a laminate having excellent performance can be obtained in a short period of time, and a prepreg having excellent storage stability. Become. In addition, since the laminated board of the present invention is manufactured using the prepreg of the present invention, even if the molding time is reduced, the laminated board performance is sufficiently ensured, so that the printed wiring is Useful as a material for boards.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification number Agency reference number FI Technical indication location C08L 63:00 (72) Inventor Tatsuya Watanabe 1048 Odakadoma, Kadoma-shi, Osaka Matsushita Electric Works, Ltd.

Claims (5)

[Claims] 1. An epoxy resin composition containing an epoxy resin having two or more epoxy groups in one molecule, an amine-based curing agent and a curing accelerator, having a melting point of 145 to 190 ° C. as a curing accelerator. An epoxy resin composition comprising a certain imidazole compound. 2. The epoxy resin composition according to claim 1, further comprising dicyandiamide as an amine curing agent. 3. An imidazole compound represented by the following formula (1):
2-phenyl-4-methylimidazole represented by the following formula or 2,4-diamino-6- [2-undecylimidazolyl (1)]-ethyl S-triazine represented by the following formula (2): The epoxy resin composition according to claim 1, wherein the composition is an epoxy resin composition. Embedded image Embedded image 4. A prepreg obtained by impregnating a substrate with the epoxy resin composition according to claim 1 and semi-curing the substrate. 5. A laminate obtained by laminating and curing the prepreg according to claim 4.