JP2000302843A - Epoxy resin composition and insulating substrate using the composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a composition which can complete its curing reaction at a low temperature for a short time to raise the production efficiency while keeping the glass transition temperature and the linear expansion coefficient by blending a polyphenylene ether, a curing agent, a curing promoter and an epoxy resin having a naphthalene skeleton as its essential components. SOLUTION: An epoxy resin having a naphthalene skeleton to be used is, for example, a compound of formulas I and II, i.e., a 1-naphthol type epoxy resin, a 2-naphthol type epoxy resin, a 1,2-dihydroxy naphthalene type epoxy resin or the like. Its content is 20-50 wt.% of the whole epoxy resin. A polyphenylene ether to be used is, for example, the one having at least one hydroxy group on the terminal and a molecular weight of not more than 10,000. A curing agent to be used is tetrahydrophthalic anhydride or the like. A curing promoter to be used is octanoic acid or the like.

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 an insulating substrate using the epoxy resin composition. More specifically, the present invention relates to an epoxy resin composition used for an electronic material such as a printed wiring board. It is about.

[0002]

2. Description of the Related Art With the miniaturization and multifunctionality of electronic devices due to the high integration of semiconductors and electronic components, with the aim of realizing high-density wiring and high-density mounting for laminated boards and printed wiring boards, etc. As a material of an insulating substrate corresponding to a high multilayer, for example,
As disclosed in JP-A-9-291148, an epoxy resin composition such as a modified polyphenylene ether (also referred to as a modified PPO) obtained by heating and melting polyphenylene ether and novolak phenol and modifying the terminal with novolak phenol. Is being adopted.

As this epoxy resin composition, a substrate is impregnated. The above-mentioned insulating substrate used in the field of information and communication is being used in a large amount and is produced in large quantities. In particular, it has been required to cure at a low temperature in order to complete the curing in a short time and improve production efficiency.

[0004]

However, such an epoxy resin composition and an insulating substrate using the epoxy resin composition require a low glass transition temperature to complete the curing in a short time at a low temperature. (Generally, T
It is represented by g. ) And the coefficient of linear expansion deteriorate, and it is inevitable that curing must be performed at a certain high temperature and for a certain long time.

The present invention has been made in view of the above-mentioned facts, and an object of the present invention is to cure at a low temperature and in a short time while maintaining the physical properties of the glass transition temperature and the coefficient of linear expansion. An object of the present invention is to provide an epoxy resin composition that can be completed to improve production efficiency and an insulating substrate using the epoxy resin composition.

[0006]

The epoxy resin composition according to claim 1 of the present invention is characterized by containing a polyphenylene ether, a curing agent, a curing accelerator, and an epoxy resin having a naphthalene skeleton as essential components. And

The epoxy resin composition according to claim 2 of the present invention is characterized in that the epoxy resin having a naphthalene skeleton is represented by the following formula [I].

[0008]

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An epoxy resin composition according to a third aspect of the present invention is characterized in that the epoxy resin having a naphthalene skeleton is represented by the following formula [II].

[0010]

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The epoxy resin composition according to claim 4 of the present invention is characterized in that the epoxy resin having a naphthalene skeleton is a mixture of the one represented by the above formula [I] and the one represented by the above formula [II]. Features.

An epoxy resin composition according to a fifth aspect of the present invention is characterized in that the epoxy resin having a naphthalene skeleton is blended in an amount of 20 to 50% by weight based on the total amount of the epoxy resin.

The epoxy resin composition according to claim 6 of the present invention contains, in place of the polyphenylene ether, a modified polyphenylene ether obtained by heating and melting the polyphenylene ether and novolak phenol and modifying the novolak phenol at the end. It is characterized by making it.

An epoxy resin composition according to claim 7 of the present invention is that the modified polyphenylene ether is obtained by heating and melting the polyphenylene ether and the novolak phenol, and then blending a radical initiator. It is characterized by.

In the epoxy resin composition according to claim 8 of the present invention, the radical initiator is benzoyl peroxide, azoisobutyronitrile, cumene hydroperoxide, t-
It is characterized by being at least one member selected from the group consisting of butyl hydroperoxide and dicumyl peroxide.

An insulating substrate using the epoxy resin composition according to claim 9 of the present invention is obtained by impregnating a glass substrate with the epoxy resin composition according to any one of claims 1 to 8 and curing the glass substrate. It is characterized by.

[0017]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, embodiments of the present invention will be described in detail.

The epoxy resin composition according to the present invention contains a polyphenylene ether, a curing agent, a curing accelerator, and an epoxy resin having a naphthalene skeleton as essential components.

The above-mentioned polyphenylene ether is referred to as PPO, and various polyphenylene ethers can be used without any particular limitation. For example, a polyphenylene ether having at least one hydroxyl group at a terminal and having a molecular weight of 10,000 or less is preferable because of good flowability and high reactivity with an epoxy resin. In order to obtain a low-molecular-weight product from commercially available polyphenylene ether, a phenol such as bisphenol A and a peroxide may be used as an initiator and heated in a solvent such as toluene. A product having a low molecular weight can be obtained.

The curing agent is selected from, for example, polyamines, acid anhydrides, polyphenols, polymercaptans, anionic polymerization type catalysts, cationic polymerization type catalysts, latent types and the like. Used alone or in combination of two or more.

Particularly, the acid anhydrides include tetrahydrophthalic anhydride, methylhexahydrophthalic anhydride,
At least one selected from the group of methylhymic anhydrides
It is preferably a species. By mixing these, the unreacted material in the cured product is reduced, so that when the cured product is heated, the volatile components are reduced, and a cured product having excellent heat resistance and adhesion can be produced. is there.

Examples of the curing accelerator include organic acids such as octanoic acid, stearic acid, acetylacetonate, naphthenic acid and salicylic acid and metal salts such as Zn and Cu.
Tertiary amines such as triethylamine and triethanolamine, and imidazoles such as 2-ethyl-4-imidazole and 4-methylimidazole are effective. These may be used alone or in combination of two or more.

As the above imidazole compound, mainly,
It is thought to contribute to the reaction between the epoxy resin and the polyphenylene ether.

In the present invention, in addition to the above essential components,
Depending on the use, fillers and additives may be added in an amount that does not impair the original properties for the purpose of imparting desired performance.

For example, examples of the filler include carbon black, silica, alumina, barium titanate, talc, mica, glass beads, glass hollow spheres, and the like.

The additives include, for example, antioxidants, heat stabilizers, antistatic agents, plasticizers, pigments, dyes,
Colorants and the like can be mentioned.

As the epoxy resin having a naphthalene skeleton, various ones can be adopted. For example, 1-naphthol type epoxy resin, 2-naphthol type epoxy resin, 1,2-dihydroxynaphthalene type epoxy resin can be used. Epoxy resins, 1,3-dihydroxynaphthalene-type epoxy resins, and the like, and naphthalene-type epoxy resins having an alkyl group, an allyl group, an alkoxy group, or a halogen-substituted form thereof, may be used alone, or may be used alone. Any of the above may be used in combination.

Other epoxy resins that can be used in combination with the epoxy resin having a naphthalene skeleton of the present invention include:
For example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, alicyclic epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, biphenyl type epoxy resin, and brominated epoxy resin thereof May be used alone or in combination of two or more.

The epoxy resin composition of the present invention can be used as a prepreg by impregnating a glass substrate in a suitable solvent, and further, after drying using the prepreg, It can be used as an insulating substrate such as a laminated board or a printed wiring board by being cured by heating.

An insulating substrate using the epoxy resin composition, such as a laminated board or a printed wiring board, completes curing at a low temperature and in a short time while maintaining the physical properties of the glass transition temperature and the coefficient of linear expansion. As a result, the production efficiency can be improved.

According to the present invention, the epoxy resin composition contains an epoxy resin having a low-viscosity naphthalene skeleton, and imparts low viscosity and workability to the obtained epoxy resin composition. In addition, the other essential components, polyphenylene ether, a curing agent, and a curing accelerator make it possible for the resulting epoxy resin composition to maintain physical properties such as a glass transition temperature and a linear expansion coefficient. In addition, the curing can be completed in a short time and the production efficiency can be surely improved.

In particular, when the epoxy resin having a naphthalene skeleton is represented by the following formula [I], an epoxy resin composition obtained from the epoxy resin having a naphthalene skeleton represented by the following formula [I] Low-viscosity and workability more reliably, while maintaining the glass transition temperature and the coefficient of linear expansion properties more reliably, complete curing at low temperature and in a short time, and improve production efficiency. It can be more reliably improved.

[0033]

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Similarly, if the epoxy resin having a naphthalene skeleton is represented by the following formula [II], the epoxy resin composition obtained by the epoxy resin having a naphthalene skeleton represented by the following formula [II] Low viscosity and short term hardening can be completed in a short period of time to improve the production efficiency while maintaining the glass transition temperature and linear expansion coefficient properties more reliably by giving low viscosity and workability to the product more reliably. It is possible to more reliably improve.

[0035]

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Further, when the epoxy resin having a naphthalene skeleton is a mixture of the one represented by the above formula [I] and the one represented by the above formula [II], the one represented by the above formula [I] and the above The epoxy resin composition having a naphthalene skeleton, which is a mixture of those represented by the formula [II], has a low viscosity and a workability that can be more reliably imparted to the epoxy resin composition, and the physical properties of the glass transition temperature and the linear expansion coefficient , The curing can be completed at a low temperature in a short time, and the production efficiency can be more reliably improved.

The epoxy resin having a naphthalene skeleton is used in an amount of 20 to 50 w with respect to the total amount of the epoxy resin.
When t% is blended, the epoxy resin composition obtained from the epoxy resin having an appropriate amount of naphthalene skeleton can more reliably impart low viscosity and workability.
While maintaining the physical properties of the glass transition temperature and the coefficient of linear expansion more reliably, the curing can be completed at a low temperature and in a short time, and the production efficiency can be more reliably improved.

In place of the above polyphenylene ether, the polyphenylene ether and novolak phenol are heated and melted to contain a modified polyphenylene ether whose terminal is modified with novolak phenol, so that polyphenylene ether and novolak phenol are used. Can be heated and melted to react, so that the end can be surely obtained as a modified polyphenylene ether modified with novolak phenol, so that the modified polyphenylene ether and an epoxy resin having a naphthalene skeleton and a curing agent, and a curing accelerator are obtained. Epoxy resin compositions that can complete curing in a low temperature and in a short period of time and more reliably improve production efficiency while maintaining the physical properties of the glass transition temperature and the coefficient of linear expansion more reliably. Becomes

When the modified polyphenylene ether is obtained by heating and melting the polyphenylene ether and the novolak phenol, and then compounding a radical initiator, the radical initiator ensures that the polyphenylene ether is formed. The radicalized polyphenylene ether and the novolak phenol are surely reacted with each other to form the modified polyphenylene ether more reliably, so that the physical properties of the glass transition temperature and the coefficient of linear expansion can be more reliably determined. While maintaining, the curing can be completed at a low temperature and in a short time, and the production efficiency can be more reliably improved.

When the radical initiator is at least one member selected from the group consisting of benzoyl peroxide, azoisobutyronitrile, cumene hydroperoxide, t-butyl hydroperoxide and dicumyl peroxide, the radical initiator may be Thus, the polyphenylene ether is reliably radicalized, and the radicalized polyphenylene ether and novolak phenol are surely reacted with each other, so that the modified polyphenylene ether can be obtained more reliably. While maintaining the physical properties more reliably, the curing can be completed at a low temperature and in a short time, and the production efficiency can be more reliably improved.

[0041]

Embodiments of the present invention will be described below in detail.

Example 1 100 g of polyphenylene ether (manufactured by Nippon GE Plastics)
65 g (product name: ESN365, manufacturer: Nippon Steel Chemical) as an epoxy resin having a naphthalene skeleton represented by the following formula [I] (formula 7), and 125 g (product name: BREN-S, manufacturer) as a brominated bisphenol A type epoxy resin : Nippon Kayaku), as shown in (Chem. 8) below,
3 g (manufacturer: Yuka Shell) as a curing agent ethacure, as shown in the following (Chemical Formula 9), a curing accelerator 2
As an ethyl-methyl-4-imidazole, 1 g (manufacturer: Shikoku Chemicals) was blended to prepare an epoxy resin composition.

[0043]

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[0044]

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[0045]

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Example 2 As polyphenylene ether, 100 g (manufacturer: Nippon GE Plastics)
95 g of an epoxy resin having a naphthalene skeleton represented by the following formula [II] (formula 10) (product name: NC7300
L, manufacturer: Nippon Kayaku), brominated bisphenol A
95g (product name: BREN-S,
Maker: Nippon Kayaku), and 3 g (maker: Yuka Shell) as a curing agent ethacure, and 1 g (2-ethyl-4-methyl-imidazole) as a curing accelerator, as in Example 1. (Shikoku Chemicals) to prepare an epoxy resin composition.

[0047]

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Example 3 100 g of polyphenylene ether (manufactured by Nippon GE Plastics)
55 g (product name: ESN365, manufacturer: Nippon Steel Chemical Co., Ltd.) as the epoxy resin having the same naphthalene skeleton as in Example 1, and 30 g (product name: NC7300L, manufacturer: Nippon Kagaku) as the epoxy resin having the same naphthalene skeleton as in Example 2 Drug), 105 g (product name: BREN-S, manufacturer: Nippon Kayaku) as brominated bisphenol A type epoxy resin, and 3 g (maker: Yuka Shell) as ethacure of curing agent as in Example 1. ,
As a curing accelerator, 2-ethyl-4-methyl-imidazole, 1 g (manufacturer: Shikoku Chemicals) was blended to prepare an epoxy resin composition.

Example 4 100 g of polyphenylene ether (manufactured by Nippon GE Plastics)
30 g (product name: ESN365, manufacturer: Nippon Steel Chemical Co., Ltd.) as the epoxy resin having the same naphthalene skeleton as in Example 1, 55 g (product name: NC7300L, manufacturer: Nippon Kagaku) as the epoxy resin having the same naphthalene skeleton as in Example 2 Drug), 105 g (product name: BREN-S, manufacturer: Nippon Kayaku) as brominated bisphenol A type epoxy resin, and 3 g (maker: Yuka Shell) as ethacure of curing agent as in Example 1. ,
As a curing accelerator, 2-ethyl-4-methyl-imidazole, 1 g (manufacturer: Shikoku Chemicals) was blended to prepare an epoxy resin composition.

Example 5 As polyphenylene ether, 100 g (manufacturer: Nippon GE Plastics)
3.5 g of novolak phenol (product name: PSM)
6200, maker: Arakawa Chemical Co., Ltd.), this polyphenylene ether and novolak phenol were heated and melted, and then used as a radical initiator in the following (Chem. 11)
4.5 g of benzoyl peroxide as shown in (manufacturer:
Nacalai Tesque), and at room temperature, 125 g (product name: BREN-S, manufacturer: Nippon Kayaku) as a brominated bisphenol A type epoxy resin, and, as in Example 1, as a curing agent ethacure , 3 g (manufacturer: oiled shell), 2-ethyl-4- as a curing accelerator
1 g (manufacturer: Shikoku Chemicals) was added as methyl-imidazole to prepare an epoxy resin composition.

[0051]

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(Comparative Example 1) As polyphenylene ether, 100 g (manufacturer: Nippon GE Plastics)
As brominated bisphenol A type epoxy resin, 19
0 g (product name: BREN-S, manufacturer: Nippon Kayaku), and as in Example 1, as a curing agent
3 g (manufacturer: oiled shell) and 1 g (manufacturer: Shikoku Chemicals) as a curing accelerator 2-ethyl-4-methyl-imidazole were blended to prepare an epoxy resin composition.

The evaluation methods for the epoxy resin compositions of Examples 1 to 5 and Comparative Example 1 obtained as described above were as follows.
It is as follows.

The epoxy resin compositions obtained in Examples 1 to 5 and Comparative Example 1 were used as resin varnishes and impregnated into glass cloth to prepare prepregs. Each was press-molded under curing conditions to produce a laminate as an insulating substrate.

The evaluation of the physical properties of this laminated plate was conducted by measuring the glass transition temperature (indicated as Tg in Table 1) and the linear expansion coefficient by JI.
Performed according to S-C6481. The results are shown in Table 1 below.
Examples 1 to 5 and Comparative Example 1 are summarized below.

[0056]

[Table 1]

As can be seen from comparison between Examples 1 to 5 and Comparative Example 1, the glass transition temperatures (Table 1)
Inside, it is shown as Tg. ), The temperature of each of Examples 1 to 5 was higher than that of Comparative Example 1 by 10 ° C. or more, showing excellent physical properties. Shows excellent physical properties that are not inferior to those of Comparative Example 1 or higher than those of the same level. Further, under the curing conditions, those of Examples 1 to 5 are better than those of Comparative Example 1. However, curing is completed at a relatively low temperature and in a short time.Conversely, if the glass transition temperature is maintained at a level similar to the conventional level, the present invention can be performed at a low temperature. The curing can be completed in a short time, and the epoxy resin composition of the present invention can be produced by completing the curing in a low temperature and in a short time while maintaining the physical properties of the glass transition temperature and the coefficient of linear expansion. Can also improve efficiency It can be seen that it can be said that it is.

[0058]

According to the epoxy resin composition according to the first aspect of the present invention, curing is completed at a low temperature and in a short time while maintaining physical properties such as a glass transition temperature and a linear expansion coefficient, thereby improving production efficiency. That can be done.

According to the epoxy resin composition according to claims 2 to 8 of the present invention, in addition to the case described in claim 1, while maintaining the physical properties of the glass transition temperature and the coefficient of linear expansion more reliably, The curing can be completed at a low temperature in a short time, and the production efficiency can be more reliably improved.

According to the insulating substrate using the epoxy resin composition according to the ninth aspect of the present invention, the curing is completed in a short time at a low temperature while maintaining the physical properties of the glass transition temperature and the coefficient of linear expansion. A substrate that can improve the efficiency can be obtained.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4J002 CD042 CH07W EG047 EL136 EN047 EU117 FD146 FD157 GQ05 4J036 AA05 AD01 AF05 AF06 AF07 AF08 AF10 AF11 AF15 DA01 DA02 FB12 JA08

Claims (9)

[Claims] An epoxy resin composition comprising, as essential components, a polyphenylene ether, a curing agent, a curing accelerator, and an epoxy resin having a naphthalene skeleton. 2. The epoxy resin composition according to claim 1, wherein the epoxy resin having a naphthalene skeleton is represented by the following formula [I]. Embedded image 3. The epoxy resin composition according to claim 1, wherein the epoxy resin having a naphthalene skeleton is represented by the following formula [II]. Embedded image 4. The epoxy resin having a naphthalene skeleton according to the above formula [I] and the above formula [II]
The epoxy resin composition according to claim 1, which is a mixture of the following. 5. The epoxy resin according to claim 1, wherein the epoxy resin having a naphthalene skeleton is blended in an amount of 20 to 50 wt% based on the total amount of the epoxy resin. Composition. 6. In place of the polyphenylene ether,
The epoxy resin composition according to any one of claims 1 to 5, wherein said polyphenylene ether and novolak phenol are heated and melted to contain a modified polyphenylene ether whose terminal is modified with novolak phenol. 7. The epoxy resin composition according to claim 6, wherein the modified polyphenylene ether is obtained by heating and melting the polyphenylene ether and the novolak phenol, and then compounding a radical initiator. object. 8. The method according to claim 1, wherein the radical initiator is at least one selected from the group consisting of benzoyl peroxide, azoisobutyronitrile, cumene hydroperoxide, t-butyl hydroperoxide and dicumyl peroxide. 7. The epoxy resin composition according to 7. 9. An insulating substrate using an epoxy resin composition, wherein the glass substrate is impregnated with the epoxy resin composition according to claim 1 and cured.