JPS63199725A - Epoxy resin composition - Google Patents

Abstract

PURPOSE:To obtain the title composition excellent in heat resistance, adhesion to metals, etc., by mixing a specified epoxy resin with a curing agent comprising a polycondensate of a (halogenated) bisphenol A with formaldehyde, a cure accelerator and a solvent. CONSTITUTION:An epoxy resin is produced by reacting a glycidyl ether (A) of a polycondensate of a (halogenated) bisphenol A with formaldehyde with a diepoxy resin (B) whose skeleton entirely consists of a skeleton of a compound such as (tetrabromo)bisphenol A or bisphenol F and (tetrabromo)bisphenol A or bisphenol F (C). An epoxy resin component based on the obtained epoxy resin is mixed with a curing agent comprising a (halogenated) bisphenol A/ formaldehyde polycondensate, a cure accelerator (e.g., 2-ethyl-4-methylimidazole) and a solvent to obtain the title resin composition.

Description

DETAILED DESCRIPTION OF THE INVENTION (a) Object of the invention (industrial application field) The present invention is capable of providing an epoxy resin composition, particularly a cured product having excellent heat resistance and adhesion to metals. The present invention relates to an epoxy resin composition that is advantageously used for manufacturing copper-clad epoxy resin laminates for printed wiring boards.

(Prior Art) In recent years, with the miniaturization of electronic devices, the density of printed wiring boards has been increasing. Therefore, the heat resistance of the base material,
Improvements in measling resistance, etc. are desired.

Furthermore, aromatic amines, dicyandiamide, acid anhydrides, BF, complexes, and the like have been conventionally used as curing agents for epoxy resins, but the heat resistance of the cured products has been insufficient.

Is phenol added to the epoxy resin used to improve the heat resistance of cured epoxy resin products? Polyfunctional epoxy resins such as polyurethane-type epoxy resin, cresol nogera, polyurethane-type epoxy resin, and triglycidyl ether of triglycidyl phenol are often added. However, the heat resistance of the cured product was still not sufficient. In addition, as a means for improving the heat resistance of synthetic resins for laminates, phenolic resins and resins have had problems in their curability.

(Problems to be Solved by the Invention) The present invention provides a cured resin with excellent heat resistance suitable for manufacturing copper-clad epoxy resin laminates used for glint wiring boards, etc., and excellent adhesion to steel foils, etc. An epoxy resin composition containing a curing accelerator and a solvent, in which the epoxy resin is composed of an epoxy resin having the following epoxy resin a as a main component, and the curing agent is an epoxy resin composition characterized in that it consists of a curing agent having the following curing agent as a main component.

Epoxy resin a: (I) At least one glycidyl ether selected from the group consisting of a glycidyl ether of a polycondensate of bisphenol A and formaldehyde, and a glycidyl ether of a polycondensate of halogenated bisphenol A and formaldehyde. A compound, (■) Pisfu, Nord A,
At least one compound selected from the group consisting of bisphenol F and tetrabromobisphenol A. Bifunctional epoxy resin having only a bone core as a bone core, cm) bispheno-/l/A, bisphenol F and tetrabromobisphenol. At least one selected from the group consisting of Tulomobisphenol A
Epoxy resin obtained by reacting seeds, bisulfur, and nol.

Curing agent b = A curing agent comprising at least one polycondensate selected from a polycondensate of bisphenol A and formaldehyde and a polycondensate of hybarodanated bisphenol A and formaldehyde.

As described above, the epoxy resin composition of the present invention uses an epoxy resin containing a specific epoxy resin a as its main component, and a curing agent containing a specific curing agent b as its curing agent. It is characterized by the use of agents.

Glycidyl etherified polycondensate of bisphenol A and formaldehyde, halogenated bisphenol A
An epoxy resin that uses glycidyl ether, a polycondensate of formaldehyde, and a polycondensate of formaldehyde, or an epoxy resin that uses these as the main component and blends a relatively small amount of other epoxy resins. If cured with andiamide or phenolic adhesive type curing agent, an epoxy resin laminate with very good heat resistance can be obtained, but it has the disadvantage that adhesive properties such as copper foil adhesion are not sufficient. (See Comparative Examples 1 to 6).

On the other hand, the epoxy resin composition of the present invention uses a specific epoxy resin a as the epoxy resin, and this epoxy resin ? Since it is cured using a curing agent with a constant IP rating of 4, it is possible to provide a cured product that has excellent heat resistance and also has excellent adhesion to metals such as copper foil.

The epoxy resin composition of the present invention has a specific epoxy resin a.
This epoxy resin a may be used alone, or may be used in combination with another epoxy resin having two or more niboxy groups in one molecule. Other epoxy resins that can be used in combination include, for example, bisphenol A type 2-gish resin, phenol nogela,
Glycidyl ether type epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, etc.
Examples include various epoxy resins such as epoxy resins, linear aliphatic epoxy resins, alicyclic epoxy resins, heterocyclic epoxy resins, and halogenated epoxy resins. The amount of these other epoxy resins used in combination is the total amount of epoxy resin, that is, the total amount of epoxy resin a and other epoxy resins used in combination 1
The amount should be as much as 50 parts by weight compared to 00 parts by weight. When the amount of other epoxy resins used in combination increases, the crosslinking density of the cured product decreases and heat resistance deteriorates.

In the epoxy resin composition of the present invention, a curing agent containing a specific curing agent b as a main component is used as the curing agent. By using such a specific curing agent, a cured product with good heat resistance can be obtained, and the reason is that
Since this curing agent is a compound with a molecular core similar to that of epoxy resin A, the compatibility between the two is improved.
This is thought to be because the crosslinking density can be increased.

In the epoxy resin composition of the present invention, the curing agent b'@ may be used alone, or in combination with other curing agents in relatively small amounts. Other curing agents that can be used in combination include:
Examples include aromatic polyamines, dicyandiamide F, acid anhydrides, various phenol-type nolas, and resins.

The blending ratio of the epoxy resin and the curing agent in the present invention is within a range where the total amount of the curing agent is 10 to 100 parts by weight per 1001 parts of the total amount of the epoxy resin. Even if the amount of the curing agent is greater or less than this range, the cured physical properties will deteriorate.

Various types of curing accelerators can be used in the NIXY resin composition of the present invention. For example, amines such as benzyldimethylamine and various imidazole compounds,
Examples include tertiary phosphines such as triphenylphosphine.

Various solvents can be used in the epoxy resin composition of the present invention. Examples of these solvents include acetone, methyl ethyl ketone, toluene, xylene, methyl isobutyl ketone, ethyl acetate, ethylene glycol monomethyl ether, N,N-dimethylformamide, N,N-dimethylacetamide, methanol, and ethanol. It is also possible to use a mixed solvent of two or more kinds as appropriate.

If necessary, various other additives, such as flame retardants, fillers, etc., may be appropriately blended into the NIXY resin composition of the present invention.

For example, a copper-clad epoxy resin laminate can be produced using the epoxy resin composition of the present invention according to a conventional method. For example, a prepreg is obtained by impregnating and applying an epoxy resin composition with glass cloth and then heating and drying it to remove the solvent, and then layering copper foil on one or both sides of one or more layers of this prepreg. Then, according to a conventional method, the material is heated and pressurized to form a laminate.

(Examples, etc.) Below, Examples and Comparative Examples will be explained in more detail.
The present invention is not limited to these examples. "1 part" and "regret" described in Examples and Comparative Examples mean "part by weight" and "% by weight", respectively.

Example 1 Glycidyl etherified product of the polycondensate of V-Sufu 1 Nor A and formaldehyde (Yuka Shi, Ruepoxy Co., Ltd. trade name Ko♂ Coat 157, Epo 1/To 8208) 80
1 part, 20 parts of bisphenol AM epoxy resin (trade name: Kozekoat 828, epoxy equivalent: 187, manufactured by Yuka Shell E4-Ki Co., Ltd.), and 40 parts of bisphenol A.
The reaction was carried out in the presence of 0.03 part of a catalyst (dimethylimidazole) to obtain an epoxy resin having an epoxy equivalent of 57°0.

This epoxy resin is called "epoxy resin, J.

Next, 100 parts of this epoxy resin, a polycondensate of bisphenol A and formaldehyde as a curing agent 2
0 parts, 0.2 parts of 2-ethyl-4-methylimidazole as a curing accelerator were mixed, and this mixture was mixed with methyl ethyl ketone/
Ethylene glycol monomethyl ether mixed solvent (mixed weight ratio 1/l) was added to prepare a varnish with a nonvolatile content of 55 liters.

A glass cloth was impregnated and applied with this varnish, and dried at 130° C. for 5 minutes to obtain a prepreg having an epoxy resin composition content of 451. 8 sheets of this prepreg were stacked, copper foil with a thickness of 0.35 μm was layered on both sides, and lamination molding was performed at a temperature of 170°C and a pressure of 40 kg/cm for 1 hour to obtain a thickness of 1.6
- A copper-clad glass Eixyx laminate was manufactured. The properties of this laminate were as shown in Table 1.

Example 2 Glycidyl etherified product of polycondensate of bisphenol A and formaldehyde (Ebicor used in Example 1) 1
57) 8 parts of bisphenol A type epoxy resin (Epicote 828 used in Example 1), and 30 parts of tetrabromobisphenol A were reacted in the same manner as in Example IK to form an epoxy resin with an epoxy equivalent of 342. I got it. This epoxy resin is called "Ko I-Kyoshi Resin 12".
That's what it means.

5 of the resin a1 used in Example I.
xy resin a and the curing agent bisphenol.
A varnish was prepared in the same manner as in Example 1 except that the blending amount of the polycondensate of A and formaldehyde was changed to 39 parts, and a copper-clad glass epoxy laminate was prepared in the same manner as in Example IKTh using the varnish. The board was manufactured. The properties of this laminate were as shown in Table 1.

Example 3 60 parts of the epoxy resin a produced in Example 2,
40 parts of brominated bisphenol A type epoxy resin (product name of Yuka Shell Epoxy Co., Ltd., Nicoat 5049, t748 per epoxy, bromine content 26%) and 30 parts of a polycondensate of bisphenol A and formaldehyde were used, and the rest were as in the example. A varnish was prepared in the same manner as in Example 1. A copper-clad glass epoxy laminate was produced in the same manner as in Example 1 using the varnish of The properties of this laminate were as shown in Table 1.

Example 4 Glycidyl etherified product of polycondensate of pro-phthalated bisphenol A and formaldehyde (epoxy equivalent: 420)
80 parts of bisphenol A type epoxy resin (Epicote 828 used in Example 1), and 30 parts of tetrabromobisphenol A were reacted in the same manner as in Example IK to produce an epoxy resin with an epoxy equivalent of 700. . This Nixi resin is called "Ki Kishi Resin A".
That's what it means.

A varnish was prepared in the same manner as in Example 1 except for using 100 parts of this epoxy resin 1 and 17 parts of a polycondensate of bisphenol A and formaldehyde. A clad glass epoxy laminate was manufactured.

The properties of this laminate were as shown in Table IK.

Example 5 A varnish was prepared according to the method of Example 1 except that 100 parts of Nixy resin a, 30 parts of a polycondensate of bisphenol A and formaldehyde, and 10 parts of a polycondensate of orthocresol and formaldehyde were used. A copper-clad glass niboxy laminate was manufactured using this varnish according to the method of Example 1. The properties of this laminate were as shown in Table 1.

Example 6 The curing agent in Example 2 was replaced with prophylated bisphenol A.
A varnish was prepared in the same manner as in Example 2 except that 42 parts of a polycondensate of The properties of this laminate were as shown in Table IK.

Comparative Example 1 60 parts of glycidyl etherified polycondensate of bisphenol A and formaldehyde (Epicote 157 used in Example 1), bisphenol A type epoxy resin (
Yuka Shi, Rue Ikkishi Co., Ltd. Product name Epicote 10
01, Niexy equivalent 478) 40 parts, 47 parts of a polycondensate of V-sulfinol A and formaldehyde as a curing agent,
and 0.2 part of 2-ethyl-4-methylimidazole as a curing accelerator. The same dimethyl ethyl ketone/ethylene glycol monomethyl ether mixed solvent used in Example 1 was added to this mixture to prepare a varnish with a nonvolatile content of 55 ml.

Using this varnish, a copper-clad glass epoxy laminate was manufactured in accordance with the method in Example IK except for the above. The properties of this laminate were as shown in Table IK. Each copper-clad glass epoxy laminate was manufactured according to the method of Example 1. The characteristics of each of these laminates are shown in Table 1.

Notes for Margin Table 1 below: *1...l-1001, E-5049, E-5050
, E-157, and E-180865 are respectively Epicor)-1001, Epicor-5049, Epicor-5050, Epicor)-157, Epicor)-
180865 (all of the above are product names of Yuka Shell Epoxy Co., Ltd.)! It is an abbreviation.

*2: Measured by dynamic viscoelasticity (-δ).

*3...Immersed in boiling water for 4 hours (soldering temperature 260℃)
)by. The evaluation results are indicated by the following abbreviations.

There is no bulging or peeling of the O plate.

Δ There is slight swelling and peeling of the board.

X There is swelling and peeling of the board.

As is clear from the results shown in Table 1, the epoxy resin compositions of each example had better heat resistance, copper foil adhesion, and measling resistance in a well-balanced manner than the composition of the comparative example. There is.

(e) Effects of the Invention When the epoxy resin composition of the present invention is used in the production of copper-clad epoxy laminates for printed wiring, it produces laminates with excellent heat resistance, copper foil adhesion, measling resistance, etc. can get.

Claims (1)

[Scope of Claims] 1) An epoxy resin composition containing an epoxy resin, a curing agent, a curing accelerator, and a solvent, wherein the epoxy resin is composed of an epoxy resin whose main component is the following epoxy resin a; An epoxy resin composition characterized in that the curing agent consists of a curing agent whose main component is the following curing agent b. Epoxy resin a: (I) At least one glycidyl ether selected from the group consisting of a glycidyl ether of a polycondensate of bisphenol A and formaldehyde, and a glycidyl ether of a polycondensate of halogenated bisphenol A and formaldehyde. (II) Bisphenol A
, bisphenol F and tetrabromobisphenol A
(III) At least one compound selected from the group consisting of a bifunctional epoxy resin whose bone core is only a bone core, and (III) at least one compound selected from the group consisting of bisphenol A, bisphenol F, and tetrabromobisphenol A. Epoxy resin obtained by reacting with bisphenol. Curing agent b: A curing agent comprising at least one polycondensate selected from a polycondensate of bisphenol A and formaldehyde and a polycondensate of halogenated bisphenol A and formaldehyde.