JPS59136319A - Epoxy resin composition for flame retardant board - Google Patents

Abstract

PURPOSE:To provide a flame retardant epoxy resin composition having high transparency and excellent heat resistance, electrical characteristics and chemical resistance and suitable for a (copper-clad) laminate board, by using a specific antimony pentoxide as a part of the flame retardant. CONSTITUTION:The objective composition is composed of (A) a non-halogenated epoxy resin having >=2 epoxy groups in the molecule (e.g. diglycidyl ether of bisphenol A), (B) a halogenated epoxy resin having >=2 epoxy groups in the molecule (e.g. diglycidyl ether of brominated bisphenol A), (C) an antimony pentoxide having an average particle diameter of 1-100mu and consisting of secondary agglomerate of primary particles having an average particle diameter of 5-100mmu, and/or an antimony pentoxide having an average particle diameter of 5-100mmu, and (D) a curing agent.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a flame-retardant epoxy resin composition for substrates suitable for laminates and copper-clad laminates.

More specifically, the present invention relates to a novel epoxy resin composition for flame-retardant substrates that has good transparency and maintains excellent heat resistance, electrical properties, and strong chemical properties.

In recent years, with the development of electrical and electronic equipment, the laminates used in these fields are increasingly required to be flame retardant in terms of safety. On the other hand, in order to streamline the inspection of printed wiring boards, even flame-retardant substrates are required to have the same transparency as flame-retardant substrates.

As a means to make such a laminate plate flame retardant.

Generally, a method using a halogenated epoxy resin or a flame retardant such as an organic halogen compound, an organic phosphoric acid ester compound, or an inorganic compound is used.

However, these methods have a sufficient flame retardant effect, especially the degree of flame retardation that has recently been strongly exceeded by tJL standard 94.
Achieving V-0 requires the use of a large amount, which may result in increased costs, a decrease in the physical properties of the laminate such as heat resistance or electrical properties, or a loss of transparency in the laminate. There is a problem with the price.

Improvements in the same layer are desired from a performance standpoint.

In particular, the inorganic flame retardant diantimony trioxide exhibits excellent flame retardant effects due to its synergistic effect with halogen atoms, so it is widely used as a flame retardant for various plastics along with various halogen-containing compounds. If this product is used as a flame retardant for laminates, especially epoxy resin to glass cloth laminates, the transparency of the laminates will be lost, which will complicate the product inspection process as mentioned above. occurs.

In view of the above circumstances, the present inventors conducted research to solve these problems, and found that by using a specific nantimony pentoxide as part of the flame retardant, good transparency can be achieved. Excellent heat resistance.

The present invention was completed based on the discovery that a flame-retardant epoxy resin composition suitable for laminates and copper-clad laminates that maintains electrical properties and chemical resistance can be obtained.

That is, 1. The present invention provides an epoxy resin composition for producing laminates and laminates, including a) a non-halogenated epoxy resin having at least two or more epoxy groups in the molecule, and b) a small amount in the molecule. C) Halogenated epoxy resin having two or more epoxy groups C) Consisting of secondary aggregates of primary particles with an average particle size of 5 to 100 millimicrons and/or an average particle diameter of 5 to 100 microns. This invention relates to an epoxy resin composition for flame-retardant substrates, characterized in that it contains as a constituent component of nantimony pentoxide having a diameter of 1 to 100 microns d) a curing agent.

When the epoxy resin composition of the present invention is used for a laminate based on glass cloth, the laminate obtained has good transparency despite the addition of an inorganic compound, diantimony pentoxide. The laminate does not become opacified as is observed when antimony trioxide is used.

Moreover, the nioantimony pentoxide used in the present invention exhibits an excellent flame retardant effect even when added in a small amount due to its synergistic effect with halogen atoms, so that cost reduction is possible. For example, as will be made clear in the examples described later, the degree of flame retardancy is UL94.
It has the advantage that the amount of expensive brominated epoxy resin used can be greatly reduced in order to achieve V-0.

Furthermore, the laminate obtained using the epoxy resin composition of the present invention has little color deterioration at high temperatures and can be used stably for a long period of time. Other excellent soldering heat resistance, electrical properties,
It maintains chemical resistance and is extremely useful as a highly reliable printed wiring board material.

Furthermore, since the antimony pentoxide used in the present invention is an ultrafine particle, an aggregate of ultrafine particles, or a mixture thereof, it has excellent uniform dispersibility even in a varnish for impregnating a base material. No sexual deterioration was observed at all.

The present invention will be explained in more detail below.

5. In carrying out the present invention, non-halogenated epoxy resins having at least two or more epoxy groups in one molecule include bisphenol A, bisphenol F, resorcinol, hydroquinone, 44'-dihydroxydiphenyl, and bisphenol S.

Dihydric phenol dilycidyl ether type such as dihydric phenol and polyglycidyl ether type polyhydric phenol such as phenol-formaldehyde resin can be mentioned.

Examples of the halogenated epoxy resin having at least two or more epoxy groups in its nine molecules include the diglycidyl ether type of brominated or chlorinated dihydric phenols mentioned above.

Furthermore, any curing agent can be used as long as it does not impair the purpose of the present invention.

For example, dicyandiamide or 7-tar acid anhydride.

Examples include acid anhydrides such as Himic anhydride, and various amine compounds. Further, a curing accelerator can be used in combination with the epoxy resin composition used in the present invention, if necessary. Examples include tertiary amines such as benzyldimethylamine and triethylamine.

Further, as mentioned above, the nioantimony pentoxide used in the present invention may be ultrafine particles having an average particle size of 5 to 100 microns, or secondary aggregates of the ultrafine particles having an average particle size of 1 to 100 microns. Any mixture of these is sufficient;
Any known method for producing such diantimony pentoxide may be used as long as the particle size satisfies the above-mentioned requirements. Those with an average particle size of 1 micron or less are difficult to manufacture, and those of 100 microns or more are undesirable because of their poor miscibility with resins.

In addition, the form in which such diantimony pentoxide is used is not particularly limited, and it may be used in a powder state or a colloid state uniformly dispersed in an organic solvent capable of dissolving the epoxy resin used. I can do it.

The ratio of the non-halogenated epoxy resin, halogenated epoxy resin, and nantimony pentoxide used in the present invention is determined as appropriate, taking into account the content of the non-halogenated epoxy resin used and the desired degree of flame retardation. Just choose.

For example, as will be clarified in the examples described later, in order to achieve the highest flame retardant degree standard of 94V-0,... bromine content of 18 to 20 wt as a rogenated epoxy resin is required.
% of brominated epoxy resin, non-halogenated epoxy resin:brominated epoxy resin-1:1. Niantimony pentoxide 5 based on 100 parts by weight of total epoxy resin
A usage ratio of approximately parts by weight is preferred.

The amount of the curing agent to be used may be appropriately determined depending on the epoxy equivalent of the epoxy resin used, the amount used, and the type of curing agent used.

Furthermore, 1. When preparing a varnish for manufacturing a laminate using the composition of the present invention, an organic solvent that uniformly dissolves a non-halogenated epoxy resin, a halogenated epoxy resin, and a curing agent is appropriately selected. After dissolving the above three components in this organic solvent, diantimony pentoxide may be added and uniformly dispersed.

In addition, various other additives may be used in combination as long as they do not impair the objectives and effects of the present invention.

The present invention will be explained in more detail with reference to Examples below.

Example 1 a) Preparation of varnish for manufacturing laminates Epikote 1001 (epoxy equivalent: 4
50-500) 50 parts by weight, Epicoat 1045B-80 (epoxy equivalent: 450-50), which is a brominated bisphenol A type epoxy resin, as a halogenated epoxy resin.
0. In a solution in which 625 parts by weight of a methyl ethyl ketone solution (containing bromine in the resin with a concentration of 18 to 20% by weight and a concentration of 80% by weight) was dissolved in 42.5 parts of methyl ethyl ketone,
A solution prepared by dissolving 4 parts by weight of dicyandiamide as a curing agent and 02 parts by weight of benzyldimethylamine as a curing accelerator in 30 parts by weight of 9-dimethylformamide is added and mixed well.

Next, 61 parts by weight of diantimony pentoxide was added and uniformly dispersed in the system by stirring and mixing to prepare a varnish for manufacturing laminates.The diantimony pentoxide used in this example was in the form of a powder with an average particle size of 68 microns. However, this is a secondary aggregate of ultrafine particles with an average particle size of 15 millimicrons.

Furthermore, the total solid content of the above varnish was 558% by weight, and the bromine content in the total solid content was 885% by weight.

The antimony content is 2.18% by weight and the bromine/antimony ratio is 406.

b) Product 1 - Manufacture of Plate A glass woven fabric having a thickness of 018 mm was impregnated with the above varnish and dried to obtain a prepreg having a resin content of 50% by weight. Eight sheets of this prepreg were stacked and press-molded under heat. The molding conditions are press temperature 170℃, press pressure cuff 0 kg.
/c4. The pressing time was 20 minutes.

Next, the obtained laminate was post-cured at 170° C. for 60 minutes to obtain a laminate.

Separately, a copper-clad laminate with a 65 μm thick copper foil was also manufactured. The method and conditions were the same as above. The physical properties, electrical properties, and flame retardance of the laminates were evaluated. The results are shown in Table 1.

Example 2 a) Preparation of varnish for manufacturing laminates Except for using nioantimony pentoxide in powder form with an average particle size of 46 microns, which is a secondary aggregate of ultrafine particles with an average particle size of 48 millimicrons. A varnish was prepared in the same manner as in Example 1-a).

Therefore, the total solid content in the varnish and the bromine/antimony ratio in the solid content are also the same as in the varnish of Example 1-8).

b) Production of laminate A laminate was produced using the same method and conditions as in Example 1-b).

The results are shown in Table 1.

Comparative Example 1 a) Preparation of varnish for manufacturing laminates NEMA standard +j R-4 or JIS standard Of!
As a typical formulation example for manufacturing J-3 compliant flame retardant laminates.

c, M, c, Technical Report J16.17 Printed wiring additives and processing technology (Edited by Torao Higaki 8 Published by CMC Co., Ltd., November 20, 1980) Based on the formulation example described on page 59 A varnish was prepared.

That is, 125 parts by weight (100 parts by weight of brominated epoxy resin) of a solution of 80 parts of brominated epoxy resin Epicoat 1045-B-80 in methyl ethyl ketone (100 parts by weight as brominated epoxy resin) used in Example 1-a) was diluted with 65 parts by weight of methyl ethyl ketone. .

Next, a solution prepared by dissolving 4 parts of dicyandiamide as a hardening agent and 02 parts by weight of benzyldimethylamine as a hardening accelerator in 30 parts by weight of dimethylformamide were added and mixed well to obtain a varnish. The total solid content of this varnish is 56.
It is 7% by weight.

b) Production of laminate A laminate was produced using the same method and conditions as in Example 1-b). The results are shown in Table 1.

As is clear from the results in Table 1, in this comparative example, a laminated board conforming to the mouth specification of 94V-0 was obtained using only an expensive brominated epoxy resin containing 18 to 20 tons of bromine. It will be done. On the other hand, in Examples 1 and 2, excellent flame retardant effects were observed even if the amount of brominated epoxy resin used was halved.

In addition, when comparing the performance of this comparative example other than flame retardance with Examples 1 and 2, the transparency of the laminate was improved in the laminate to which nantemon pentoxide was added, and the transparency of the laminate was improved. It can be seen that the diantimony pentoxide is extremely finely and uniformly dispersed. In addition, Examples 1 and 2 have improved bending strength and stain-resistant properties.

It is clear that the laminate to which 13-nium antimony pentoxide is added has excellent performance, with no inferiority in soldering heat resistance, boiling water absorption, etc.

Comparative Example 2 a) Preparation of varnish for manufacturing laminates All Example 1- except that diantimony trioxide powder with an average particle diameter of 05 microns was used instead of diantimony pentoxide.
The varnish was coated using the same method as in a).

The total solids content in the varnish was 558% by weight.

The bromine/antimony ratio in the solids is 367.

b) Production of laminate A laminate was produced using the same method and conditions as in Example 1-b). The results are shown in Table 1.

As is clear from the table, the laminate to which antimony trioxide is added has flame retardancy and electrical properties.

The mechanical properties, soldering heat resistance, boiling water absorption rate, etc. were compared with the results of Examples 1 and 2 [7] and it was found that although there were no major differences, the transparency was significantly deteriorated. In fact, the laminated plate obtained in this comparative example has a white color and its transparency is significantly impaired, and in this state, the object of the present invention cannot be achieved at all.

Claims (1)

[Scope of Claims] An epoxy resin composition for producing a laminate or a copper-clad laminate containing a) a non-halogenated epoxy resin having at least two or more epoxy groups in the molecule; b) at least one epoxy resin in the molecule; Halogenated epoxy resin having two or more epoxy groups C) Consisting of secondary aggregates of primary particles with an average particle size of 5 to 100 millimicrons and/or an average particle diameter of 5 to 100 millimicrons; An epoxy resin composition for a flame-retardant substrate, characterized in that it contains as a constituent component nantimony pentoxide having a particle diameter of 1 to 100 microns; d) a curing agent.