JPS60158215A - Epoxy resin composition for laminate - Google Patents

Abstract

PURPOSE:The titled resin composition which can prevent a flame retarding filler from being settled, has good wettability with a resin and can form a laminate excellent in measling resistance, and soldering-heat resistance, prepared by mixing an epoxy resin with a curing agent, a flame-retarding filler and a surface treating agent at a specified ratio. CONSTITUTION:An epoxy resin (A) (e.g., bisphenol A glycidyl ether) is mixed with a curing agent (b) (e.g., dicyandiamide), a flame retarding filler (c) (e.g., aluminum hydroxide or antimony trioxide) and a surface treating agent (D) comprising an organic titanate of formula I or II (wherein X is an alkoxy, carboxylic acid, sulfonic acid, phosphoric acid, phosphorous acid or metaphosphoric acid group). The mixing ratio is such that 5-50pts.wt. component C is present per 100pts.wt. total of components A and B, and component D is present in an amount of 0.01-1.5wt% based on component C.

Description

DETAILED DESCRIPTION OF THE INVENTION [Technical Field of the Invention] The present invention relates to an epoxy resin composition for laminates that has excellent wettability between resin and filler.

[Technical background of the invention and its problems] Epoxy resin laminates are widely used as circuit boards or structural materials in electronic devices, etc., but due to the rationalization of printed wiring board processing processes and the miniaturization of electronic devices, packaging density has increased. Due to the increase in metallurgy and flame retardant regulations, there has been a demand for laminates that have excellent measling resistance and soldering heat resistance as well as flame retardancy.

There are various methods for making the resin flame retardant, such as adding a flame retardant filler to the epoxy resin, using a flame retardant resin component, or using a combination of these.

Conventionally, among the various flame retardant methods mentioned above, the most economical method has been to incorporate M flammable filler.
There are problems such as compatibility with flame retardants and resins. In other words, an epoxy resin composition containing a flame-retardant filler is used by diluting it with a solvent in order to impregnate and coat the base material, but in this case, the filler in the composition may settle. This has the disadvantage that the wettability between the filler and the epoxy resin deteriorates.

Laminated plates using this composition also have the disadvantage of poor measling resistance and soldering heat resistance.

[Object of the Invention] The object of the present invention was to solve the above-mentioned drawbacks, and it is possible to prevent the sedimentation of the flame retardant filler, have good wettability with resin, and improve measling resistance and solder resistance. The object of the present invention is to provide an epoxy resin composition from which a laminate with excellent heat resistance can be obtained.

[Summary of the Invention] As a result of intensive research to achieve the above objects, the present invention has been developed to prevent the sedimentation of the flame retardant filler and improve its wettability with the resin by adding a surface treatment agent. It has been found that this can be improved.

That is, the present invention has (a) an epoxy resin, (b) a curing agent, (c) a flame-retardant filler, and (d) a surface treatment agent as its main components, and the flame-retardant filler (C) is a resin component [(
a) + (b)'] 5 to 5 per 100 parts by weight
0! Quantity of the surface treatment agent (d) above (C)
This is an epoxy resin composition for a laminate, characterized in that it is blended in an amount of 0.01 to 1.5% by weight based on the flame retardant filler.

As the epoxy resin (a) used in the present invention, any epoxy resin having two or more epoxy groups in one molecule can be used. For example, bisphenol A
Examples include glycidyl epoxy resins such as glycidyl ether of , glycidyl ether of halogenated bisphenol, glycidyl ether of novolac, non-glycidyl epoxy resins such as epoxidized polyolefin, and epoxidized soybean oil. These epoxy resins can be used alone or in a mixed system of two or more.

As the curing agent (b) used in the present invention, any commonly used epoxy resin curing agent can be used. Examples include dicyandiamide, 71-nol novolak resin, acid anhydride, polyamine, etc., and these can be used alone or in a mixture of two or more.

Examples of the flame-retardant filler (C) used in the present invention include aluminum hydroxide, antimony trioxide, and the like, and these can be used alone or as a mixture of two or more.

The blending portion of this filler is the resin component [(a)+
(b)] It is necessary that the amount is 5 to 50 parts by weight per 10 parts by weight. If the proportion of the filler is less than 5 parts by weight, there is no effect on flame retardancy, and if it exceeds 50 parts by weight, the impregnation of the resin composition into the base material becomes undesirable.

The surface treatment agent (d) used in the present invention has the general formula % [] (where X is an alkoxy group, a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, a phosphorous acid group, or a metaphosphoric acid group). isopropyl triisoste aroyl titanate, isopropyl tridodecylbenzenesulfonyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, tetraisopropyl bis (dioctyl phosphite) titanate, tetraoctyl bis (ditridecyl phosphite) titanate, tetra(2,2-diallyloxymethyl-1-butyl) bis(ditridecyl) phosphite titanate, bis(dioctyl pyrophosphate) oxyacetate titanate, bis(dioctyl pyrophosphate) ethylene titanate, etc. These can be used alone or in combination of two or more.

The amount of this surface treatment agent is required to be 0.01 to 1.5% by weight of the flame retardant filler (C).

This is because if the blending amount is less than 0.01% by weight, there is no effect on wettability, whereas if the blending amount exceeds 1.5% by weight, the effect will not change and the cost will increase, which is not preferable.

[Effects of the Invention] By adding a surface treatment agent, the epoxy resin composition for laminates of the present invention does not cause sedimentation of the flame retardant filler and has good wettability with the resin. The resulting laminate has excellent measling resistance and soldering heat resistance.

[Examples of the Invention] Next, Examples of the present invention will be described, but the present invention is not limited to the Examples. In the following Examples and Comparative Examples, "1 part" means "part by weight."

Examples 100 parts of brominated bisphenol A epoxy resin, 3.5 parts of dicyandiamide, 30 parts of aluminum hydroxide, and 0.45 parts of tetraoctyl bis(ditridecyl phosphite) titanate as a surface treatment agent (as a flame retardant filler) 2-ethyl-
0.1 part of 4-methyl-imidazole and acetone were added to prepare a varnish for an epoxy resin composition for laminates.

Next, this varnish was impregnated and coated on a glass cloth of 0.1 g in thickness and ml, and dried to obtain a prepreg with a resin content of 40.5% by weight. 8 sheets of prepreg and a thickness of 35μ on the front and back sides.
40kg/am for 60 minutes at 170℃
Laminated and molded together under heat and pressure under the conditions of 2, thickness 1.61
A copper clad laminate of No. 111 was obtained. This laminate was tested for solder heat resistance, measling resistance, and flame resistance, and the results are shown in Table 1.

Comparative Example A varnish was prepared in the same manner as in the Example except that no surface treatment agent was added, and then a laminate was obtained.
The obtained laminate was similarly tested for soldering heat resistance, measling resistance, and flame resistance, and the results are shown in the first section.
Shown in the table.

Table 1 *1 Approximately 200ml of varnish was placed in a glass cylinder and left to stand for a day and night, and the depth at which it became transparent was measured *2 According to J15-C-6481, 260℃, 1
The presence or absence of sagging after 0 minutes was checked. It can be seen that the invention is an epoxy resin composition for laminates that has no sedimentation and has good wettability.

Claims (1)

[Scope of Claims] 1 (a) an epoxy resin (b) a curing agent (c) a flame retardant filler (d) a surface treatment agent as a main component, the flame retardant filler being a resin component [(a>+ (
b)] 5 to 50 parts by weight per 100 parts by weight, and 0.01 to 1.5 parts of the surface treatment agent to the flame retardant filler.
An epoxy resin composition for laminates, characterized in that it is blended in a weight percent. 2. An organic titanate compound whose surface treatment agent is represented by the general formula % (where X represents an alkoxy group, a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, a phosphorous acid group, or a metaphosphoric acid group). The epoxy resin composition for a laminate according to claim 1, characterized in that: