JPS6368617A - Flame-retardant resin composition and laminate using the same - Google Patents

Abstract

(57) [Abstract] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a flame-retardant resin composition and its use,
In particular, the present invention relates to a laminate suitable for multilayer printed circuit boards that has excellent long-term flammability, heat resistance, and electrical properties.

[Conventional technology]

Conventionally, laminates made of phenol resins, epoxy resins, polyimide resins, etc. using brominated modified resins or additive flame retardants have been mainly used as laminated materials for multilayer plant circuit boards to impart flame retardancy. . In particular, high density is desired for large computers.

A polyimide resin with excellent heat resistance and two-dimensional stability is used. However, in recent years, with the increase in high-speed calculation processing of large computers, printed circuit boards with excellent electrical characteristics are required to improve signal transmission speed. In particular, shorten the signal transmission delay time, and.

Low dielectric constant printed circuit boards are needed to reduce circuit thickness. Tetrafluoroethylene resin, polybutadiene resin laminates, and the like have been developed as such low dielectric constant laminate materials. This type of laminate includes, for example, Proceedings N.B.C.O.N.
(1981) pp. 160-169 (Pro
c, NEPCON (1981) pp160-169)
and Japanese Patent Publication No. 5g-21926.

[Problem that the invention seeks to solve]

In the conventional technology described above, PTFE laminates have problems such as a high coefficient of thermal expansion at high temperatures and insufficient dimensional stability because the resin is thermoplastic and the glass transition temperature is low. There are concerns about through-hole reliability, etc., and when applied to multilayer printed circuit boards, it has a wiring density similar to that of epoxy resin, so it does not have much merit as a low dielectric constant material, and it is not suitable for PTFE. Since there is no solvent, bonding methods using heat melting and pressure bonding are generally used, but this method has the disadvantage that the melting temperature is extremely high. Polybutadiene resin has the disadvantage of being easily flammable due to its molecular structure, so additives such as decabromodiphenyl ether and triphenyl phosphate, as well as tribromophenyl methacrylate and tribromophenyl acrylate, are used to impart flame retardancy. Although it is necessary to add a reactive flame retardant, there is a problem in that the addition of these impairs the electrical properties, heat resistance, and two-dimensional stability inherent to the polybutadiene resin.

The purpose of the present invention is to create a resin composition of a flame-retardant, low-permittivity laminate material that enables high-density wiring comparable to that of polyimide laminate materials, as a material that can replace polyimide-based multilayer printed wiring boards used in large-scale computers. thing.

Our objective is to provide laminates.

[Means for solving problems]

The first aspect of the present invention relates to a flame-retardant resin composition, the characteristics of which are (
This is a flame retardant resin composition comprising a) dimethacrylate, a tetrabromobisphenol A/ethylene oxide reactant, and (b) 1,2-polybutadiene and its derivatives as essential components.

The second relates to a laminate formed by laminating and molding prepregs obtained by impregnating and drying a base material with a flame-retardant resin composition.

The 1,2-polybutadiene component in the resin composition of the present invention includes 1,2-polybutadiene homopolymerization, cyclized 1,2-polybutadiene, terminal epoxy-modified,
-Polybutadiene, 1,2-polybutadiene glycol, 1,2-polybutadiene dicarboxylic acid, urethane-modified 1,2-polybutadiene, maleated 1,2-polybutadiene, terminal acrylic-modified 1,2-polybutadiene, terminal ester-modified Various polymers and derivatives such as copolymers containing 1,2-polybutadiene having a vinyl side group such as 1,2-polybutadiene as a basic component can be used.

The blending ratio (polymerization) of tetrabromobisphenol A/ethylene oxide reactant dimethacrylate and 1,2-polybutadiene is selected in the range of 80:20 to 20:80, and if the content of the former is higher than this, curing occurs. The relative dielectric constant of the resin becomes high, and if it is too low, the flame retardant effect becomes insignificant.

In addition, the number average molecular weight of 1,2-polybutadiene is s, o
The molecular weight is selected within the range of o to so, ooo, and if the molecular weight is smaller than this range, a problem will arise in the tack-free property of the bristle, and if it is larger than this range, the solubility in organic solvents will be reduced.

Next, a general method for manufacturing a laminate according to the present invention will be explained.

First, a varnish is prepared by dissolving the tetrabromobisphenol A/ethylene oxide reactant dimethacrylate and 1°2-polybutadiene or a derivative thereof in an organic solvent. Examples of organic solvents include toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, and N.

Examples of the solvent include N-dimethylformamide, N-methylpyrrolidone, dimethylsulfoxide, trichloroethylene, trichloroethane, methylene chloride, and dioxane, and any solvent that can uniformly dissolve the resin composition can be used without limitation. A radical polymerization initiator is added to the prepared varnish to obtain a varnish for impregnation.

Typical examples of radical polymerization initiators are benzoyl peroxide, dicumyl peroxide, methyl ethyl ketone peroxide, t-butyl peroxylauate, di-
t-Butylperoxyphthalate, dibenzyl oxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane.

t-butylcumyl peroxide, t-butyl hydroperoxide, di-t-butyl peroxide.

2.5-dimethyl-2,5-di(t-butylperoxy)hexyne (3), diisopropylbenzene hydroperoxide, p-menthane hydroperoxide, vinylane hydroxide, 2゜5-dimethylhexane-2
, 5-sibide lobar oxide, cumene hydroperoxide and the like. These are preferably added in an amount of 0.1 to 10 parts by weight per 100 parts by weight of the resin composition.

Next, the obtained impregnating varnish is impregnated and coated on a sheet-like base material and dried at room temperature to 170°C to obtain a non-tacky prepreg. The setting of the drying temperature at this time is determined by the solvent and initiator used. Finally, the required number of prepregs obtained are stacked, and a heat curing reaction is performed at 100 to 250°C under a pressure of 1 to 10 kgf/d to obtain a laminate.

As the sheet-like base material, almost all those generally used for laminated materials can be used. The inorganic fiber is Si
E glass, C whose components are Ox, AQ zoa, etc.
Glass, A glass, S glass, D glass.

There are various glass fibers such as YM-31-A glass and Q glass using quartz. Furthermore, examples of organic fibers include aramid fibers containing a polymer compound having an aromatic polyamide-imide skeleton.

〔Example〕

Hereinafter, one embodiment of the present invention will be described in detail.

<Example 1> Tetrabromobisphenol A/ethylene oxide reactant dimethacrylate (manufactured by Dai-Kogyo Seiyaku) and 1,2-
Polybutadiene (number average molecular weight about 13.000) was dissolved in toluene to obtain a varnish with a polymer blending ratio of 5:5 (weight ratio) and a solid content of 40%.

Furthermore, 2,5-dimethyl 2.5 di(t-butylperoxy)hexyne 3 was added to the varnish 100 as a radical polymerization agent.
After adding 2 parts by weight to 2 parts by weight, this varnish was applied to a glass cloth cloth (E glass manufactured by Nittobo Co., Ltd.).

The prepreg was impregnated to a thickness of 0.1 m) and dried at 110° C. in a sufficient amount of constant temperature air to obtain a tack-free prepreg. Next, stack ten sheets of this prepreg and apply a pressure of 30 kgf/
j, heated at a temperature of 130℃ for 30 minutes, and further heated to 220"
The adhesive curing reaction was carried out in a press for one hour by raising the temperature to C. to obtain a laminate.

<Example 2> A laminate was obtained in the same manner as in Example 1, except that 20% by weight of cyclized 1,2-polybutadiene was used in 1,2-polybutadiene.

Comparative Example> 1. A laminate was obtained in the same manner as in Example 1 using only 2-polybutadiene.

The main properties of the laminates according to Examples and Comparative Examples are shown in the table.

〔Effect of the invention〕

According to the present invention, a tack-free prepreg can be easily produced from a known base material by applying conventional equipment and processes as is, and is more flame retardant than conventional products.

Claims (1)

[Scope of Claims] 1. (a) Tetrabromo represented by the following chemical formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ Bisphenol A/ethylene oxide reactant dimethacrylate and (b) 1,2-polybutadiene or its derivative as an essential component, and the blending ratio of (a) and (b) is 8.
A flame retardant resin composition characterized in that the ratio is 0:20 to 20:80. 2. In a laminate in which prepregs formed by impregnating and drying a synthetic resin into a base material are laminated and bonded, the synthetic resin is (a) tetrabromobisphenol A/
ethylene oxide reactant dimethacrylate and (b)
1. A laminate comprising a flame-retardant resin composition containing 1,2-polybutadiene or a derivative thereof as an essential component.