JPS61103914A - Curable resin composition, laminate using same and manufacture thereof - Google Patents

Abstract

PURPOSE:To provide the titled composition capable of giving laminates of low dielectric constant, high copper foil adherability and heat resistance and outstanding high-frequency electrical properties, comprising a prepolymer constituted, as recurring unit, by specific s-triazine compound and 1,2-polybutadiene (derivative). CONSTITUTION:The objective composition comprising (A) a prepolymer constitut ed, as recurring unit, by a s-triazine compound of formula I (R1, R2 and R3 are each H or organic group, at least two of which being polymerizable unsatu rated bond-contg. organic groups) or II (R4, R5, and R6 are each H or organic group, at least two of which being polymerizable unsaturated bond-contg. organic groups) and (B) 1,2-polybutadiene preferably in a weight ratio (A)/(B) of 30/70-70/30. Said composition is impregnated in a base material followed by drying to prepare prepregs, which are then mutually bonded through lamina tion, thus obtaining the other objective laminate(s) with high mechanical strength, dimensional stability and heat resistance and low dielectric constant, suitable for multilayered printed circuit board.

Description

Detailed Description of the Invention [Field of Application of the Invention] The present invention relates to a curable resin composition and its uses, and more particularly to a laminated material suitable for multilayer printed circuit boards having excellent heat resistance and high frequency electrical properties. .

[Background of the invention]

Conventionally, laminates made of phenol resin, epoxy resin, polyimide resin, etc. have been mainly used as laminate materials for multilayer printed circuit boards. However, in recent years, with the increase in high-speed calculation processing in large-scale computers, there has been a demand for i-printed circuit boards with excellent high-frequency electrical characteristics in order to improve signal propagation speed. In particular, printed circuit boards with low dielectric constants are needed to shorten signal transmission delay times and reduce circuit thickness.

As such low dielectric constant laminate materials, polytetrafluoroethylene resin (PTFE) laminates, butadiene resin laminates, and the like have been developed. Since the resin is thermoplastic, PTFE laminates tend to have problems such as a high coefficient of thermal expansion at high temperatures and insufficient dimensional stability, and there are concerns about the reliability of through holes, especially when bonding multiple layers. Therefore, it is difficult to apply it to multilayer printed circuit boards. Also, PTFH
Since there is no suitable solvent for this, adhesive methods are generally used, such as heating and melting, but this method has the drawback that the melting temperature is extremely high. As described above, compared to conventional methods, PTFE has many difficult aspects in terms of workability and moldability, and it is necessary to significantly change the manufacturing method.

In addition, butadiene resin is a curing type different from PTFE, but it has the ability to be impregnated into base materials as a phenolic resin.

Polymers with good curability often remain sticky during the prepreg stage, causing problems in winding, lamination, and other operations. In addition, as a laminate, 1. There were complaints about the beer strength, mechanical strength, and heat resistance of the bonded copper foil. Tackiness is improved by incorporating higher molecular weight polymers. However, since other properties such as copper foil adhesion strength are related to the nature of the resin, their improvement must be achieved by other means. Therefore, solutions have been proposed, such as providing a coating layer on the prepreg made of different types of resins with excellent properties in question (for example, Japanese Patent Application Laid-open No. 74869/1983). However, it is undeniable that the lamination process becomes complicated, and the properties of the butadiene resin may not be fully utilized unless the resulting laminate has a plurality of layers with different properties.

On the other hand, a cured resin of a triazine compound in which two to three diphonic unsaturated groups are bonded is mechanically strong and has excellent heat resistance, and thus can be applied to a laminated material for a multilayer printed circuit board. However, since the resin is very brittle and lacks flexibility,
Avoid creating cracks when laminating layers or forming through holes.
It was difficult to put it into practical use by itself.

In consideration of these circumstances, the present invention aims to solve the above-mentioned difficulties by copolymerizing and curing a triazine resin and a butadiene resin.

[Purpose of the invention]

The object of the present invention is to provide a low dielectric constant laminate material that has excellent mechanical strength, dimensional stability, and heat resistance, and is applied to multilayer printed circuit boards, and a cured material that has a low dielectric constant and high copper foil adhesion suitable for the production thereof. An object of the present invention is to provide a synthetic resin composition, a laminate using the same, and a method for manufacturing the same.

[Summary of the invention]

To summarize the present invention, the first aspect relates to a curable resin composition, the characteristics of which are (a) the following general formula I or '、B、
5l-IJ azine represented by s spx R6 each represents a hydrogen atom or an organic group, and at least two of the three groups belonging to each formula are organic groups containing a polymerizable unsaturated bond) It consists of a prepolymer containing the compound as a repeating unit and (b) 1,2-polybutadiene or a derivative thereof. A second aspect of the present invention relates to a laminate formed by laminating and molding prepregs obtained by impregnating a base material with the curable resin composition and drying the same, and a third aspect of the present invention relates to a method for producing the laminate. In the curable resin composition, inclusion as a repeating unit means that the prepolymer is a homopolymer or copolymer of the 9-IJ azine compound represented by the general formula I or II, or a combination of the compound and other It means a copolymer with a polymerizable unsaturated monomer.

A plastic which is an essential component of the curable resin composition of the present invention
r.

As mentioned above, repolymers include S-)IJ azine compounds (hereinafter abbreviated as polymerizable polyfunctional triazine compounds) represented by the general formula (1) or (II) and containing at least two polymerizable unsaturated bonds in one molecule. ) is included as a repeating unit. Specific examples include triallylisocyanurate and diallylisocyanurate as compounds corresponding to the above general formula I.

Tris(acryloyloxyethyl)in cyanurate, tris(methacryloyloxyethyl)isocyanurate, tris(acryloyloxymethyl)isocyanurate, etc., and compounds corresponding to the general formula (■) include triallyl cyanurate and diallyl cyanurate. ,
Diallylmethyl cyanurate, sialyl phenyl cyanurate.

Examples include dimethallylphenyl cyanurate and tris(acryloyloxyethyl) cyanurate.

One or more of these may be used as desired.

The polymerizable polyfunctional triazine compound can be made into a soluble prepolymer by a polymerization reaction.

Since the prepolymer generally undergoes a crosslinking reaction very quickly, cracks may easily occur in the molded product during the curing process. In such cases, when preparing the prepolymer, it is possible to copolymerize two or more polymerizable polyfunctional triazine compounds, or to copolymerize with a polymerizable unsaturated monomer different from the compound. Preferably, this can moderate the crosslinking rate of the prepolymer and improve the moldability of the resin composition. The polymerizable unsaturated monomer used in this case has the general formula ■R-AI"-R凰 (wherein, Ar represents a divalent aromatic group, and R is an organic group having a polymerizable unsaturated bond. and R1 represents a hydrogen atom or an organic group) Examples of useful compounds include diallyl isophthalate, diallylthenephthalate, bisphenol diallyl ethers, styrene, allylbenzene, and α-methylstyrene. The molar ratio of the polymerizable polyfunctional triazine compound and the polymerizable unsaturated compound is 75:25 to 2.
5:75, preferably copolymerized in the presence or absence of a solvent.

In addition, the 1,2-polybutadiene component in the resin composition of the present invention includes 1,2-voriptadiene homopolymer, yielded 1,2-polybutadiene, and 1,2-polybutadiene 1,2-terminated 7-terminated 1,2-polybutadiene. - polybutadiene glycol, 1. ♀-Bolybutadiene dicarboxylic acid, urethane modified 1゜2-polybutadiene, maleated 1.2-
Use derivatives such as polymers and copolymers of a, which contain 1,2-polybutadiene with a hinyl side chain group as a basic component, such as polybutadiene, acrylic-terminated 1,2-polybutadiene, and ester-terminated 1,2-polybutadiene. be able to.

The blending ratio (weight) of the prepolymer containing the monopolyfunctional triazine compound as a repeating unit and the 1,2-polybutadiene quasi is selected in the range of 80:20 to 20:80,
If the content of the former is higher than this, an increase in the contact rate and brittleness of the cured resin will be observed, and if it is low, the tack-free property of the prepreg, adhesion with copper foil, and other laminate properties will be affected. The effect of prepolymers containing triazine compounds on A particularly preferred ratio of both components is approximately 30 to 30 Nia.

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

First, a prepolymer obtained by polymerization or copolymerization of a polymerizable polyfunctional triazine compound and 1°2-polybutadiene or a derivative thereof are dissolved in an organic solvent to prepare pheno. At this time, for the purpose of promoting dissolution, heating may be performed at a temperature of 80C or less for about 30 minutes.

Examples of organic solvents include acetone, methyl ethyl ketone, toluene, xylene, 2-methoxyethanol, 3-
Examples include methoxypropanol, N,N-dimethylformamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide, trichlorethylene, 1.1.2-trichloroethane, etc., and are limited to solvents that can uniformly mix the component polymers. It can be used without being affected. A radical polymerization initiator was added to the prepared pheno and an impregnating wax was prepared.
Let it be i-varnish. Typical examples of radical polymerization initiators include benzoyl peroxide, dicumyl peroxide, methyl ethyl ketone peroxide, 1-phthyl peroxide, t-butyl peroxylaut, and di-t-butyl peroxy. Tallate, dibenzyl peroxide, etc. are added in an amount of 0.1 to 10 parts by weight per 100 parts by weight of the resin composition. Next, the obtained phenol for impregnation is applied to a sheet-like base material and dried at room temperature to 170C to obtain a non-tacky prepreg. The selection of the drying temperature at this time is determined by the solvent, initiator, etc. used. Layer the required number of prepregs obtained at the end, 100 to 250
A heat curing reaction is carried out at C under a pressure of 1 to 100 f/cd to obtain a laminate.

[Embodiments of the invention]

Example 1 Prepolymer of triallylisocyanurate (manufactured by Nippon Kasei) and 1,2-polybutadiene (molecular weight approximately 1.5×10
', side chain vinyl group content of 90% or more) was dissolved by heating at 60C for 30 minutes in methyl ethyl ketone, and the polymer blending ratio was 5:
5 (weight ratio) and a solid content of 40% was obtained. Furthermore, after adding 5 parts by weight of dicumyl peroxide as a radical polymerization initiator to 100 parts by weight of the varnish, this phenol was added to a glass cloth cloth (Nittobo IKE Glass, thickness: 0.05 mm).
A duck-free prepreg was obtained by impregnating and coating the material (1) and drying it in constant temperature air at 110C for 20 minutes. Next, 10 sheets of the prepreg were stacked at a pressure of 30 rCyf/i.

Heated at a temperature of 130C for 30 minutes, further raised the temperature to 170C to perform an adhesive curing reaction in a press for 1 hour, and then
A laminate was produced by applying after-cure in air at a constant temperature of 20tZ'' for 2 hours.

Example 2 A polybutadiene component consisting of the 1,2-polybutadiene used in Example 1 and 1,2-polybutadiene with a lower molecular weight (molecular weight 3 x 103, manufactured by Nippon Soda), and triallyl isocyanurate-diallylisophthalate (mol. Ratio 3 near) copolymerized prepolymer and 8C in xylene.
I' was heated and dissolved for 30 minutes to prepare a phenol having a polymer blending ratio of 5:5 (by weight) and a solid content of 40%.

The subsequent steps were performed in the same manner as in Example 1 to obtain a laminate.

Example 3 1,2-polybutadiene used in Example 1 and Tris(2
-Hydroxyethyl) esterified product of isocyanurate acid and acrylic acid (manufactured by Hitachi Chemical).

FA-731A)' was heated and dissolved in a #cinema for 800.30 minutes, polymer blending ratio 723 (weight), solid content 4.
Obtained 0% pheno. The subsequent steps were the same as in Example 1 to produce a laminate.

Example 4 A copolymer of 1,2-polybutadiene (EPB-42M, manufactured by Nippon Soda) and triallyl isocyanurate-bisphenol F diallyl ether (molar ratio 7:3) was prepared in xylene at 80°C. The mixture was heated and dissolved for 30 minutes to obtain pheno with a polymer blending ratio of 5:5 (weight ratio) and a solid content of 40%. The subsequent steps were carried out in the same manner as in Example 1 to produce a laminate.

Example 5 Diallyl cyanurate and triplyl cyanurate (weight ratio 5:5) were dissolved in xylene, the polybutadiene used in Example 1 was mixed in a weight ratio 5:5, and the resin content was 40%. I got it. The subsequent steps are Example 1
A laminate was produced in the same manner as above.

Comparative Example A plywood board was produced in the same manner as in Example 1, using only 1,2-polybutadiene without mixing the triallylisocyanurate prepolymer described in Example 1.

The main characteristics of the test boards and the heat resistance of the cured resins according to the examples and comparative examples are shown in the table.

[Effects of the Invention] By using the resin composition of 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 it is also υ equivalent to that of conventional products. It has become possible to produce a low dielectric constant laminate material that has improved copper foil adhesion strength, mechanical strength, and heat resistance, and is suitable for use in multilayer printed circuit boards.

Claims (1)

[Claims] 1. (a) The following general formula I or II ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [ I ] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [II] (In the formula, R^1 , R^2 and R^3, R^4, R^5
and R^6 each represent a hydrogen atom or an organic group, and at least two of the three groups belonging to each formula are organic groups containing a polymerizable unsaturated bond) A curable resin composition comprising as essential components a prepolymer containing as a repeating unit, and (b) 1,2-polybutadiene or a derivative thereof. 2. The prepolymer is an s-triazine compound represented by the general formula I or II and the general formula III R-Ar-R^1 (wherein Ar represents a divalent aromatic group, and R represents a polymerizable unsaturated The resin composition according to claim 1, which is a copolymer with a polymerizable compound represented by an organic group containing a bond, and R^1 represents a hydrogen atom or an organic group. 3. The resin composition according to claim 1 or 2, wherein the blending ratio (weight) of the prepolymer and 1,2-polybutadiene or its derivative is from 80:20 to 20:80. 4. In a laminate in which prepregs made by impregnating and drying a synthetic resin into a base material are laminated and bonded, the synthetic resin has (a) the following general formula I or II ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [ I ] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [II] (In the formula, R^1, R^2, and R^3, R^4, R^5
and R^6 each represent a hydrogen atom or an organic group, and at least two of the three groups belonging to each formula are organic groups containing a polymerizable unsaturated bond) 1. A curable resin composition comprising, as essential components, a prepolymer containing as a repeating unit, and (b) 1,2-polybutadiene or a derivative thereof. 5. (a) General formula I or II below ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [ I ] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [II] (In the formula R^1, R^2 and R^ 3, R^4, R^5 and R^6 each represent a hydrogen atom or an organic group,
and at least two of the three groups belonging to each formula are organic groups containing a polymerizable unsaturated bond)
- a step of impregnating a sheet-like base material with a varnish containing a prepolymer containing a triazine compound as a repeating unit, (b) 1,2-polybutadiene or a derivative thereof, and (c) a radical polymerization initiator, the impregnated body A method for manufacturing a laminate, which comprises the steps of: drying the prepreg to form a prepreg; and laminating the prepreg and integrally molding the prepreg under pressure.