JPS6356548A - Thermosetting resin composition, laminated sheet produced by using same and production thereof - Google Patents

Abstract

PURPOSE:To obtain a composition suitable for the production of a multilayer printed circuit board having excellent flame-retardance, heat-resistance and electrical characteristics, by adding a specific flame-retardant and a polybutadiene prepolymer III to a prepolymer composed of a poly(p- hydroxystyrene) derivative. CONSTITUTION:A prepolymer composed of a poly(p-hydroxystyrene) derivative of formula I (A is H, alkyl or halogen; R is 2-4C alkenyl or alkenoyl; m is 1-4; n is 1-100) is compounded with a flame-retardant of formula II (X is H or alkyl) and a 1,2-polybutadiene prepolymer III having unsaturated group at the side chain. The group R in the formula I is preferably allyl, vinyl, isobutenyl, acrynoyl, etc. A prepreg can be produced by using the composition as a varnish and impregnating in a sheet substrate.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a thermosetting resin composition, and particularly to a laminated material suitable for multilayer printed wiring boards having excellent flame retardancy, heat resistance, and electrical properties. .

[Conventional technology]

Conventionally, laminates made of 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 of large computers, printed circuit boards with excellent electrical characteristics are required to improve signal transmission speed. In particular, a printed circuit board with a low dielectric constant is required in order to shorten signal transmission delay time and reduce circuit thickness. Polybutadiene-based materials are currently being developed as lower dielectric constant laminate materials to replace the polyimide laminate materials used in large-scale computers.

(Japanese Patent Publication No. 5G-21926) [Problems to be Solved by the Invention] However, the polybutadiene materials currently being developed have a lower specific m-electricity than polyimide materials.

Although it is a material suitable for high-speed signal transmission, it has many problems such as low adhesiveness during prepreg, low mechanical strength, and insufficient heat resistance. Also, since polybutadiene is flammable,
It is necessary to consider flame retardancy.

For polybutadiene, the addition of low-molecular crosslinked flame retardants is generally being considered. However, these low-molecular crosslinked flame retardants have the problem that they have a significant adverse effect on electrical properties and that the thermal decomposition initiation temperature, which is a measure of heat resistance, becomes low. Therefore, studies are being conducted on high molecular weight crosslinked flame retardants.

Typical examples include alkenyl and alkenoyl esters of poly(p-hydroxystyrene), which have the advantage of having a relatively low dielectric constant and not impairing heat resistance. However, polybutadiene and a polymeric flame transport agent alone do not provide sufficient fluidity of the resin during lamination and bonding under pressure.

An object of the present invention is to provide a flame-retardant, low dielectric constant laminate material with excellent heat resistance.

[Means for solving problems]

To summarize the present invention, the first aspect relates to a thermosetting resin composition, and its characteristics are the following general formula I (wherein A is hydrogen, an alkyl group, or a halogen group, and R has 2 carbon atoms ~4 alkenyl or alkenoyl group, and 1
m is 1-4. A prepolymer made of a poly(p-hydroxystyrene) derivative represented by (n represents a number from 1 to 100) and a flame retardant represented by the following general formula (wherein, X represents hydrogen or an alkyl group). The second aspect of the present invention is to impregnate a sheet-like base material with a thermosetting resin composition, which contains a 1゜2-polybutadiene prepolymer (m) having an unsaturated group in the side chain as an essential component. The third aspect relates to a method for producing a laminate, which is formed by laminating and molding prepregs obtained by drying.

Among the prepolymers that are essential components of the thermosetting resin composition of the present invention, specific examples of those represented by the general formula I include poly(p-hydroxystyrene) vinyl ether, isobutenyl ether, allyl ether, and acrylic ester. , methacrylate ester, epoxy acrylate ester,
These include epoxy methacrylic acid ester and its bromide.

In addition, 1,2-polybutadiene prepolymers (III) with unsaturated bonds in side chains include 1,2-polybutadiene homopolymers, cyclized 1,2-polybutadiene, and epoxy-modified 1,2-polybutadiene. Polybutadiene, terminal epoxidized 1,
2-polybutadiene, 1゜2-polybutadiene glycol, 1,2-polybutadienecarboxylic acid, urethane-modified 1,2-polybutadiene, maleated 1,2-polybutadiene, terminal acrylic-modified 1,2-polybutadiene, terminal ester There are various polymers and derivatives such as copolymers containing 1,2-polybutadiene having a vinyl group in the side chain as a basic component, such as modified 1,2-polybutadiene.

The weight mixing ratio of these two prepolymers ■ and ■ is 80
:20 to 20:80, and if the amount of the former is larger than this, there will be problems with electrical properties, cracking during molding, etc. Moreover, if the latter is added in a large amount, there are problems with flame retardancy, mechanical strength, etc.

Preferably, the blending ratio of both is 60:40 to 40:6.
It is 0.

A thermosetting resin composition made by combining these two prepolymers is a flame-retardant, low dielectric constant resin with excellent heat resistance.
Sufficient resin fluidity cannot be obtained during laminate molding. Therefore, by replacing part of the general formula (2) with a low molecular weight flame retardant having a relatively low melting point, the fluidity of the resin can be significantly improved. Low-molecular cross-linked flame retardant without compromising heat resistance.

In addition, as a flame retardant with a low melting point, an ester of bisphenol A with diacrylate or dimethacrylate contains an ether bond.

The melting point is around 70°C, which is more than 100°C lower than that of a material that does not contain an ether bond, and the fluidity can be significantly improved. These low molecular weight fuels are represented by the general formula (2), and specific examples include diacrylate, citacrylate, and diacrylate of the reaction product of tetrabromobisphenol A and ethylene oxide.

The amount of the prepolymer represented by the general formula 1 to be replaced with this flame retardant is determined by selecting a polymerization blending ratio of the prepolymer represented by the general formula 1 and the general formula 2 in the range of 90:10 to 40:60. If the amount of general formula (2) is greater than this range, there will be no effect of improving fluidity, and if it is less than this range, problems will arise with heat resistance, prepreg adhesiveness, etc.

Next, a method for manufacturing a laminate according to the present invention will be explained. First, a festival is prepared by dissolving general formula (1), general formula (2), and polybutadiene prepolymer (2) in a predetermined formulation in an organic solvent. At this time, it may be heated at an appropriate temperature to promote dissolution. Examples of organic solvents include toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone,
ethanol, methanol, 3-methoxypropertool,
N, N-dimethylformamide, N-methylpyrrolidone, dimethyl sulfoxide, trichlorodiethylene, 1,
Examples include 1.2-trichloroethane.

Any solvent that can uniformly mix the component polymers mentioned above can be used without limitation. A radical polymerization initiator is added to this 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 perbenzoate, t-butyl peroxylaurate, di-t-butyl peroxy phthalate, dibenzyl peroxide. There are oxides, etc., and resin composition 1
It is preferably added in an amount of 0.1 to 10 parts by weight. 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. Layer the required number of prepregs finally obtained at 1-1oO at 1oO-250℃.
A heat curing reaction is performed under a pressure of kgf/d to obtain the product MFi.

As the sheet-like base material, almost all those commonly used for laminated materials can be used. Inorganic fibers include E glass containing 5iOz, AL20a, etc., and C
Glass, A glass, S glass, D glass, YM-31-
There are various types of glass fibers such as A glass and Q glass using quartz. Also.

Examples of organic fibers include aramid fibers containing a polymer compound having an aromatic polyamide-imide skeleton.

〔Example〕

<Example 1> Methacrylate prepolymer of bromide poly(p-hydroxystyrene) (manufactured by Maruzen Oil Co., Ltd.), dimethacrylate (dimethacrylate) of the reaction product of tetrabisphenol A and ethylene oxide
Industrial pharmaceutical layer) and epoxy-modified polybutadiene (manufactured by Nippon Soda) were dissolved by heating at 80'C for 30 minutes using methyl isobutyl ketone as a solvent at a weight mixing ratio of 35:50:15.
A varnish with a solid content of 40% was obtained. Furthermore, 2 parts by weight of dicumyl peroxide (manufactured by NOF Corporation) as a radical polymerization initiator and 4 parts by weight of 2E4MZ and ADINE (manufactured by Shikoku Kasei) as epoxy curing agents were added to 100 parts by weight of the solid content of the varnish. Thereafter, this varnish was impregnated and coated on glass cloth (Nittobo E glass, thickness O, OS mm) and dried in constant temperature air at 100 to 120° C. for 20 minutes to obtain a tack-free prepreg. Next, 20 sheets of prepreg were stacked and heated at a pressure of 3.degree. kgf/an and a temperature of 130.degree. C. for 30 minutes, and then the temperature was raised to 220.degree. C. for an hour to conduct an adhesive curing reaction in a press to produce a laminate.

<Example 2> Bromide poly(p-hydroxystyrene) (Maruzen Sekiyu T!5)
) acrylate prepolymer and tetrabisphenol A
and ethylene oxide reactant diacrylate (No.
Industrial pharmaceutical layer) and epoxy-modified polybutadiene (manufactured by Nippon Soda) were dissolved by heating at 80° C. for 30 minutes using methyl isobutyl ketone as a solvent at a weight mixing ratio of 35:50:15 to obtain a varnish with a solid content of 40%. Thereafter, a laminate was obtained in the same manner as in Example 1.

<Comparative Example 1> Brominated poly(p-hydroxystyrene) used in Example 1
The methacrylate and epoxy-modified polybutadiene were mixed in a weight ratio of 50:50, and then a varnish was prepared in the same manner as in Example 1, and a laminate was also obtained.

Ratio Example 2> Brominated poly(p-hydroxystyrene) used in Example 2
7 acrylate and epoxy-modified polybutadiene in a weight mixing ratio of 50:50, a varnish was prepared in the same manner as in Example 2, and a laminate was obtained.

As shown in the table, by using a low molecular weight flame retardant in the present invention in combination, resin fluidity during molding can be significantly improved without impairing heat resistance and flame retardancy.

〔Effect of the invention〕

According to the present invention, as a polybutadiene material, the dielectric constant is 3.5, which is lower than that of conventional polyimide materials (relative dielectric constant 4.7), and when applied to multilayer printed circuit boards, the signal transmission speed can be significantly increased. We can expect improvement. Furthermore, resin fluidity during molding can be significantly improved without sacrificing properties such as heat resistance, making it a low dielectric constant laminate suitable for use in multilayer printed circuit boards with flame retardancy and heat resistance, replacing polyimide materials. 0,) which can produce materials

Claims (1)

[Claims] 1. The following general formula I ▲There are numerical formulas, chemical formulas, tables, etc.▼... I (In the formula, A is hydrogen, an alkyl group, or a halogen group, and R has 2 to 4 carbon atoms. is an alkenyl or alkenoyl group, m represents a number from 1 to 4, and n represents a number from 1 to 100)
A prepolymer made of a poly(p-hydroxystyrene) derivative represented by the following, and a flame retardant represented by the following general formula II ▲ Numerical formula, chemical formula, table, etc. ▼ (wherein, X represents hydrogen or an alkyl group). , a thermosetting resin composition comprising as an essential component a 1,2-polybutadiene prepolymer III having an unsaturated group in a side chain. 2. Claim 1 is characterized in that R of the prepolymer represented by general formula I is an allyl group, a vinyl group, an isobutenyl group, an acrinoyl group, a methacrynoyl group, an epoxyacrynoyl group, or an epoxymethacrynoyl group. A thermosetting resin composition. 3. 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 has a general formula
I, ▲Mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, A is hydrogen, an alkyl group, or a halogen group, R is an alkenyl or alkenoyl group having 2 to 4 carbon atoms, and m is 1 to 4. 4, n represents a number from 1 to 100) and the following general formula II ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ (In the formula, X is hydrogen or alkyl A laminate, characterized in that it is a thermosetting resin composition comprising a flame retardant represented by (representing a group) and a 1,2-polybutadiene prepolymer (III) having an unsaturated group in a side chain as essential components. 4. The following general formula I ▲ Numerical formulas, chemical formulas, tables, etc. 1 to 4, n represents a number from 1 to 100)
A prepolymer made of a poly(p-hydroxystyrene) derivative represented by the following general formula II ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ A varnish containing a thermosetting resin composition whose essential components are a flame retardant represented by the following formula and a 1,2-polybutadiene prepolymer (III) having an unsaturated group in the side chain is applied to a sheet-like base material. A method for manufacturing a laminate using a thermosetting resin composition, which comprises the steps of impregnating the prepreg, and laminating the prepregs and integrally molding them under pressure.