JPH05329986A - Composite laminated sheet - Google Patents

Abstract

PURPOSE:To improve interlaminar bonding strength, heat resistance, electric insulating properties, dielectric characteristics and through-hole reliability in a composite laminated sheet containing a thermosetting resin having an unsaturated bond in its molecule as a resin matrix. CONSTITUTION:A composite laminated sheet consists of a surface layer composed of a thermosetting resin modified with a butadiene polymer having an unsaturated bond and a vinyl group or a carboxyl group in its molecule and a center layer composed of a thermosetting resin containing the butadiene polymer in a smaller amount as compared with the surface layer or containing no butadiene polymer.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a composite laminate. The composite laminate of the present invention is particularly suitable for electrical insulation or printed wiring boards, but is not limited thereto.

[0002]

2. Description of the Related Art A composite laminated board is a laminated board using two or more kinds of base materials. Usually, a surface layer base material is a glass cloth, and a central layer base material is a glass nonwoven fabric (glass paper,
It is a laminated plate made of glass mat), paper, organic fiber cloth, organic fiber non-woven fabric or mixed-textured non-woven fabric of various fibers. Epoxy resins are often used as matrix resins for composite laminates, but thermosetting resins having unsaturated bonds in the molecule, such as unsaturated polyester resins and vinyl ester resins that are liquid at room temperature, are also used. This resin impregnates the base material with a liquid resin that does not contain a solvent and cures it.
It does not require solvent removal, is suitable for continuous lamination method, and is excellent in safety and resource saving. However, when the unsaturated polyester resin or vinyl ester resin is used as the matrix resin, the interlayer adhesive strength becomes weak. Therefore, it has been proposed to add a butadiene polymer to improve the adhesive strength (see JP-A-63-145338).

[0003]

However, when the butadiene polymer is added to the unsaturated polyester resin or vinyl ester resin, the interlayer adhesion is improved, but the heat resistance,
The electrical insulation, dielectric properties, and through hole reliability will be reduced.

An object of the present invention is to improve the heat resistance, electrical insulation, dielectric properties and through-hole reliability of a composite laminate using a thermosetting resin having an unsaturated bond in the molecule as a matrix resin. It is a thing.

[0005]

In the present invention, a thermosetting resin having an unsaturated bond in the molecule and modified with a butadiene-based polymer is used as a resin for the surface layer, and the amount of the butadiene-based polymer is in the surface layer. And a thermosetting resin having an unsaturated bond in the molecule, which is less than or does not contain a butadiene-based polymer, is used as a resin for the central layer.

The butadiene-based polymer in the present invention includes a polybutadiene polymer having at least one vinyl group or a carboxyl group in the molecule or a butadiene-acrylonitrile copolymer, and these are used alone or in combination.

These butadiene-based polymers are reacted with a thermosetting resin to be incorporated in the resin skeleton or added to the thermosetting resin. The ratio of these butadiene-based polymers to the resin impregnated with the base material is about 10 to 25% by weight of the total amount of the resin for the surface layer, and 0 for the central layer, that is, not contained at all or 9% by weight or less. To do. When the surface layer is less than 10% by weight, the effect of improving the interlayer adhesive force of the base material of the surface layer is small, and is 25% by weight.
When it is more, the heat resistance and electric insulation of the laminated plate will be deteriorated. About 9% by weight of the central layer,
Heat resistance, electrical insulation, and through-hole reliability are reduced.

As the thermosetting resin having an unsaturated bond in the molecule, unsaturated polyester resin vinyl ester resin, thermosetting acrylic resin, diallyl phthalate resin,
and so on. Of these, unsaturated polyester resins and vinyl ester resins are preferable. These are single or 2
You may use it in combination of 2 or more types. Curing of the resin composition is performed by a method using an organic peroxide by a usual method, a method by light or electron beam irradiation, or the like. If necessary, a curing accelerator and a sensitizer are also used.

When an unsaturated polyester resin, vinyl ester resin or the like is used, a continuous laminating method in which the steps of impregnating a substrate with a resin, laminating and curing are continuously performed is desirable. In this case, the base material may be impregnated with each of the base materials individually or with a plurality of the base materials simultaneously.

Resins containing a polymerizable monomer such as styrene, such as unsaturated polyester resins and vinyl ester resins, generally have poor adhesiveness with metals, and therefore, for example, when a metal-clad laminate is used. 2 to 10% by weight of (meth) acrylic acid in the resin of the surface layer in contact with the metal foil
When blended, the adhesion and physical properties with metal foil can be improved.

If necessary, known flame retardants and inorganic fillers are added to these thermosetting resins. Flame retardants include bromine-based, phosphorus-based, and antimony-based compounds. As the inorganic filler, clay, talc, wollastonite, silica, glass powder, aluminum hydroxide, magnesium hydroxide, alumina, calcium aluminate, calcium carbonate and the like can be used. When a filler is used, the compounding amount of the resin for impregnating the base material of the central layer is minimized. Then, the decrease in interlayer adhesive strength is small and the effect of the present invention becomes more remarkable.

[0012]

[Function] Since the amount of the butadiene-based polymer of the resin for the central layer is reduced, heat resistance, electric insulation, dielectric properties,
Through hole does not reduce reliability.

[0013]

【Example】

Synthesis of Resin A Biphenol A type epoxy resin (epoxy equivalent 190g
/ Eq) 202 parts (parts by weight, the same applies hereinafter), tetrabromobisphenol A type epoxy resin (epoxy equivalent 400
g / eq) 450 parts, 188 parts of methacrylic acid and 100 parts of styrene are reacted in the presence of triethylamine at 90 ° C. for 9 hours, and then 260 parts of styrene are added thereto to obtain 18% by weight of bromine and 30% by weight of styrene. Of vinyl ester resin was obtained.

Synthesis of Resin B Biphenol A type epoxy resin (epoxy equivalent 190 g
/ Eq) 186 parts, tetrabromobisphenol A type epoxy resin (epoxy equivalent 400 g / eq) 450 parts,
A terminal carboxyl group-containing butadiene-acrylonitrile copolymer 202 and 120 parts of styrene were reacted in the presence of triethylamine at 90 ° C. for 9 hours, 172 parts of methacrylic acid was further reacted, and then 313 parts of styrene was added, and bromine was added. A butadiene acrylonitol copolymer-modified vinyl ester resin containing 15% by weight, 14% by weight of butadiene-acrylonitrile copolymer and 30% by weight of styrene was obtained.

Synthesis of Resin C Bisphenol A type epoxy resin (epoxy equivalent 190
g / eq) 157 parts, tetrabromobisphenol A type epoxy resin (epoxy equivalent 400 g / eq) 407
Parts, 208 parts of a terminal carboxyl group-containing polybutadiene and 100 parts of styrene in the presence of triethylamine,
React at 95 ° C for 2 hours, then add 290 parts of styrene to obtain 16% by weight of polybutadiene and 30% by weight of styrene.
To obtain a polybutadiene-modified vinyl ester resin.

Example 1 A resin composition prepared by mixing 100 parts of resin B with 1 part of cumene hydroperoxide was applied to a surface layer base material (having a thickness of 0.2 mm and a glass cloth having a basis weight of 210 g / m ² for one glass cloth). A6
A resin composition containing 0 part, 40 parts of resin B, 50 parts of aluminum hydroxide and 1 part of cumene hydroperoxide was used as a center layer base material (thickness 0.45 mm, ^two glass nonwoven fabrics having a basis weight of 50 g / m ² ). Each was impregnated continuously, laminated, and laminated with copper foil having a thickness of 18 μm on both sides, continuously passed through a curing oven and heated at 100 ° C. for 30 minutes and subsequently at 170 ° C. for 30 minutes.

Example 2 A resin composition prepared by mixing 100 parts of Resin C with 1 part of cumene hydroperoxide was used as a resin for a surface layer substrate (having a thickness of 0.2 mm and a glass cloth having a basis weight of 210 g / m ² ). A8
A resin composition containing 0 part, 20 parts of resin C, 50 parts of aluminum hydroxide and 1 part of cumene hydroperoxide was used as a central layer base material (thickness 0.45 mm, ^two glass nonwoven fabrics having a basis weight of 50 g / m ² ). Each was impregnated continuously, laminated, and laminated with copper foil having a thickness of 18 μm on both sides, continuously passed through a curing oven and heated at 100 ° C. for 30 minutes and subsequently at 170 ° C. for 30 minutes.

Example 3 Vinyl group-terminated butadiene-acrylonitrile copolymer 1
5 parts, resin A 75 parts, cumene hydroperoxide 1
Part of the resin composition, the surface layer base material (thickness 0.2 m
m, a glass cloth having a basis weight of 210 g / m ² addressed to 100 parts of resin A, 50 parts of aluminum hydroxide, and 1 part of cumene hydroperoxide was used as a center layer base material (thickness: 0. 45 mm and ² g of glass non-woven fabric having a basis weight of 50 g / m ² ) were continuously impregnated and laminated,
18 μm thick copper foil was attached to both sides and continuously passed through a curing oven for heating at 100 ° C. for 30 minutes, followed by 17
Heated at 0 ° C. for 30 minutes.

Comparative Example A resin composition consisting of 100 parts of Resin B and 1 part of cumene hydroperoxide was continuously impregnated and laminated on the same surface layer base material and center layer base material as in Example 1 to obtain a thickness of 18 μm on both sides.
m of copper foil were laminated and continuously passed through a curing oven for heating at 100 ° C. for 30 minutes and then at 170 ° C. for 30 minutes.

The obtained laminate was examined for interlayer adhesion, heat resistance, insulation resistance, dielectric properties and through hole reliability. The results are shown in Tables 1 and 2. The test method is as follows.

Heat resistance: A laminated plate cut into 50 × 50 mm is 121 ° C., 0.2M
Abnormality after treatment for 4 hours in saturated steam of Pa for 30 seconds in 260 ° C. solder.

Insulation resistance For a laminated plate treated for 6 hours under the same conditions as heat resistance,
Measured according to JIS C6481.

Interlayer adhesion strength The peel strength of the glass cloth of the surface layer is determined by JISC6.
Measured in the same way as the copper peel strength in 481.

Dielectric properties (dielectric constant and dielectric loss tangent) Measured according to JIS C6481 (normal value).

Through-hole reliability 200 through-holes with a diameter of 1 mm are formed on a double-sided copper-clad laminate.
The individual sample is placed in water at 20 ° C for 10 seconds and 260 ° C.
The number of cycles until the rate of change in resistance value exceeds 10% after repeating the cycle of dipping in the oil for 10 seconds.

[0026]

[Table 1]

[0027]

[Table 2]

[0028]

According to the present invention, the central layer is made of a resin composition containing a small amount of a butadiene-based polymer, and the surface layer is made of a resin composition containing a necessary butadiene-based polymer. It is possible to obtain a composite laminate having excellent heat resistance, electrical insulation, dielectric properties, and through hole reliability.

Claims (2)

[Claims] 1. A thermosetting resin having an unsaturated bond in the molecule and modified with a butadiene-based polymer is used as the resin for the surface layer, and the amount of the butadiene-based polymer is less than that of the surface layer or the butadiene-based polymer is less than the surface layer. A composite laminate comprising a thermosetting resin having an unsaturated bond in the molecule as a resin for the central layer, which does not include coalescence. 2. The laminate according to claim 1, wherein the butadiene-based polymer is a polybutadiene polymer having at least one vinyl group or a carboxyl group in the molecule or a butadiene-acrylonitrile copolymer.