JPH0590719A - Manufacture of glass fiber reinforced laminate plate for electrical use - Google Patents

Abstract

PURPOSE:To furnish a manufacture of a glass fiber reinforced laminate plate for electrical use which enables attainment of the laminate plate for electrical use being improved in terms of adhesion of an inside nonwoven fabric base to resin for impregnation and excellent in a water-absorbing characteristic. CONSTITUTION:In a manufacture of a laminate plate for electrical use comprising processes wherein a plurality of lines of bases each formed by disposing glass cloth outside oppositely and nonwoven fabric inside are conveyed in parallel continuously, the lines of the bases are impregnated discretely, in the course of conveyance, with a hardening resin liquid being liquid of itself and not producing a reaction subproduct, the impregnated bases are laminated in one body, a cover sheet and/or a metal leaf is laminated thereon, hardening is made continuously and then cutting is made in a desired size, the nonwoven fabric is subjected to pretreatment with a radical polymerization type hardening resin liquid beforehand. Thereby the laminate plate for electrical use being excellent in a water-absorbing characteristic is obtained.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for producing a glass fiber reinforced electrical laminate. Here, the electrical laminate means an insulating laminate used as a substrate for various electric and electronic components and a metal foil-clad laminate used as a printed circuit board.

[0002]

2. Description of the Related Art In recent years, demands for the quality of laminated boards used in consumer and industrial electronic devices have become more and more severe, and as the printed circuit boards have become lighter, thinner, shorter and smaller, high-density mounting of components has progressed. The usage rate of double-sided metal foil clad laminates is increasing. Conventionally in these fields, FR-4, G-10, CEM mainly by the combination of glass base material and epoxy resin is used.
-3 and the like are used, and particularly in recent years, the use ratio of CEM-3 has been increasing.

Japanese Patent Laid-Open Nos. 55-4838 and 5 of the present applicant
No. 6-98136 discloses a continuous method for producing an electrical laminate, and as the above method, a curable unsaturated resin such as an unsaturated polyester resin or an epoxy acrylate resin is suitable. It is known that various good characteristics can be imparted as compared with the system, and that it has many advantages as a method for producing a CEM-3 type copper clad laminate. A conventional method for manufacturing a glass fiber reinforced electrical laminate will be described below.

A method for producing a glass cloth reinforced electrical laminate is disclosed in Japanese Patent Laid-Open No. 62-268632 of the present applicant. The above method is a radical polymerization in which at least two base material rows having glass cloth on both outer sides are continuously conveyed in parallel, and are individually liquidized to the above-mentioned base material rows without generating a reaction product upon curing. In a method for manufacturing an electrical laminate, which includes a step of impregnating a mold resin solution, laminating an impregnated base material, laminating a cover sheet and / or a metal foil, continuously curing, and cutting to a desired size. The method further includes a step of pretreating the glass cloth with a radical polymerization type curable resin solution having high adhesion to the glass cloth with the impregnating resin solution. As described above, in the conventional manufacturing method, the non-woven fabric used in the middle is generally not pretreated.

[0005]

However, in the above-mentioned conventional method, the adhesion between the inner non-woven fabric substrate and the impregnating resin is poor, and the water absorption rate or moisture absorption rate of the laminated plate may not be sufficient.

The present invention solves the above-mentioned problems of the prior art. By pretreating a non-woven fabric with a radical-polymerizable curable resin solution in advance, it is possible to improve the water absorption rate and moisture absorption rate of a laminated plate. An object of the present invention is to provide a method for manufacturing a laminated board for reinforced electricity.

[0007]

In order to achieve this object, the method for producing a glass fiber reinforced electrical laminate of the present invention comprises:
Glass cloth on both outside and nonwoven fabric on the inside are continuously conveyed in parallel to a plurality of rows of base materials, and each of the base material rows is individually cured in a liquid state without causing a reaction by-product during curing. In a method for producing an electrical laminate, which includes a step of impregnating a resin solution, laminating an impregnated base material, laminating a cover sheet and / or a metal foil, continuously curing, and cutting to a desired dimension. First, there is a step of pretreating the above-mentioned non-woven fabric with a radical polymerization type curable resin liquid.

[0008]

With the above structure, the adhesion between the inner non-woven fabric substrate and the impregnating resin is improved, so that a glass fiber reinforced electrical laminate having excellent water absorption characteristics can be obtained.

[0009]

EXAMPLES In carrying out the present invention, the non-woven fabric substrate to be placed inside is used after being subjected to the pretreatment described here, and is disclosed in, for example, JP-A-62-268632 of the present applicant. The applied technology can be applied.

It is preferable to use glass paper as the non-woven fabric. Glass paper is 1 / 20μ thick
It is a long sheet-like material obtained by dispersing m glass fibers in water and wet-making paper using an acrylic resin, polyvinyl alcohol, epoxy resin, melamine resin or the like as a binder. In addition, as the non-woven fabric, a glass mixed paper made of paper and glass fibers, a non-woven fabric made of synthetic fibers such as polyester and aramid, rayon, and asbestos may be used.

The resin used for the pretreatment of the non-woven fabric is not only epoxy acrylate resin and urethane acrylate resin, but also the same as impregnating resin such as unsaturated polyester resin, polyester acrylate resin, diallyl phthalate resin and other radical polymerization type curing. Any resin can be used. A rubber component may be incorporated or blended into the polymer backbone to improve adhesion, the amount being 2
To 50% by weight is preferred.

A catalyst or a polymerization initiator is preferably used for curing the radical-polymerizable resin used for the pretreatment of the nonwoven fabric, but it is not always necessary. As the polymerization initiator, known general organic peroxides can be used. For the purpose of the present invention, JP-A-55-53013 is used.
The aliphatic peroxides disclosed in Japanese Patent Laid-Open Publication No. 2003-242242 are preferable, and it is more preferable to use one selected from the aliphatic peroxyesters alone or in combination. Specifically, for example, di-t-butyl peroxide, 2,5-dimethyl-2,5- (t-butylperoxy) hexane, acetyl peroxide, isobutyryl peroxide, t-butylperoxy-2- Ethyl hexanoate and the like. Aliphatic peroxyesters include, for example, t-butyl peroxyacetate, t-
Butyl peroxyisobutyrate, t-butyl peroxy-2-ethyl hexanoate, t-butyl peroxy laurate and the like.

The pretreatment resin liquid for the non-woven fabric is diluted with a solvent or a liquid polymerizable crosslinking agent monomer to an appropriate viscosity before use.
The amount of the pretreatment resin liquid deposited is 10 to 300 parts by weight, preferably 50 to 150 parts by weight, and more preferably 70 to 1 part by weight as a solid content per 100 parts by weight of the glass nonwoven fabric.
20 parts by weight. If the adhered amount is too large, the impregnating property of the impregnating resin will be deteriorated, and if the adhered amount is too small, the intended effect will not be sufficiently exhibited.

The method of pretreating the non-woven fabric is arbitrary, but for example, the pretreating resin is diluted with a polymerizable monomer such as styrene which also serves as a solvent of 10 to 50% to prepare a pretreatment liquid having an appropriate viscosity. It may be attached by applying it to a non-woven fabric or dipping it.

Further, since a curing catalyst such as an organic peroxide is added to the resin solution for pretreatment of the nonwoven fabric, if the glass cloth after the adhesion is pre-cured, the curable resin solution is impregnated later. This is a preferred embodiment because it is possible to prevent the pretreatment resin attached at that time from being dissolved in the later impregnated resin solution, and thereby to reduce the treatment effect. The pretreatment can be carried out by incorporating it into a laminated plate continuous production line, or can be wound up on a roll and used.

The glass cloth used in the present embodiment is usually a glass filament having a thickness of about 9 .mu.m.
800 yarns are bundled into a satin weave, plain weave, plain weave,
This is a generic name for cloth woven in the vertical and horizontal directions by various weaving methods such as Aya. In the present invention, such a glass cloth is pretreated, and one layer is used on each of both outer sides.

In this embodiment, a mixture of unsaturated polyester resin and epoxy acrylate resin is used as the curable resin liquid. One of the features of the continuous manufacturing method is JP-A-55-483.
No. 8, JP-A-56-98136, JP-A-62-268.
As disclosed in Japanese Patent No. 632 or the like, a radical polymerization type curable resin liquid which is liquid itself and does not generate a reaction by-product upon curing is used for impregnation of a substrate. Therefore, it is sufficient that the resin before curing contains a radically polymerizable double bond unsaturated group and is cured by a radical polymerization reaction of the unsaturated group. The unsaturated polyester is a typical one, but other examples include epoxy acrylate resin, polyester acrylate resin, urethane acrylate resin, spirane resin, diallyl phthalate resin and the like. In addition, it is common to mix an inorganic filler such as aluminum hydroxide, antimony trioxide, alumina, clay, or talc with these impregnating liquids, but it is not always necessary in the present invention.

For the purpose of improving the warp characteristic, Japanese Patent Application No. 3-0.
Techniques similar to those shown in 49081 can be used.
In this case, the impregnating resin liquid contains an oligomer having a reactive group. As the oligomer having a reactive group, for example, aliphatic polyethers, polycaprolactones,
Vegetable oils, liquid polybutadiene rubbers, nitrile butadiene rubbers and the like are used. Examples of the aliphatic polyethers include polyethylene oxide, polypropylene oxide, polytetramethylene oxide, and copolymers of two or more kinds thereof. Moreover, what introduced the bis A skeleton to these aliphatic polyethers may be used. Examples of polycaprolactones include ε-caprolactone having a hydroxyl group having 1 to 3 functional groups. The molecular weight is 500 to 8000, preferably 1000 to 4000,
More preferably, it is 1500 to 3000. Molecular weight is 5
When it is 00 or less, the effect of improving the warp is small, and when it is 8000 or more, the compatibility with the unsaturated resin may deteriorate. The reactive group includes a double bond and a triple bond having radical reactivity, an epoxy group, an amino group, a hydrosyl group, a carboxyl group, and a silano group. In particular, an ethylene propylene oxide copolymer having a double bond at the terminal,
Propylene oxide is a string of oligomers with good reactive groups in the present invention. When such an oligomer having a reactive group is contained in the dipping resin liquid, the adhesiveness between the inner non-woven fabric substrate and the impregnating resin is often decreased, and the effect of the present invention is remarkable, which is a preferred embodiment. An embodiment of the present invention will be described below.

Example 1 Each outermost layer of the base material layer had a thickness of 180 μm and a basis weight of 210 g /
using a glass cloth m ^2, intermediate basis weight 40 g / m ²
A double-sided copper foil-clad unsaturated polyester laminate having a thickness of 1.2 mm, in which a copper foil having a thickness of 18 μm coated with an epoxy adhesive having a thickness of 40 μm was stretched on both sides using two layers of the glass paper of No. 2 was produced by a continuous production method. Glass paper
A urethane acrylate resin containing 50% of a styrene monomer was impregnated and dried at 160 ° C. for 5 minutes for pretreatment. The amount of resin adhered at this time was 100% by weight in terms of solid content per 100 parts by weight of glass paper. The glass cloth was impregnated with a urethane acrylate resin containing 50% of a styrene monomer, dried at 160 ° C. for 5 minutes, and pretreated. The resin adhesion amount at this time was 15% by weight in terms of solid content per 100 parts by weight of the glass cloth. As the impregnating resin, 70 parts by weight of flame-retardant unsaturated polyester resin (bromine content: 14% by weight), 30 parts by weight of epoxy acrylate resin, 4 parts by weight of antimony trioxide, 1 part by weight of benzoyl peroxide, 30 parts by weight of aluminum hydroxide. A liquid resin in which the parts were uniformly mixed was used. While placing the glass cloth on both outermost sides and the pretreated glass paper on the inner side and continuously conveying each base material,
After individually impregnating with the resin solution, they are combined and laminated with a copper foil on both side plates, and then continuously passed through a tunnel-type curing oven for 15 minutes at 100 ° C. and 10 minutes at 150 ° C. for thermal curing. It was

Example 2 As in Example 1, except that a liquid resin obtained by adding 10 parts of a maleinized terminal ethylene oxide propylene oxide random copolymer (KPX-1, Sanyo Kasei) to the impregnating resin was used. A 2-mm double-sided copper foil-clad unsaturated polyester laminate was manufactured by a continuous manufacturing method.

Example 3 A glass paper was pretreated by impregnating it with a urethane acrylate resin containing 75% styrene monomer and drying at 160 ° C. for 5 minutes. The resin adhesion amount at this time was 50% by weight in terms of solid content per 100 parts by weight of the glass paper. As in Example 1, except that this glass paper was used.
A 2-mm double-sided copper foil-clad unsaturated polyester laminate was manufactured by a continuous manufacturing method.

Example 4 A glass paper was pretreated by impregnating it with a urethane acrylate resin containing 25% of a styrene monomer and drying at 160 ° C. for 5 minutes. The resin adhesion amount at this time was 200% by weight in terms of solid content per 100 parts by weight of the glass paper. A 1.2 mm double-sided copper foil-clad unsaturated polyester laminate was produced by the continuous production method in the same manner as in Example 1 except that this glass paper was used.

Comparative Example 1 A 1.2 mm double-sided copper foil-clad unsaturated polyester laminate was produced by the continuous production method in the same manner as in Example 1 except that glass paper not treated with resin was used.

Comparative Example 2 The same procedure as in Comparative Example 1 except that a liquid resin obtained by adding 10 parts of a terminal maleated ethylene oxide propylene oxide random copolymer (KPX-1, manufactured by Sanyo Kasei) to the impregnating resin was used. A 2-mm double-sided copper foil-clad unsaturated polyester laminate was manufactured by a continuous manufacturing method.

Comparative Example 3 A glass paper was pretreated by impregnating it with a urethane acrylate resin containing 95% of a styrene monomer and drying at 160 ° C. for 5 minutes. The resin adhesion amount at this time was 5% by weight in terms of solid content per 100 parts by weight of the glass paper. 1.2 as in Example 1 except that this glass paper was used.
mm double-sided copper foil-clad unsaturated polyester laminate was manufactured by a continuous manufacturing method.

Comparative Example 4 A glass paper was pretreated by impregnating it with a urethane acrylate resin containing 5% of styrene monomer and drying at 160 ° C. for 5 minutes. The resin adhesion amount at this time was 500% by weight in terms of solid content per 100 parts by weight of the glass paper. When this glass paper was used, the impregnating resin did not impregnate well, and the laminate could not be produced successfully.

The characteristics of the glass fiber reinforced laminate according to this example, the water absorption of the conventional glass fiber reinforced laminate after boiling, and the warpage after etching and after heating were measured and shown in comparison with Table 1.

[0028]

[Table 1]

As is clear from Table 1, according to the method for manufacturing a glass fiber reinforced electrical laminate of the present embodiment, a laminate excellent in water absorption characteristics can be obtained. (1) Method of measuring water absorption after boiling A laminated plate with copper foil on both sides removed by etching is 50 ×.
Cut to a size of 50 mm and weigh it to obtain the initial weight. This sample is boiled in distilled water for 2 hours, and the weight after this is measured. The water absorption rate is calculated as a percentage of (weight after boiling-initial weight) / initial weight. (2) Method of evaluating warpage after heating The laminated plate is cut into a size of 250 x 250 mm, and the copper foil on one side is completely removed by etching. The sample was further heated at 170 ° C. for 30 minutes and cooled to room temperature. The sample was placed on a glass flat plate with the side where the copper foil remained, and the distance from the square glass flat plate of the laminated plate was measured to obtain the average value. As described above, according to the method for manufacturing a laminated board of the present invention, the glass fiber reinforced electrical conductivity in which the water absorption rate or the moisture absorption rate of the laminated board is sufficient by pretreating the nonwoven fabric with the radical polymerization type curable resin liquid in advance. Can be manufactured.

[0030]

INDUSTRIAL APPLICABILITY As described above, according to the present invention, by pretreating a non-woven fabric with a radical-polymerizable curable resin solution, a glass fiber-reinforced electrical laminate having excellent water absorption rate and moisture absorption rate of the laminated board can be obtained. The manufacturing method can be realized. Further, the effect of the present invention is remarkable when an oligomer having a reactive group is added to the impregnated resin in order to improve the warp.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification number Office reference number FI technical display location H05K 3/00 R 6921-4E

Claims (7)

[Claims] 1. A reaction by-product upon curing individually in a liquid state to each of the above-mentioned substrate rows while continuously conveying a plurality of substrate rows having glass cloth on both outer sides and a nonwoven fabric on the inner side. Laminating for electrical use, which includes a step of impregnating a curable resin liquid that does not generate a substance, laminating and impregnating impregnated base materials, laminating a cover sheet and / or a metal foil, continuously curing, and then cutting into desired dimensions. In the method for producing a plate, a method for producing a glass fiber reinforced electrical laminate, characterized in that the non-woven fabric is pretreated with a radical polymerization type curable resin solution in advance. 2. The method for producing a glass fiber reinforced electrical laminate according to claim 1, wherein the radical-polymerizable curable resin liquid used in the pretreatment is an epoxy acrylate resin liquid and / or a urethane acrylate resin liquid. 3. The method for producing a glass fiber reinforced electrical laminate according to claim 1, wherein the non-woven fabric is glass paper. 4. The glass fiber reinforced electrical laminate according to claim 1, wherein the amount of the resin adhered to the nonwoven fabric base material in the pretreatment is 10 to 300 parts by weight per 100 parts by weight of the nonwoven fabric. Method of manufacturing a plate. 5. The glass fiber reinforced electrical laminate according to claim 1, wherein the amount of the resin adhered to the nonwoven fabric base material in the pretreatment is 50 to 150 parts by weight per 100 parts by weight of the nonwoven fabric. Method of manufacturing a plate. 6. The method for producing a glass fiber reinforced electrical laminate according to claim 1, wherein the impregnating resin liquid is an unsaturated polyester resin and / or a vinyl ester resin. 7. The method for producing a glass fiber reinforced electrical laminate according to claim 1, wherein the impregnating resin liquid contains an oligomer having a reactive group.