JPH05318657A - Production of single-sided copper clad lamianted sheet and laminated sheet - Google Patents

Abstract

PURPOSE:To obtain a single-sided copper clad laminated sheet and laminated sheet free from the adhesion of foreign matters and excellent in appearance using a novel releasable metal foil. CONSTITUTION:A plurality of sets each obtained by superposing a release film on both surfaces of one or more prepreg or by superposing the release film on one side of one or more prepreg sheets and superposing a copper foil on the opposite surface thereof are combined through a mirror surface plate and heated under pressure to produce a single surface copper clad laminated sheet and laminated sheet. In this method, a releasable metal foil obtained by forming a releasable cured thermosetting resin layer on both surfaces of a metal foil is used as the release film.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is a method for producing a single-sided copper clad laminate and a laminate using a novel releasable metal foil, which is preferably used for printed wiring boards, carbon coating or insulation. It is something.

[0002]

2. Description of the Related Art Conventionally, in a single-sided copper-clad laminate and a method for producing a laminate, a set in which a release film is laminated on both sides of one or more prepregs, or one or more prepregs on one side It is manufactured by combining a set of a release film and a set of copper foils on the opposite side through a mirror plate, putting them in a hot platen, and heating and pressing.

As the release film, films of polypropylene, poly-4-methylpentene-1, other polyolefins, acetylcelluloses such as triacetylcellulose, fluororesins such as polytetrafluoroethylene are used. .. However, polypropylene and the like have poor heat resistance and are difficult to use at high temperatures of 180 to 200 ° C or higher. Further, there is a problem that the plasticizer used for film production bleeds during the laminating molding to contaminate the mirror surface plate. Further, a film made of a fluororesin or the like is excellent in heat resistance and releasability, but it is expensive and the laminated plate produced is expensive because it cannot be reused.

[0004]

DISCLOSURE OF THE INVENTION The present invention provides a release film which can be used even at a high temperature exceeding 200 ° C., does not contaminate a mirror surface plate, has good heat resistance, and is inexpensive. By the finding, it is possible to manufacture a single-sided copper-clad laminate and a laminate at a relatively low cost.

[0005]

Means for Solving the Problems That is, the present invention provides a set in which a release film is superposed on both sides of one or a plurality of prepregs, or a release film on one surface of one or a plurality of prepregs, and a release film on the opposite surface. In a method of manufacturing a single-sided copper-clad laminated plate or laminated plate in which a plurality of sets of copper foils are combined through a mirror surface plate and heated / pressurized, the mold release film is formed on both sides of the metal foil. A method for producing a single-sided copper-clad laminate and a laminate, which comprises using a release metal foil formed by forming a cured thermosetting resin layer. Also,
In a preferred embodiment of the present invention, the thermosetting resin layer of the releasable metal foil has a thickness of 1 to 8 μm, and the thermosetting resin layer of the releasable metal foil serves as a release agent. A single-sided copper-clad laminate and a method for producing a laminate, comprising a thermosetting resin composition containing 0.02 to 0.8% by weight of a fluororesin copolymerized oligomer having an oily chain.

The structure of the present invention will be described below. First, the single-sided copper-clad laminate and the laminate of the present invention are printed wiring boards, laminates used for carbon coating, insulation, and the like. As a method for producing the present laminated plates, known methods such as a multi-step pressing method, a multi-step depressurizing press, and a continuous press can be used. Here, as the reinforcing base material for producing the prepreg of the present invention, glass woven cloth, glass nonwoven cloth (glass mat, paper, etc.), glass fiber such as glass roving, inorganic reinforcing base material such as other ceramic fiber, and perfume Examples thereof include group polyamide, liquid crystalline polyester, and other heat-resistant organic reinforcing base materials. This reinforcing substrate is
It is used as a surface-treated product such as a silane coupling agent.

As the impregnating resin, epoxy resin,
Unsaturated polyester resin, cyanate resin, bismaleimide-cyanate resin, polyimide resin, and other thermosetting resins; compositions prepared by appropriately mixing two or more of these; further thermosetting resins, two or more thereof Polyvinyl butyral, acrylonitrile-butadiene rubber, polyfunctional acrylate compound,
Other known resins, modified with additives, etc .; crosslinked polyethylene, crosslinked polyethylene / epoxy resin, crosslinked polyethylene / cyanate resin, polyphenylene ether / epoxy resin, polyphenylene ether / cyanate resin, polyester carbonate / cyanate resin, other modifications A cross-linking curable resin composition (IPN or semi-IPN) made of a thermoplastic resin is exemplified. Among these, in the present invention, particularly, a cyanate resin, a bismaleimide-cyanate resin, a single-sided copper-clad laminate using a polyimide resin, etc., which requires a lamination molding temperature of 200 ° C. or more, a mold release for producing a laminate. It is preferably used as a film.

[0008] The above-mentioned resin may be blended with a filler as appropriate, and examples thereof include silicas such as natural silica, fused silica and amorphous silica, white carbon, titanium white, aerosil, clay, talc, wollastonite and natural mica. , Synthetic mica, kaolin, aluminum hydroxide, magnesia, alumina, perlite, E-glass, A-glass, C-glass, L-glass, D-glass, S-glass, M-glass, G20-glass, etc. Fine powder and the like are mentioned as suitable ones. Also,
For other purposes, flame retardants, lubricants, and other additives can be added.

In the present invention, when the above prepreg, or a set of a prepreg and a copper foil laminated on one side thereof, is laminated and molded, a releasability in which a thermosetting resin layer cured to at least the prepreg surface is formed is formed. It uses a metal foil. Here, as the metal foil used in the production of the releasable metal foil of the present invention, aluminum, nickel, tin, copper,
Other alloys may be mentioned, and those having a thickness of 20 to 50 μm are usually preferable. Among these, aluminum and copper are particularly preferable in terms of cost.

A cured thermosetting resin layer for release is formed on both surfaces of the above-mentioned metal foil. Examples of the thermosetting resin include those exemplified for prepreg impregnation, but epoxy resin, cyanate resin, and bismaleimide-cyanate resin are particularly preferable. Further, as the release agent to be added to the thermosetting resin for imparting releasability, various compounds such as olefin type, ester type, silicone type and fluorine type can be used and can be used. However, in the present invention, it is preferable that there is no transferability to the prepreg surface,
From this point, an oligomer or a low molecular weight polymer is more preferable. In particular, a silicone-based copolymer oligomer or a fluorine-based copolymer oligomer having a lipophilic chain as a copolymerization portion having an affinity for a thermosetting resin is preferable, and a lipophilic chain having a molecular weight of about 3,000 to 15,000 is particularly preferable. Fluorine-based copolymer oligomers having The amount used is in the range of 0.01 to 1% by weight, preferably 0.02 to 0.8% by weight of the solid content in the resin composition.

As a method for forming the release layer, the thermosetting resin composition containing the above-mentioned release agent is dissolved in a solvent to obtain a viscosity of 500.
Adjust to about 2,000 centipoise (at 25 ° C) and apply it continuously on one side of the metal foil with a roll coater to a thickness of 0.1-10 μm, preferably 1-8 μm, and heat. A method in which the solvent is removed and the thermosetting resin composition is pre-cured, a release layer is formed on both surfaces in the same manner on the opposite side and pre-cured, and the pre-cured release layers on both sides are heat-cured. Or, in the above, after applying the thermosetting resin composition on one surface of the metal foil, pre-curing, further curing, to form a cured thermosetting resin layer for release on both surfaces in the same manner on the opposite surface. by.

[0012]

The present invention will be described below with reference to examples. The "parts" and "%" in the examples are based on weight unless otherwise specified. Example 1 1,000 parts of 2,2-bis (4-cyanatophenyl) propane
A preliminary reaction was carried out at 50 ° C for 150 minutes, and this was dissolved in methyl ethyl ketone. Bisphenol A type epoxy resin
(Product name: Epicoat 1001, Yuka Shell Epoxy Co., Ltd., epoxy equivalent 450-500) 600 parts, Fluorine-based copolymer oligomer (Product name: Surflon SC-101, Asahi Glass Co., Ltd.) 5 parts and zinc octylate 0.18 A part was dissolved to obtain a releasing resin solution having a viscosity of 1020 centipoise (at 25 ° C).

The resin solution obtained above was coated with a roll while continuously winding an aluminum foil having a thickness of 40 μm from the roll, followed by drying and curing under heating, and a cured release layer having a thickness of 7 μm was coated on both sides. Forming a thermosetting resin layer that has high heat resistance and cutting at a predetermined interval, 1080mm × 1080mm
To obtain a releasable metal foil (hereinafter referred to as "release foil A").

On the other hand, 900 parts of 2,2-bis (4-cyanatophenyl) propane and bis (4-maleimidophenyl) methane 1
Preliminarily react with 00 parts at 150 ° C for 100 minutes, dissolve this in a mixed solvent of methyl ethyl ketone and N, N'-dimethylformamide, add 0.20 parts of zinc octylate to this and mix evenly to prepare a varnish ( , Varnish A). This varnish A was impregnated into an E-glass plain woven fabric having a thickness of 0.1 mm, dried, and cut at predetermined intervals to obtain a prepreg (hereinafter referred to as PP1) having a size of 1080 mm × 1080 mm.

On the stainless steel mirror surface plate, three release foils A and PP1 described above and electrolytic copper foil with a thickness of 18 μm were stacked in this order, and the stainless steel mirror surface plate was repeatedly stacked to form a single-sided copper clad laminate. Assembled 15 sets of boards. The set consisting of 15 sets was placed between the hot plates of a multi-stage press and set to 20 kg / cm ² , 250
The laminate was molded under the condition of 2 ° C. for 2 hours, and after cooling, the mirror surface plate and the release foil A were removed to obtain a single-sided copper clad laminate having a thickness of 0.3 mm.
The resin surface of the one-sided copper-clad laminate and the release foil A have good releasability, and the stainless mirror surface plate and the release foil A have good releasability. The conductive resin layer did not peel off and remained on the resin surface of the single-sided copper-clad laminate or on the stainless specular plate surface.

Comparative Example 1 The same procedure as in Example 1 was performed except that the release foil A was replaced with a polypropylene film having a thickness of 50 μm. As a result, the polypropylene film adheres to the resin surface of the single-sided copper-clad laminate and cannot be peeled off, and the polypropylene film also adheres to the stainless specular plate, which is not possible if it is a spatula peeling, but peeling is very difficult. Met.

[0017]

As is clear from the detailed description of the invention as described above, according to the method for producing a laminated sheet or a single-sided copper-clad laminated sheet in which the releasing metal foil of the present invention is used in place of the releasing film, 200
Even in the laminated molding at a high temperature of ℃ or more, it is possible to easily maintain the releasability and manufacture laminated plates. Further, since the releasable layers are formed on both surfaces, metal powder or the like does not remain on the mirror-finished plate, and the cause of "dakon" does not occur. Furthermore, the releasable metal foil of the present invention can be manufactured relatively easily and inexpensively, and its industrial significance is extremely high.

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Claims (3)

[Claims] 1. A set of a release film laminated on both sides of one or a plurality of prepregs, or a set of a release film on one side of one or a plurality of prepregs and a copper foil on the opposite side, and a mirror surface plate. In the method for producing a single-sided copper-clad laminate or laminate in which a plurality of sets are combined through heating and pressurization, a release-cured cured thermosetting resin layer is formed on both sides of the metal foil as the release film. Single-sided copper-clad laminate, characterized by using a releasable metal foil 2. A single-sided copper-clad laminate according to claim 1, wherein the thermosetting resin layer of the release metal foil has a thickness of 1 to 8 μm. 3. The thermosetting resin layer of the releasing metal foil is formed of a thermosetting resin composition containing 0.02 to 0.8% by weight of a fluororesin copolymer oligomer having a lipophilic chain as a releasing agent. The single-sided copper-clad laminate according to claim 1, and a method for producing the laminate.