JPH04192597A - Manufacture of double side copper-clad laminated board - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a method for manufacturing a copper-clad laminate having a functional resin layer, particularly a tracking-resistant thermosetting resin layer, directly under a copper foil by a continuous method. It is. In particular, it is possible to form a tracking-resistant thermosetting resin layer during the introduction of the laminated molding material into continuous laminated molding, imparting the desired functionality without the use of special prepregs or copper foils. is possible,
This provides a manufacturing method with excellent productivity.

[Conventional technology and its problems]

Conventionally, copper-clad laminates produced using the continuous method are manufactured by introducing one or more sheets of long prepreg into a continuous press machine so as to overlap long sheets of copper foil on both sides, and continuously heating and pressurizing the sheets. has been done.

On the other hand, the conventional method for manufacturing copper-clad laminates with improved functions such as tracking resistance has been conventional lamination molding using prepregs that have been given such functions or copper foil with a resin layer that has these functions. In particular, the only known continuous manufacturing method was a method using a prepreg that had been given this function in advance.

[Means to solve the problem]

As a result of studying a method for manufacturing a laminate with more rational functionality, the present inventors used a continuous method and formed a tracking-resistant thermosetting resin layer during the process. We have found a way to combine these methods and have completed the present invention.

That is, the present invention provides a copper-clad laminate that is continuously laminated and formed by stacking a long copper foil (b) on one or both sides of one or more sheets of long prepreg (al) and introducing it into a continuous press. In the manufacturing method, a functional resin layer (
c) is a method for producing a copper-clad laminate, characterized in that the functional resin layer (c1) is formed of a thermosetting resin composition (c1) having excellent tracking resistance.
), and the thermosetting resin composition (c1) contains amorphous saturated polyester, unsaturated polyester,
Compounded with one or more selected from the group consisting of low molecular weight polyolefin, saturated rubber, polydicyclopentadiene, aliphatic petroleum resin, polycaprolactone, polyalkylene glycol, dimer acid-based polyamide, polyurethane, and melamine. It is requested that the functional resin layer (c1) is formed by applying a solvent-free thermosetting resin composition before introducing the prepreg or copper foil into the continuous press. This is a method for manufacturing copper-clad laminates consisting of

The configuration of the present invention will be explained below.

First, the continuous press of the present invention is typified by a double belt press.

Here, the heating and pressurizing conditions may be the same as conventional ones, but the use of preliminary fusion of laminated materials under vacuum (Japanese Patent Application Laid-Open No. 1-146740
(Japanese Patent Application Laid-Open No. 1-221), Utilization of Preheating of Laminated Materials
No. 244), and others are used in combination as appropriate, and in particular, prepregs that exhibit chemical resistance and other physical properties by post-curing as prepregs used in laminated molding are selected, and then processed under normal continuous pressing conditions. , the adhesive strength of the copper foil is 0.2 kg/cd or more, preferably 0.3 kg/car
As described above, it is also a preferable method to produce a semi-cured resin copper clad plate having a glare of 0.4 dazzle/d or more, and to post-cure this in an inert gas or reducing gas atmosphere, if necessary.

The long prepreg (a) refers to phenolic resins, epoxy resins, unsaturated polyester resins, cyanato resins, and other thermosetting resins; a composition formed by appropriately blending two or more of these; A resin, a composition formed by blending two or more thereof, modified with polyvinyl butyral, acrylonitrile-butadiene rubber, a polyfunctional acrylate compound, other known resins, additives, etc.;
Cross-linked polyethylene, cross-linked polyethylene/epoxy resin,
A cross-linked curable resin composition (IPN or semi-1PN) consisting of cross-linked polyethylene/cyanato resin, polyphenylene ether/cyanato resin, polyphenylene ether/cyanato resin, polyester carbonate/cyanato resin, and other modified thermoplastic resin is used as a matrix resin, and kraft Paper, linter paper, glass (E, D, S, T, quartz and other various glass fibers) woven and non-woven fabrics, fully aromatic polyamide, polyphenylene sulfide, polyetheretherketone, polyetherimide, polytetrafluoroethylene Woven fabrics, non-woven fabrics, and porous sheets made of heat-resistant engineering plastic fibers, such as woven fabrics, non-woven fabrics, and porous sheets made of heat-resistant engineering plastic fibers, as well as composite fabrics and non-woven fabrics made by appropriately mixing or combining these, are used as the base machining material, and the impregnated resin is applied to the B-stage L/te. Examples include prepreg. In particular, a resin composition containing an epoxy resin composition as a main component is used as a matrix resin,
A base gusset made of glass woven fabric or nonwoven fabric is preferably used.

The copper foil (b) of the present invention is an electrolytic copper foil, a rolled copper foil, etc.
It has a surface treated for adhesion.

In the present invention, a material having a functional resin layer formed on at least the back surface of the copper foil (b) described above or one surface of the prepreg fa) to which the copper foil is bonded is used. The functional resin layer (c) performs a specific function during the manufacture or use of the printed wiring board, and typically provides UV absorption to enable simultaneous exposure on both sides, and UV absorption by water droplets, etc. One example of this is the provision of tracking resistance so that electrical leakage is temporary and does not develop into a fire or the like.

As the resin composition (c1) for imparting UV absorbability, to the resin composition used as baize material,
Examples include resin compositions containing about 0.1 to 6% of ultraviolet absorbers, fluorescent brighteners, radical polymerization initiators, sensitizers, and the like. In addition, as the resin composition (c1) for imparting tracking resistance, epoxy-modified unsaturated polyester resin and the like can be used as is, but there are other resin compositions that can be used as baize material. selected from the group consisting of crystalline saturated polyesters, unsaturated polyesters, low molecular weight polyolefins, saturated rubbers, polydicyclopentadiene, aliphatic petroleum resins, polycaprolactones, polyalkylene glycols, dimer acid-based polyamides, polyurethanes and melamines Examples include resin compositions containing one or more types of resins, and the amount of these compounds varies depending on the type, but generally 50% by weight or less and 1% or more, particularly 4 to 15% by weight. The selection should be made in consideration of the level of tracking resistance to be achieved.

In the present invention, the method for forming the above-mentioned functional resin layer (c) includes preparing a functional resin composition and applying it to one side of the prepreg or the back side of the copper foil by roll coating, spray coating, or other methods. A method in which a solvent-free functional resin composition is prepared and applied during the process of continuously introducing copper foil or prepreg into a continuous press. The latter method, in-line coating, is particularly preferred from the standpoint of effectively utilizing continuous press. In addition, a functional resin layer (c
) has a thickness in the range of 20 to 200, preferably 30 to
100 ux.

〔Example〕

Example 1 An epoxy resin-modified unsaturated polyester resin composition liquid was applied to one side of a long glass woven fabric-epoxy resin prepreg (hereinafter referred to as rPPI J) with a thickness of 8 mm.
A prepreg with a layer (hereinafter referred to as rPP2 J) having a thickness of about 0.05 mm was produced by preheating at 0°C.

2 pieces of 2 yen, 2 pieces of PP2 on both sides with the coating layer side facing outward, and 3 pieces of PP2 on the outside.
5m of copper foil is layered and continuously fed into a double belt press at a temperature of 200℃ and a pressure of 40kg/crl.
The adhesive strength of the copper foil was 0.85.
kg/cm of prepreg resin was semi-cured and cut at a predetermined position to produce a semi-cured resin copper-clad laminate with a thickness of 0.8 cm.

This semi-cured resin copper-clad laminate was post-cured in a drying oven at a temperature of 120° C. for half a day to obtain a copper-clad laminate in which the resin was completely cured.

When the tracking resistance of the obtained copper-clad laminate was measured, it was found to be 600 V or more, which was good.

Example 2 As a melamine resin, a melamine resin in which hexamethylol melamine was reacted with ethanol and four methylol groups were converted to ethyl ester was used, and this was blended with 15% by weight epoxy resin to produce a solvent-free melamine-modified epoxy resin. A composition was obtained.

The structure was such that four sheets of PPI were layered with a 35 m thick copper foil on the outside, which were continuously fed into a double belt press. At this time, the copper foil was coated with the solvent-free melamine-modified epoxy resin composition obtained above to a thickness of about 0.07 mm on the back side, and placed on the drawing side drum of a double belt press preheated to 120°C. It was designed to be supplied while being in contact with each other.

Heat and pressure molding was performed at a temperature of 200°C and a pressure of 40 kg/cffl for 1 minute to semi-cure the prepreg resin, which has an adhesion strength of 0 to 7 kg/cm to the copper foil, and was cut at a predetermined position to give a thickness of 0. An 8 mm semi-cured resin copper-clad laminate was manufactured.

This semi-cured resin copper-clad laminate was post-cured in a drying oven at a temperature of 120° C. for half a day to obtain a copper-clad laminate in which the resin was completely cured.

When the tracking resistance of the obtained copper-clad laminate was measured, it was found to be 400V, which was good.

[Operation and effects of the invention]

As is clear from the above detailed description of the invention, according to the continuous manufacturing method of the method for manufacturing a laminate with a functional resin layer of the present invention, a laminate with a functional layer can be produced extremely efficiently. It is possible.

Furthermore, since the anti-tracking resin layer suitably used in the present invention is only the surface layer, the basic physical properties remain essentially unchanged. Furthermore, according to a more preferred method for producing a semi-cured resin laminate, chemical resistance and other physical properties can be reproduced in the same manner as in the conventional lamination molding method, so that it can be suitably used in terms of physical properties.

Patent applicant: Mitsubishi Gas Chemical Co., Ltd.

Claims (1)

[Claims] 1. Copper-clad laminate in which a long copper foil (b) is layered on one or both sides of one or more sheets of long prepreg (a) and introduced into a continuous press to form a continuous layer. In the method for producing a copper plate, a copper foil comprising a functional resin layer (c) formed on the copper foil side surface of the prepreg (a) or the prepreg side surface of the copper foil (b) is used. Manufacturing method for stretched laminates. 2. The method for producing a double-sided copper-clad multilayer board according to claim 1, wherein the functional resin layer (c) is formed of a thermosetting resin composition (c1) having excellent tracking resistance. 3 The thermosetting resin composition (c1) contains amorphous saturated polyester, unsaturated polyester, low molecular weight polyolefin, saturated rubber, polydicyclopentadiene, aliphatic petroleum resin in the resin composition used for producing the prepreg. ,
3. The method for producing a double-sided copper-clad multilayer board according to claim 2, which contains one or more selected from the group consisting of polycaprolactone, polyalkylene glycol, dimer acid-based polyamide, polyurethane, and melamine. 4. The functional resin layer (c) is formed by applying a solvent-free thermosetting resin composition before introducing the prepreg or copper foil into a continuous press. A manufacturing method for double-sided copper-clad multilayer boards.