JPS5963795A - Method of producing additive plating 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] The present invention relates to a method for manufacturing a laminate for plating.

A typical plating laminate has a structure in which a layer of a plating adhesive composition comprising a thermosetting resin component and a diene rubber component is provided on the surface. In order to produce a laminate having a layer of such an adhesive composition, there is a known method in which the base laminate is degreased, and then a solution of the composition is applied to the surface and dried and cured. In the adhesive composition, it is preferable to use phenol resin, epoxy resin, etc. as the thermosetting J91 resin component, and polybutadiene, acrylonitrile butadiene rubber, etc. as the diene rubber component. In general, these compositions are made into a solution using ketones or other reproducible solvents, and then applied to the surface of the laminate and dried and cured. Apply this solution and dry it, integrate it with Gripreg, which is the material for the laminate, and then mechanically peel off the carrier or chemically remove elatin to produce a laminate for plating. Can be done.

Prudential stripping rr+! A small amount of phospholipid, etc. may be added to the adhesive composition to make it easier.In the lamination and integration method, the adhesive coating film is not directly formed on the surface of the substrate.
Since the film is formed on the carrier film, the coating film can be formed continuously on the roll-shaped carrier film -E, and in integral molding (・j, it is set just like the molding of copper-clad laminates). Laminate molding is sufficient.Therefore, there is no need to apply adhesive intermittently to the cured substrate surface and dry it, making it a very useful manufacturing method in practice.However, in the conventional integrated molding method, The melting point is the penetration of the JN>W+ agent layer by the base material fiber.In other words, the resin in the prepreg melts due to heat and pressure in the press, the adhesive composition also softens, a chemical reaction progresses, and the resin crosslinks and hardens. There are many cases in which the uniformly thick coating made from the adhesive composition is penetrated or broken through by the base material in the Gripreg until the adhesive composition has sufficiently progressed. Possible ways to solve this problem include increasing the number of resin leaves in the prepreg, occupying the melt viscosity of the resin (reducing fluidity), and making the coating film stronger so that it cannot be broken through by the base material. However, it was not an easy method to implement.The first method, that is, the method of increasing the number of resin groups in the prepreg, tends to result in a relatively large flow of resin.Therefore, the amount of flow in the peripheral area is excessive compared to the central area. As a result, the plate thickness decreases significantly.As a result, it is difficult to adjust the overall plate thickness.

When manufacturing prepreg, increasing the amount of resin by about 20% from the usual 40 to 50% has a remarkable effect, but problems such as uneven coating and stickiness on the roll in the drying oven are likely to occur. Therefore, it is not easy to manage this process. The next method is to increase the melt viscosity of the resin in the prepreg, and it can be carried out by changing the drying conditions during prepreg production or by changing the resin formulation itself. However, if the flow of the resin in the prepreg is suppressed too much, the moldability of the laminate itself is impaired, so there is a tendency for the process control to be extremely low and the yield to be reduced. A specific resin formulation for a coating film that makes the coating strong enough to prevent it from being penetrated by the base material after R has not been found yet. That is, if the toughness of the coating film under heat is pursued, the tonality of the plating on the appearance of the coating layer will be significantly reduced, which is a practical problem.

The present invention solves the above-mentioned problems and provides a method for manufacturing a plating laminate having a large practical value and having an adhesive coating film of uniform thickness on its surface by integral molding.

In the present invention, first, a plating adhesive silk composition solution consisting of a thermosetting resin component and a diene-based rubber component is prepared, and this is used as a releasable film. : Apply to one side of shaped Kanai foil and dry. Coating JjF & after drying is 10μ or more 50
Desirably less than μ. More preferably 30μ or more - 40μ
It is as follows. If the coating film is too thin, the coating film will be damaged in subsequent steps, which will prevent the deposition and adhesion of homogeneous plating.

This is because if it is too thick, volatile components tend to accumulate in the coating film and reduce the solder heat resistance and air heat resistance after the plating is formed. When the thickness of the coating film is 40 μm or more, it is difficult to form a coating film with a uniform appearance as the coating thickness increases during the coating and drying process, and problems such as bubbles, uneven streaks, and fading are likely to occur. Conventionally, the coating film with a carrier obtained in this way was laminated with other prepregs for integral molding and heated under pressure. 4.It is characterized by applying a 1-fat paste and curing it by irradiating it with ultraviolet rays in advance. Polybutadiene derivatives containing acrylic or methacrylic groups are those obtained by introducing various functional groups into both ends of liquid polybutadiene and then acrylating or methacrylating it. Furthermore, examples of the liquid polyfridiene include homopolymers of butadiene, and copolymers of butadiene with acrylonitrile, styrene, acrylic acid esters, Nisdel methacrylate, etc.; There are no restrictions on L4V.When making a paste, it is necessary to add each of the 414 reactive diluents, photoinitiators, etc. to the polybutadiene derivative containing an acrylic or methacrylic group. xyacrylate, urethane acrylate, or polyester acrylate (,, F
11? It is possible to adjust the hardness after curing, thermal properties, electrical properties, water absorption, solvent resistance, dimensional stability, etc. according to the properties. As the reactive diluent, monomers having an unsaturated double bond and a thiol group can be used, and those that are compatible with the acrylic or methacrylic group-containing polybutadiene derivative may be used. For example, various acrylic esters,
Methacryl esters, styrene or derivatives thereof, etc. are preferable. The amount of the reactive diluent and acrylate prepolymer to be added is suitably 10 to 400 parts per part of the polybutadiene fatty acid containing acrylic or methacrylic groups. If it is less than 10i, sufficient dilution effect will not be exhibited and the ultraviolet curing speed will be slow. On the other hand, if it is 400 parts by weight or more, the flexibility, heat resistance, electrical insulation,
Some of the excellent properties such as moisture resistance may be impaired.

Light M [The intermediate initiator is not particularly limited as long as it causes photolysis or hydrogen abstraction reaction with light in the visible to ultraviolet wavelength range to generate radicals and initiate polymerization. Examples include benzophenone and benzoin ether. The amount of these added is 0.1 to 5 to the total resin composition.
Heavy M% is sufficient. Further, a photopolymerization accelerator such as a tertiary amine may be added as necessary. Furthermore, in addition to the above-mentioned basic composition, the ultraviolet curable ink composition according to the present invention may contain an inorganic and/or organic filler for the purpose of adjusting fluidity and coating thickness.

In the present invention, such an ultraviolet curable resin base is applied to the surface of the coating film of the above-mentioned
/ + i further applied, and the ultraviolet side is J! (T & J to harden the paste. Then, separately prepared i and uncured r. To'
A feature of the present invention is that the material is molded into a single piece by a pressure reaction to form the material into 6'M. That is, in the present invention, during integral molding, the wood in the prepreg is melted in a bath, and the softened adhesive composition is recoated using the 1-rigid base material in the prepreg, such as glass fiber or paper pulp. In order to prevent fibers and the like from entering, an ultraviolet curing resin layer is formed on the surface of the beneficial insects fif%, which acts as a strong barrier. When forming a durable protective wall, it must meet several requirements for a practically effective coating. Firstly, it is durable and melts only when heated under pressure.1. 'c<, it needs to be tough even at room temperature. In order to function as a durable barrier, it is desirable that the resin be sufficiently strong to withstand the invasion of the base material under pressure and heat, and for this purpose the resin should be sufficiently cross-linked and have high heat resistance. Since it is covered with a thin coating film, if it does not have a certain degree of flexibility, it will suffer from deterioration such as cracking.

Second, it must adhere well to both the coating film of the adhesive composition and the prepreg layer.

? Thirdly, it has excellent general properties as an electrical insulating material.
It is necessary to. It is desirable that the electrical insulation properties, dielectric properties, moisture resistance, and solvent resistance are not significantly inferior.

Fourthly, it is desirable that the process of forming a new coating film not impair the workability and productivity of the entire process.

The present invention can satisfy these requirements. The laminate thus produced has the layers shown in FIG. 1. To perform plating using this laminate, the carrier film on the surface is first removed.

If it is a film or metal foil that is easy to peel off, it may be peeled off mechanically, but chemical dissolution may also be used. The surface of the adhesive composition exposed when the carrier is removed using a chromic acid/sulfuric acid mixture is chemically roughened. and,
Catalyst treatment and accelerator treatment are applied to the roughened surface as a pretreatment for electroless plating, and a homogeneous electroless 1-noa plating film can be adhered to the entire surface by immersing it in an electroless plating bath.

Example carrier gold maple foil and 45μ thick aluminum '7% II
This one side contains phenol mt as a thermosetting resin component.
+bypr<-50232<Durezun epoxy resin Epikote-1001 (Sixil Chemical) Epoxy resin curing agent DDM-diaminodiphenylmethane, Acrylonitruptadiene rubber Nippor 1oo1 (E1 Zeon) as a diene rubber component, respectively solid. Blended at a weight ratio of 40.18.2.40 and coated with MEK as a 20wt% solution suitable for the coater.
After 1 minute at 130°C, dry for 2 minutes at 130°C.

As a result, a coating film of the adhesive composition with a thickness of about 35 μm was formed. Next, an ultraviolet curable resin paste was applied to the surface of this coating film to a thickness of 10 to 20 μm, and was cured by irradiating ultraviolet rays. The composition of the paste is as follows. Terminal acrylic group-containing polybutadiene (Idemitsu Petrochemical fM'
Polybb R-45ACR) 70 wt%, l
・Rimethylolpropane triacrylate) 15wt%
, 2-hydroxyethyl methacrylate) 13 wt%, 2
- 3 wt % of ethyl anthraquinone and 40 wt % of these fine powders of titanium oxide for viscosity adjustment. The obtained coating agent and glass cloth base epoxy resin prepreg EI678
Five sheets of a low resin content RC=40% special product of No. 7 (Jumin Bakelite) were stacked on top of each other in a layered structure as shown in FIG. 2, and were integrated by heating and pressing to obtain an additive substrate. After removing the aluminum foil on the surface by etching with an aqueous ferric chloride solution, the exposed coating film of the adhesive composition was roughened with chromium sulfuric acid. No unevenness due to the influence of the glass cloth grain was observed on the roughened surface, and a fine and uniform roughened state with a depth of 1 μnt or less was obtained. Cr03100f, H2SO43 in acid bath
00IIIe was included, and the conditions were immersion treatment at 50°C for 10 minutes. After thoroughly washing the roughened substrate with water, it was subjected to catalyst treatment and accelerator treatment in a conventional manner to deposit electroless steel plating to a thickness of about 1 ptn, and then to deposit electrolytic copper plating to a thickness of about 25 ptn. The adhesion of plating is 1.9
The heat resistance in ky/cm1 was good for 30 seconds or more in a semi-B3 bath at 260° C., with no abnormalities.

Comparative Example 1 Aluminum foil with a coating film of about 35 μm thick obtained in the process of Example is one example. Low RC special product 5 of glass cloth base epoxy resin prepreg El-6787 used in Example.
The substrates were stacked together in a layered structure as shown in FIG. 2 and integrated by heating and pressing to obtain an additive substrate. As a result of the same evaluation as in the example, the chromium sulfate roughened surface had irregularities with a depth of about 51 mm due to the influence of the glass texture.

Comparative Example 2 Epoxy acrylate (Lipoxy S manufactured by Showa Kobunshi Co., Ltd.) was used instead of using 70 wt.
P-1509) 70 wt % was used, but a coating agent could be obtained using the same materials and processes as in the example.

However, in this coating agent, the cured layer of ultraviolet curable resin paste is brittle and easily cracks. This was layered with several sheets of glass cloth base epoxy resin prepreg EI6787 low RC special product and integrally molded by heating and pressing, but a defective board with built-in cracks that occurred in the hardened layer of the paste was obtained. . Half-11 heat resistance after plating was as low as 260°C for 5 seconds. That is, as shown in the examples, the present invention, in manufacturing an element for additive plating, removes the process based on integral molding transfer of an adhesive composition suitable for forming a footrest, and applies the base material in the substrate to the surface. This is a highly practical manufacturing method that can virtually eliminate unevenness caused by fibers. Comparative Example 1, which is a typical example of the conventional manufacturing method, has a large surface unevenness, and Comparative Example 2 shows that it is necessary to limit the material so that the cured layer of the ultraviolet curable resin paste does not become brittle. These problems have been solved by the present invention.

[Brief explanation of the drawing]

Box 1 shows the cross-sectional configuration of a plating laminate manufactured according to the present invention. FIG. 2 shows the structure of the materials during laminated molding. 1 is a carrier (aluminum foil, etc.). 2 is a plating adhesive composition layer. 3 is ultraviolet curing (6 (fat paste cured material layer. 4
is an rN curable resin substrate layer. 5 is a thermosetting resin prepreg. FIG. 3 1 &j: A diagram showing the measurement of surface irregularities after chemical ratio treatment using a surface phase meter. (2L) is a substrate (
+)) is a substrate obtained by the conventional method (Comparative Example 1). The ↑ mark indicates a convex portion due to the grain of the glass cloth base ladle.

Claims (3)

[Claims] (1) A plating adhesive composition solution consisting of a thermosetting resin component and a diene rubber component is coated and dried, and an acrylic base is applied to the surface of the composition of a release film or a release metal foil. Or apply an ultraviolet curing resin paste whose main component is a polybutadiene derivative containing methacrylic groups,
This is irradiated with ultraviolet rays to cure only the paste first, and then one or more sheets of thermosetting resin prepreg are layered on top of this, and the paste is arranged so that the film or metal foil faces outward. A method for producing a laminate for plating, in which the laminate is formed into one piece by a pressure-heat curing reaction. (2) The method for producing a plating laminate according to claim (1), which is an ultraviolet curable resin paste mixed with a reactive diluent or an acrylate prepolymer. (3) 10 to 100 parts by weight of polybutadiene derivative
The method for producing a plating laminate according to claim (2), wherein the reactive diluent or acrylate prepolymer contains 1 part of 400%.