JPS6047355B2 - Metal foil with good adhesion - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a metal or alloy foil with excellent adhesive properties that eliminates the need for applying an adhesive to the metal foil when manufacturing a metal-clad laminate.

To put it simply, micro cells (hereinafter abbreviated as microcapsules) made of an organic or inorganic substance insoluble in the plating solution are formed by separately incorporating an adhesive or a hardening agent as a core substance on the surface of a metal or alloy foil. It is a metal foil made by electrolytically depositing one or both of them, and the microcapsule-deposited surface of the metal foil is overlaid with the surface of various base materials and compressed to destroy the microcapsules and remove the adhesive or The present invention relates to a metal foil that can be easily bonded to a base material through the cooperation of an adhesive and a hardening agent. Now, metal foil is widely used as a metal-clad laminate in the production of architectural and decorative laminates and reflective plates, and with the advancement of electronic technology, it is also widely used as a copper foil-clad laminate.

In addition, various other uses for products and parts are also possible. Among metal-clad laminates, rigid laminates are usually made by coating the surface of the metal foil with an adhesive, which has a roughened surface, and then layering this with a resin-impregnated filler (prepreg), which is the base material, and heat it. Manufactured by applying pressure with a press to finish adhesion and lamination at the same time, and when using a soft base material, heat and press the metal foil after applying adhesive to the base material surface. method. Therefore, when the objective is to achieve good performance, a method has been adopted in which both the base material and the metal foil are coated with an adhesive and then processed by heating under pressure. That is, manufacturing a metal-clad laminate requires an adhesive coating process in any case. However, most of the adhesives currently in use are organic solvent-based adhesives because they are convenient to use. Therefore, it is necessary to promptly remove it by a method that does not cause environmental pollution. For this reason, a large number of additional equipment are required for the work in order to prevent danger and pollution, including the health management of workers, and this has been a major drawback in the work. If the metal or alloy foil of the present invention is used, the adhesive coating operation described above becomes unnecessary, and in addition to simplifying the process, it becomes possible to safely manufacture a homogeneous metal-clad laminate.

Continuing the description of the present invention, the metal foil referred to in the present invention may include single metals and alloy foils, as well as composite materials such as plated metal foils, foils made by bonding multiple types of metals such as bimetallic foils, etc. It can also be used for metal foils that have a compound coating, such as an oxide coating, on their surface.

Regarding adhesives, in addition to thermosetting and thermoplastic one-component adhesives based on organic polymers, there are also known two-component resins such as epoxy resins, polyester resins, and polyurethane resins. There are no restrictions on the adhesive, as combinations with curing agents and inorganic adhesives can also be used. In addition, when selecting the product, consider the mechanical properties such as adhesive strength, tensile strength, precipitation/bending resistance, and tearability required for the product or part, and the chemical properties such as chemical resistance.
An appropriate one may be selected and used in consideration of physical properties such as melting point, specific gravity, and expansion coefficient. Furthermore, the foil of the present invention. Regarding the base material used for adhesives, the matrix is a natural material such as leather or cloth, or a thermosetting synthetic resin material such as epoxy resin or phenol resin, and organic or inorganic fiber filaments or fabrics are used as a matrix. , non-woven fabric,
A material in which paper or the like is dispersed, a veneer of thermoplastic resin such as polyvinyl chloride or a film thereof, or an inorganic board can also be used as the base material.

Next, to explain the microcapsules used in the present invention, the outer wall of the cell is made of an organic or inorganic material that can contain an adhesive or a hardening agent therein by utilizing a chemical reaction or a change in solubility. It is necessary that the material be insoluble.

For example, it may be a powder of an inorganic material such as calcium carbonate, carbon, or titanium dioxide, or a combination of an organic material and an inorganic material.

Furthermore, it may be composed of an organic paste such as gelatin, alginic acid, carboxymethylcellulose, or polyvinyl alcohol. Next, regarding the particle shape of the above-mentioned microcapsules, those having a diameter of 1 to 300 microns can be used, preferably 2 to 150 microns.

However, there are restrictions on the thickness of the metal layer and the diameter of microcapsules that can be eutectoid. That is, the thickness of the electrodeposited layer formed on the metal or alloy foil needs to be at least 30% or more of the capsule diameter. This allows the microcapsules to be firmly eutectoid-held on the surface of the metal or alloy foil. In addition, to briefly explain the method for producing the metal or alloy foil of the present invention using microcapsules, microcapsules containing an adhesive or microcapsules containing a hardening agent are added to a known metal plating bath or alloy plating bath. The metal or alloy foil of the present invention in which microcapsules are eutectoid can be obtained by dispersing and suspending the necessary amount thereof and electrolytically treating the metal or alloy foil using the metal or alloy foil as a cathode. Next, in order to manufacture a laminate using the metal foil of the present invention, the microcapsule eutectoid surface of the foil is layered on a suitable base material, and this is thermally compressed from above and below to destroy the capsules. Then, the adhesive in the capsule or the adhesive and the hardening agent in the capsule wets the interface, and the hardening reaction of these substances makes it possible to firmly bond the foil and the base material. Hereinafter, the present invention will be explained in more detail with reference to Examples. Example 1 One side of a long aluminum foil with a thickness of 50 mm was anodized and dyed, then the surface was covered with a protective film, the other side was degreased using a weak alkaline bath, and then exposed to a normal zincate bath. When immersed in water, a long foil with a substituted zinc coating formed on its surface is produced.

After washing this foil with water, 300y1' of zinc sulfate and 30y1 of aluminum sulfate suspended microcapsules 50y with a diameter of 30 to 80μ containing a phenolic resin adhesive consisting of 25% chloroprene rubber and 75% phenolic resin.
It was immersed in an acidic galvanizing bath consisting of e1 sodium chloride 15 daIel boric acid 20f1e and dextrin 5y1e, and the bath temperature was 35° C1 and the current density was 5 AIdd.
Plating was carried out for 20 minutes, and the microcapsules were deposited on the surface of the foil for 20 minutes.
An aluminum foil with a galvanized layer deposited by % was obtained. Next, this eutectoid foil is washed with water, dried, and its eutectoid surface is overlaid on one side of paper (prepreg) impregnated with phenolic resin, and it is formed by passing through hot rolls under a pressure of 50k91c11, and then the whole is made into a large-sized paper. In the furnace 7
When heated at 0°C for 3 hours, an aluminum cladding material for building materials having a decorative alumite surface on one side was obtained. This material had excellent adhesion between the aluminum foil and the base material, had good weather resistance, was long, easy to work with, and was an excellent product in terms of economy. Example 2 Nickel sulfate 240y1 was applied to the rough side of a 70μ thick copper foil.
Nickel plating with a thickness of 10μ is applied using a nickel plating solution with a composition of e1 nickel chloride 45y1e and boric acid 30y1e, and then nickel ammonium sulfate 4
A metal foil was prepared by plating black nickel to a thickness of 3 μm using a black nickel plating solution consisting of 50yIf1 Rodan Ammon 15y1e and subsulfite 15f1Ie, and covering the surface with a protective film.

On the other hand, microcapsules 50 with a diameter of 30 μm containing Epicoat 823 (trade name of epoxy resin manufactured by Shell Co., Ltd.)
y, microcapsules 10y with a diameter of 20p containing diaminodiphenylsulfone (DDS), and microcapsules 3V with a diameter of 20μ containing boron trifluoride monoethylamine were mixed with 300 g of copper sulfate 1. e1 sulfuric acid 50
The copper foil plated with black nickel was immersed in an acidic copper sulfate plating bath consisting of yIe, and the copper foil was immersed under the conditions of a bath temperature of 40°C and a current density of 10AIdd while stirring the bath.
Plating was performed for 0 minutes to produce a metal foil having a 40μ plating layer on the surface of which 20% of microcapsules were eutectoid.

After washing this foil with water and drying it, the diameter is 150rrLIrr.
The microcapsule portion was broken and adhered by winding it around an L stainless steel pipe and pressing the outer periphery with a rotating roll to obtain a heat-absorbing stainless steel vibrator with a black outer periphery. When this vibrator was used as a heat-receiving vibrator for a solar water heater, it showed good weather resistance and heat absorption, compared to a heat-absorbing vibrator manufactured by applying copper plating, nickel plating, and black treatment to a conventional stainless steel vibrator. ,
It was found that it is easy to manufacture and has excellent workability, such as being able to manufacture long products. Example 3 Stuffix (trade name of polyester adhesive manufactured by Fuji Photo Film Co., Ltd.).

) containing microcapsules 50y with a diameter of 30μ,
Nickel sulfate 250qIe1 Nickel chloride 45V1f1
and boric acid 30y1', and dipped a nickel foil with a thickness of 10p into the plating solution. While stirring the plating solution, the bath temperature was 45°C and the current density was 7A1drr1.
Powder plating was performed under the following conditions to obtain a nickel foil with 40% eutectoid of 15μ microcapsules on its surface. This foil was washed with water and dried in a conventional manner, the microcapsule eutectoid side of the foil was superimposed on the 25μ thick polyester film substrate side, and 30 kg was rolled using a hot roll at 120°C.
The microcapsules were destroyed and bonded by applying pressure of IcIL and moving the foil and the base material at a speed of 1 rrL for 1 minute. Then, this was left standing in a drying room maintained at 50°C to complete curing. The performance of the thus obtained nickel-foiled polyester film was measured in accordance with JIS-C-6481, and the results shown in the table below were obtained. It was confirmed that the nickel foil-covered polyester film board prepared from the front fully satisfied the adhesive strength and other properties required for a flexible printed wiring board.

Claims (1)

[Claims] 1. Electrolytic eutectoid deposition of one or both of microcells in which an adhesive and a hardening agent are separately contained in organic or inorganic particles insoluble in a plating solution on the surface of a metal or alloy foil. A metal foil characterized by the fact that it has been made into a metal foil. 2 The thickness of the electrodeposited layer formed on the metal or alloy foil is
The metal foil according to claim 1, which has a thickness of at least 30% or more of the diameter of the microcell to be eutectoid. 3. The metal foil according to claim 1, wherein micro cells having a particle size in the range of 1 to 300 μm are electrolytically eutectoided on the surface of the metal or alloy foil. 4. The metal foil according to claim 1, in which only microcells containing a one-component organic adhesive are electrolytically eutectoided on the surface of the metal or alloy foil. 5. The method described in claim 1, in which microcells containing a two-component organic adhesive and microcells containing a hardening agent are electrolytically eutectoided on the surface of a metal or alloy foil. metal foil.