JPH01259176A - Production of thin metal film type composite material - Google Patents

Abstract

PURPOSE:To obtain a dense uniform thin metal film type composite material having high adhesive strength by forming thin metal films on a base metal in many layers by repeating coating with organometalic ink and calcining. CONSTITUTION:Organometalic ink consisting of an organometalic compd., a binder and an org. solvent which dissolves both the compd. and binder is prepd. Thin metal films are formed on the base metal in many layers by repeating coating with the ink, drying and calcining.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a method for manufacturing a metal thin film composite material.

(Prior art and its problems) Conventional manufacturing methods for composite materials involve pressure bonding, thermal bonding, or using various brazing fillers for bonding between metal materials processed into wire or tape shapes to different base metals. There is a method of brazing, and commonly used methods include electroplating, electroless plating, and applying a metal paste and baking.

Problems with these methods include the lack of adhesion strength and lack of plating baths suitable for the type of metal base material and alloy plating, etc.; Manufacturing the material is difficult due to the spreadability and alloy properties of metals, and the method of applying metal paste and baking it uses metal powder, which has the drawbacks of large variations in film thickness and poor adhesion. there were.

Recently, vapor deposition methods have been used, but there are problems such as the need for special equipment as vapor deposition equipment, and only special materials are used.

(Purpose of the Invention) The present invention has been made to solve the problems of the conventional method described above, and in particular, a thin film layer with a thickness of 1 μm or less is made of a single metal or an alloy of two or more types, and moreover, it is formed into several layers. It is an object of the present invention to provide a method for manufacturing a dense and uniform thin film composite material that can be bonded to a thin film and has strong adhesion.

(Means for Solving the Problems) The present invention involves forming one or more metal thin films by applying an organic metal ink onto a base metal, drying it, and then firing it. This is a method for producing a characteristic metal thin film composite material.

The present invention will be explained in more detail below.

Organometallic ink consists of an organometallic compound (in a narrow sense, a compound with a direct bond □ between a metal atom and one or more carbon atoms), various resins as a binder, □ the metal compound and the resin. It is a homogeneous solution consisting of an organic solvent common to

The organometallic compound is preferably a metal salt of a resin acid, and the resin added as a binder is selected from alkyd resins, urea resins, melamine resins, rosin derivative resins, asphalt, cellulose resins, epoxy resins, acrylic resins, and terpene resins. In addition, as a solvent, menthanol, terpineol, butylcarboxytol, methyl ethyl ketone, propylene glycol, ethylene glycol, cyclohexanone, ethyl acetate, benzyl acetate,
One or more mixed solvents of amyl acerade, cellosolve, butyl cellosolve, butanol, nitrobenzene, toluene, xylene, petroleum ether, chloroform, 5-carbon tetrachloride, pinene, dipentene, dipentene oxide, and essential oil. It was synthesized by

In the process of coating the metal base material with the organic metal ink, drying it, and then firing it, the solvent first evaporates and separates at a temperature of room temperature to about 200°C. Next, the resin and the metal salt of the resin acid are 300 to 1.0
It decomposes into metals or metal oxides at 00°C. At this time, the thin film of metal or metal oxide diffuses and adheres to the metal base material. The depth of diffusion varies depending on the firing temperature and time, the melting point of the metal base material, and the alloy properties of the metal or metal oxide formed by firing with the metal base material, so the conditions are selected depending on the application.

Various organic metal inks are applied onto base metals of various shapes by methods such as screen printing, brush painting, rolling spray, stamping, dipping, etc., dried at room temperature for 10 to 30 minutes, and then heated to 180 to 220°C for 10 to 15 minutes. Heat and dry. Next, by firing at 300 to 1000°C for 5 to 10 minutes, a thin film of various metals with a thickness of 0.05 to 0.1 μm can be formed. Although it is possible to obtain an arbitrary film thickness by repeating this operation, the film thickness is preferably 2 μm or less.

Furthermore, it is natural that the film thickness of various metals varies depending on the metal concentration of various organic metal inks and the coating method.
The film thickness of 0.05 to 0.1 μm is an average result obtained by screen printing.

The firing temperature varies depending on the type of organic metal ink, especially when a metal or two or more metals are mixed together, but it is necessary to select the firing temperature taking into consideration deformation of the base metal. But 30
It is not preferable to heat the organic metal ink below 0°C because it will not completely decompose, and if it is heated above 1000°C, other effects such as deformation of the base metal or alloying with the base metal will occur.

Furthermore, the firing can be performed in an oxidizing atmosphere or a reducing atmosphere to oxidize the target thin film of various metals or to prevent the oxidation of the base metal.

In addition, when layering two or more metals, it is possible to first apply a first layer with an arbitrary thickness to the base metal using the above method, and then apply a second thin layer in the same manner. By repeating similar operations, it is also possible to form several layers of thin films of different metals or alloys.

Organometallic inks remain in a solution state even when two or more types are mixed.
After firing, the metal can be highly uniformly dispersed.

Examples of the method for manufacturing a metal thin film composite material according to the present invention will be described below, but the examples are not intended to limit the present invention.

(Example 1) Nickel plate (width 5.mm, length 200m
Organic gold ink was applied by rolling onto a sheet (0.8 mm thick), dried at room temperature for 10 minutes, and then heated at 200°C for 10 minutes.
It was dried by heating for 0 minutes, and then baked at 400° C. for 5 minutes. After repeating this operation three times, the film thickness was measured, and it was found that a thin gold film of 0.3 μm in thickness was formed which was dense and closely adhered to the nickel plate without voids.

A portion of this gold-nickel plate approximately 20++n from both ends was bent at right angles, and a portion approximately in the middle was twisted by 90°, but no cracking or peeling occurred.

The organic gold ink used here was a mixture of the following:

Gold resin acid 20.0% by weight Base metal resinate 05% by weight Resin 230% by weight Organic solvent 565% by weight (Example 2) Copper-Nisokel alloy (containing 65% Ni) plate (width 5 mm, length (length 200mm, thickness 0.8mm)
An organometallic ink containing an organic gold ink and an organic silver ink was applied by dipping to the surface, dried at room temperature for 10 minutes, heated and dried at 100°C for 10 minutes, and then baked at 300°C for 5 minutes. After repeating this pattern five times, the film thickness was measured, and it was found that a thin film of gold and silver alloy (75% by weight of gold, 25% by weight of silver) of 0.5 μm could be formed.

This gold, silver alloy-copper, nickel alloy plate was subjected to bending and twisting tests in the same manner as in Example 1, but no cracking or peeling occurred.

The organometallic ink used here was a mixture of the following:

Gold resinate 15.0% by weight Silver resinate 5.0% by weight Base metal resinate 05% by weight Resin 23.0% by weight Organic solvent 56.5% by weight (Example 3) Base metal copper plate (width 5 mm, length length 200mm, thickness 0.8
An organic alloy ink consisting of a mixture of organic platinum ink and organic iridium ink was applied to the surface (mm) by brushing, and
After drying for 0 minutes, heating and drying at 200°C for 10 minutes, baking at 500°C for 5 minutes, and further increasing the heating temperature to 700°C.
℃ and baked for 5 minutes. The film thickness of platinum and iridium is 01μm, and the ratio of platinum and iridium is 90°10
It was a weight ratio.

The organometallic ink used here is a mixture of the following:

Platinum resinate 7.0% by weight Iridium resinate 1.2% by weight Base metal resinate 05% by weight Resin 44.5% by weight Organic solvent 46.8% by weight (Example 4) Base metal copper pipe (outer diameter 8 mm) , length 100 mm, thickness 1 mm), an organic alloy ink containing an organic silver ink and an organic copper ink was applied to the outside of the pipe by brushing, dried at room temperature for 30 minutes, and then heated at 500°C in a reducing gas atmosphere for 20 minutes.
Baked for 0 minutes. When this imitation was repeated three times, 0.
A pipe on which a 3 μm thick silver and copper alloy thin film was formed was obtained.

The ratio of silver to copper was 70°30 weight/medium ratio.

The organometallic ink used here was a mixture of the following:

Silver resinate 140% by weight Copper resinate 585% by weight Other base metal resinates 0.5% by weight Resin 42.0% by weight Organic solvent
38.0% by weight (Example 5) The organic gold ink used in Example 1 was applied by brush to the pipe on which the silver and copper alloy thin film prepared in Example 4 was cut in half, and the pipe was heated at room temperature. After drying for 10 minutes, 200
℃ for 10 minutes and then heated to 400℃ in a reducing gas atmosphere.
, and baked for 5 minutes. This imitation was repeated three times to obtain a pipe material with three layers: a gold thin film layer, a silver and copper alloy thin film layer, and a copper base material.

(Effects of the Invention) The present invention can form a thin film layer with a thickness of 1 μm or less as a single metal or two or more metals, and can also be formed into several layers, and further has a dense and uniform thin film composite with strong adhesion strength. Contact materials and brush materials manufactured using various conventional metals and powder metallurgy methods have drawbacks due to their respective characteristics, such as alloys that tend to segregate or alloys made using powder metallurgy. It is possible to solve problems such as brittleness and produce composite materials with characteristics suitable for various uses, and their utility value can be said to be extremely high.

The present invention has the features described in the claims, and examples of its embodiments are as follows.

(2) As organic metal inks, organic gold ink, organic platinum ink, organic silver ink, organic palladium ink, organic iridium ink, organic rhodium ink, organic rhodium ink, organic nickel ink, organic copper ink, organic zinc ink, organic The production of the metal thin film synthetic material according to claim 1, which comprises one or more organic metal inks selected from the group consisting of tanksten ink, organic cadmium ink, organic indium ink, organic molybdenum ink, and organic magnesium ink. Method.

Procedural amendment by Tanaka Kikinzoku Kogyo Co., Ltd. (voluntary) 1. Indication of the case Showa fi 3 Patent Application No. 3'F No. 8 [i 7 II No. 3 2. Name of the invention Method for producing metal thin film composite feed 3゜Relationship with the case of the person making the amendment Detailed explanation of the invention in the patent applicant's specification Column 5 Contents of the amendment (1) Page 3 of the specification, lines 4-6, 1 (in a narrow sense, a compound having... )” is deleted.

Claims (1)

[Claims] 1. A method for producing a metal thin film composite material, which comprises forming one or more metal thin films by applying an organic metal ink onto a base metal, drying it, and then firing it.