JPH0561296B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a method for producing a polymer having a metal layer on its surface.

Polymers with a metal layer on the surface are used as surface heating elements, circuit boards, capacitors, electromagnetic shielding plates, electrically conductive fibers, etc. by utilizing their conductivity, and they are also used as visible light by utilizing their reflective properties. Or used as an infrared reflector.

PRIOR ART AND PROBLEMS TO BE SOLVED BY THE INVENTION Vacuum deposition or sputtering methods are widely used as methods for producing polymers having a metal layer on the surface. The degree of adhesion is small and it is easy to peel off, and the equipment therefor is expensive.

A method has been proposed in which the surface of a polymer film containing an organometallic complex is brought into close contact with a suitable substrate for metallization and then heat treated to obtain a polymer whose surface is metallized (for example, in JP-A No. Showa 59-
No. 207938). Since the metal layer obtained by this method is integrated with the polymer, it has the advantage that peeling problems do not occur. However, the method described in JP-A No. 59-207938 requires the surface of the polymer to be brought into close contact with the metallized substrate, so it can only be applied to film-like or plate-like polymers; It cannot be used for polymers in shapes such as fibers or rods. In addition, the heat treatment temperature is relatively high (100 to 350℃),
Furthermore, the manufacturing equipment is relatively expensive.

An object of the present invention is to solve the problems of the prior art as described above, to obtain a metal layer that is integrated with a polymer and has no fear of peeling relatively easily and at a low temperature, and to be able to form a metal layer of any shape. It is an object of the present invention to provide a method for producing a surface-metallized polymer, which is applicable to the polymers of the present invention.

Means and Effects for Solving the Problems The method for producing a surface metallized polymer of the present invention involves dissolving a polymer and an organometallic complex in a solvent, and forming a polymer containing the organometallic complex into a desired shape from this solution. The molded article is then reduced with a reducing gas. When the polymer is placed in a reducing gas, the organometallic complex contained in the polymer is reduced, forming a metal layer that is integrated with the polymer over the entire surface that is in contact with the reducing gas.

The type of polymer used in the present invention is not limited as long as it is soluble in a solvent and has an affinity for the organometallic complex. Examples of polymers used include polyimides, polyamides, poly(meth)acrylates, polyacrylonitrile, polycarbonates, polystyrene, polyvinyl chloride, polyurethanes, saturated or unsaturated polyesters, epoxy resins, etc.

As the organometallic complex used in the present invention, one is selected that is soluble in the same solvent as the polymer,
Also, those that are stable against the atmosphere or moisture are preferred.
As the central metal of the organometallic complex used in the present invention, various metals of groups B, B, B, B, B and groups of the periodic table are used. Examples include gold, silver, copper, platinum, iridium, osmium, palladium, rhodium, ruthenium, iron, cobalt, nickel, manganese, rhenium, chromium, molybdenum, tungsten, vanadium, titanium, and zirconium. Ligands of organometallic complexes include, for example, tertiary phosphites, tertiary phosphites, carbon monoxide, linear or cyclic olefins,
Can be selected from combinations of one or more of conjugated olefins, aryl compounds, heterocyclic compounds, organic cyano compounds, organic isonitrile compounds, organic mercapto compounds, or compounds having an alkyl group, a vinyl group, an allyl group, an ethyridine group, an acyl group, etc. . The organometallic complex is used at any concentration depending on the purpose of use. For example, about 1 part of the complex is used per 10 parts of the polymer.

The solvent used in this invention is a solvent for both the polymer and the organometallic complex. For example, single or mixed solvents such as chloroform, methylene chloride, trichloroethylene, tetrachloroethylene, benzene, toluene, xylene, acetone, ethyl acetate, dimethylformamide, dimethyl sulfoxide, dimethylacetamide, N-methylpyrrolidone, etc. are used. The amount of solvent used for the polymer is selected so that the polymer has a viscosity and fluidity suitable for mixing the organometallic complex and is suitable for forming the polymer into a film, fiber, etc.

A polymer containing an organometallic material is formed into an arbitrary shape from a solution consisting of a polymer, an organometallic complex, and a solvent. For example, film-like or plate-like moldings can be obtained by casting the solution onto heated glass, and fibrous polymers can be obtained, for example, by wet spinning.

In the present invention, the reducing gas includes, for example,
H ₂ , CO, HI, H ₂ S, etc. can be used.

A polymer molded article containing an organometallic complex is metallized by placing it in such a reducing gas atmosphere for an appropriate period of time. The temperature of the reducing gas is preferably 20 to 90°C, the pressure is preferably 1 to 2 kg/cm ² , and the reaction time is suitably about several tens of seconds to more than ten minutes. The polymer may be preheated before the reaction. Although the solvent in the polymer may be removed before reduction, it is usually preferable to reduce the solvent with at least a portion remaining. For example, after forming a film by casting, the solvent may remain in the polymer. Refunds can be made immediately.

The reduction may be carried out in a stream of air or in a closed container.

In the method of the present invention, by appropriately selecting the type of polymer and organometallic complex used, and by changing operating conditions such as reducing gas conditions, the electrical conductivity of the metallized polymer obtained Surface reflection etc. can be adjusted depending on the purpose.

Effects of the Invention The present invention makes it possible to obtain surface-metallized polymers by a very simple, quick and inexpensive method. Since the metal layer is integrated with the polymer, there is no risk of peeling off unlike metal layers formed by vapor deposition or sputtering. Since the polymer surface is metallized in a gas, there are no restrictions on the shape of the treated polymer, and a surface metal polymer with any shape can be obtained depending on the purpose. It is also easy to adjust the electrical conductivity, surface reflectance, and other properties of the surface metallized polymer depending on the purpose. Furthermore, relatively low temperatures (10 to 90
Since metallization can be achieved by treatment at temperatures (°C), there is little risk of adversely affecting the original physical properties of the polymer.

In addition, since the reduction is carried out in a gas, after a polymer solution containing an organic metal is cast into a film or spun into a thread, it can be immediately reduced even if the film or thread still contains residual solvent, and the solvent can be removed easily. Can be done at the same time.

If the method of the present invention is used, for example, the solution of the present invention may be applied to the surface of fibers such as natural/synthetic fibers, glass fibers, etc. by dipping or coating, and then placed in a reducing gas atmosphere to remove the surface metal. Furthermore, surface metallized plastics can be obtained by coating plastics etc. by spraying or the like and then placing them in a reducing gas atmosphere. The metallized plastic surface thus obtained can also be used as a plating base. In addition, the method of the present invention can be used as a lightweight conductive material for power transmission lines, communication line battery electrodes, communication waveguides, transformer core materials, etc., or as a functional material for sensors, memory hard disks, etc.
Possible uses include compact disks, catalysts, and transparent conductive films.

Example 1 After dissolving 10 g of polyacrylonitrile (manufactured by Toho Rayon) in 50 ml of DMF, benzonitrile-Pd
Add 5g of complex and mix and dissolve. The obtained mixed solution was cast on a glass plate of 100 mm x 100 mm x
A 50μ film was obtained. Add this to hydrogen gas (30
After being placed in a closed container with a volume of 5 for 10 minutes, the hydrogen in the container was replaced with a reduced pressure of 0.1 atm, and then placed again under the same conditions (30°C, 1 atm) for 10 minutes. A film with metallic luster was obtained with Pd metal precipitated on the film surface. Further, leave the film at 0.1 atm and 60℃ for 10 minutes to remove residual DMF in the film.
was removed. The surface resistance of this material was 300Ω/□.

Example 2 A film measuring 100 mm x 100 mm x 50 μm was obtained in the same manner as in Example 1. Hydrogen gas (30
in a container of volume 5 with an atmosphere of 1 atm)
After leaving it for 60 minutes with an air flow of 0.1/min, the film surface
A film with metallic luster was obtained in which Pd metal was precipitated. The film was further left at 60°C for 10 minutes to remove residual DMF in the film. The surface resistance of this material is
It was 100Ω/□.

Claims (1)

[Claims] 1. A process for producing surface metallized polymers, which consists of dissolving a polymer and an organometallic complex in a solvent, molding a polymer containing the organometallic complex into a desired shape from this solution, and then reducing this molded product with a reducing gas. Production method.