JPS637378A - Production of material coated with hyperfine particle metal - Google Patents

Abstract

PURPOSE:To produce a high-polymer material coated with an hyperfine particle metal having excellent electromagnetic characteristics by bringing a transition metal salt and transition metal carbonyl compd. into contact with each other on the surface of the high-polymer material at a specific temp. and dispersing and sticking the metallic particles of a specific grain size onto the surface thereof. CONSTITUTION:The surface of the org. or inorg. high-polymer material is subjected to an oxidation treatment at need and is then immersed into an aq. hydrochloric acid soln. of the transition metal salt so that the transition metal salt is stuck onto the surface thereof. Metal salts of Cu, Ni, Co, Pd, Fe, etc., are used for the transition metal salt. The high-polymer material is then brought into contact with the transition metal carboxyl compd. at <=120 deg.C to thermally decompose the metal carboxyl compd. and to disperse and stick the metallic particles having <=0.2mu average grain size onto the surface of the high-polymer material. The carbonyl compds. of metals such as Fe, Ni, Co, W, Mo, and Cr are used for the transition metal carboxyl compd. The high-polymer material on which the hyperfine particle metal is well dispersed and is stuck and held with the practicable strength is thus obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for producing a polymeric material coated with ultrafine metal particles having excellent electromagnetic properties.

[Conventional technology]

Fine particles of transition metals such as iron, cobalt, and nickel have unique electromagnetic properties and are used in electronic component materials.

Methods for making practical materials by dispersing and adhering these fine particles to the surface of polymeric materials include, for example, mixing metal fine particles with paint and applying it to the surface of polymeric materials, or using electroless plating to manufacture polymeric fine particles. There is a method in which fine particles are attached to the surface of the particles.

[Problem that the invention seeks to solve]

However, with conventional methods, metal fine particles aggregate on the material surface and adhere in a lump, making it impossible to take advantage of the characteristics of the fine particles, or not being able to adhere and hold them with sufficient strength for practical use. is difficult to apply,
In addition, there are problems such as the contamination of impurities such as reducing agents, and disadvantages such as failure to obtain fine metal particles as desired.

[Means for solving problems]

The present invention aims to solve these problems by reacting a transition metal carbonyl compound on the surface of a polymeric material at a low temperature, thereby achieving this objective and applying unprecedentedly ultrafine metal particles to the surface of the material. This was done after discovering that it is possible to deposit it in a dispersed manner and that this provides excellent electromagnetic properties.

That is, the present invention is directed to [a transition metal salt and a transition metal carbonyl compound are brought into contact with each other at 120° C. or lower on the surface of a polymeric material, and reacted to reduce the average particle size.

A method for producing a material coated with ultrafine metal particles, which comprises dispersing and adhering metal particles of 0.2 microns or less onto the surface of the polymer material.

〔Effect of the invention〕

By the method of the present invention, a polymer material in which ultrafine metal particles are well dispersed and adhered and held with sufficient strength for practical use can be easily obtained by reaction at a low temperature.

This method can be applied to polymer materials having complex shapes as well as particles, fibers, and plates.

The obtained coating material has excellent electromagnetic properties because the metal particles are homogeneously dispersed as ultrafine particles, and is useful for applications such as conductive materials, magnetic materials, and optical materials.

[Function] The polymeric materials used in the present invention are organic and inorganic polymeric materials, and can be applied to polymeric materials in any shape such as powder, fiber, plate, etc.

Specifically, natural polymers such as valves and cotton; thermoplastic resins such as polyolefins and polyamides; epoxy resins,
Thermosetting resins such as unsaturated polyester; graphite,
Examples include carbon materials such as carbon fiber.

Further, the transition metal salt used in the present invention is, for example, Cu.

Salts of metals such as Ni, Go, Pd, Fe, etc. Among them, N
i, Pd salts are preferred.

Furthermore, the transition metal carbonyl compound used in the present invention is
It is a carbonyl compound of a metal such as Fe, Ni+ Co+ W+ Mo, or Cr. These may be used in combination.

Next, the following method is generally suitable for bringing the above transition metal salt and transition metal carbonyl compound into contact and reacting on the surface of the polymeric material.

First, a transition metal salt is deposited on the surface of a polymeric material, but prior to the deposition, the surface of the polymeric material is oxidized if necessary. This oxidation treatment is carried out, for example, by treatment with a sulfuric acid acidic potassium dichromate solution.

This polymeric material is immersed in an acidic hydrochloric acid aqueous solution of tinnous chloride, and then immersed in an acidic hydrochloric acid aqueous solution of a transition metal salt to adhere the transition metal salt to the surface.

Next, the polymeric material to which the transition metal salt is attached is brought into contact with the metal carbonyl compound to thermally decompose the metal carbonyl compound.

The temperature during this thermal decomposition is 120°C or less, preferably 10°C or less.
It is important to keep the temperature below 0°C.

If the temperature exceeds 120°C, decomposed metals may precipitate on the walls of the reactor other than on the surface of the polymer material, carbon may be produced as impurities due to side reactions, and the average particle size of the metal may also be 0.
It becomes larger than 2 microns (μ).

The above reactions can be carried out in the gas phase and also in the liquid phase using catalysts. When carrying out the decomposition reaction in a liquid phase, the metal carbonyl compound can be dissolved in an inert solvent such as toluene or decane, and the polymeric material can be immersed in this solution to carry out the decomposition reaction.

In order to prevent the generated ultrafine metal particles from oxidizing, anti-oxidation treatment is performed as necessary. An effective antioxidant for this purpose is a silane coupling agent. Specific examples of silane coupling agents include vinyl silane compounds such as vinyltriethoxysilane and γ-methacryloxypcobyltrimethoxysilane; γ-aminoprobyltriethoxysilane, N
-Phenyl-γ-aminopropyltrimethoxysilane and other amino-based silane compounds; and γ-glycidoxypropylmethyljethoxysilane and other epoxy-based silane compounds. Among these, amino-based silane coupling agents are particularly effective.

The oxidation prevention treatment method involves applying a silane coupling agent to the ultrafine metal coating material in the gas phase or liquid phase at 50 to 150°C.
This can be done by contacting the

〔Example〕

Example 1 Polyethylene terephthalate (PET) with a thickness of 100μ
The surface of the film was coated with a dichromic acid solution (KzCr2(h
50g S? a Sulfuric acid 400ml, water 6Q 0ml
) at room temperature, and then oxidized with a stannous chloride solution (Sn
Cffz 100 g,,HCj250mj! , water Il
), palladium chloride solution (pacx 20.5 g,
Sequentially immersed in 10ml of concentrated hydrochloric acid, 41ml of water, and finally 50ml of water.
It was dried at ℃ for 3 hours and subjected to transition metal treatment.

Next, the above-treated PET film was immersed in a 5% solution of Fe(Co)s in toluene and heated at 60° C. for 30 minutes. As a result, ultrafine particles of decomposed Fe were supported on the film. Next, this film was immersed in a 1% by weight solution of γ-aminopropyltriethoxysilane in toluene and heated at 80° C. for 1 hour to prevent the supported Fe from oxidizing.

Observation of the surface morphology using an electron microscope revealed that spherical ultrafine particles Fe with an average particle size of 0.08 μm were uniformly dispersed and supported on the PET film surface.

The magnetic properties of the obtained supported PET film were measured using a vibrating sample magnetometer. The results are shown in Table 1.

Example 2 Ultrafine Fe-supported carbon fibers were obtained in the same manner as in Example 1 except that carbon fibers were used instead of the PET film, including the antioxidant treatment.

Electron microscopic observation of this material revealed that spherical ultrafine particles Fe with an average particle size of 0.1 μm were uniformly dispersed and supported on the carbon fiber surface.

The magnetic properties of this product were as shown in Table 1.

Comparative Example 1 P that was not subjected to transition metal salt treatment in Example 1
Fe was prepared in the same manner as in Example 1 except that the ET film was used.
A catalytic reaction of (Co)s was carried out.

As a result, no decomposed Fe was observed on the surface of the film.

Comparative Example 2 The same procedure as in Example 1 was carried out except that the decomposition temperature in the catalytic reaction of Fe (CO) s in Example I was changed to 130°C.

As a result, decomposed Fe was generated on the PET film surface and on the reactor wall other than the film surface.

The decomposed Fe on the surface of the PET film was spherical fine particles with an average particle size of 0.8 μm. Also, the magnetic properties of this material are the first
It was as shown in the table.

Table 1

Claims (1)

[Claims] A transition metal salt and a transition metal carbonyl compound are brought into contact with each other at a temperature of 120°C or lower on the surface of a polymeric material, and the metal particles having an average particle size of 0.2 microns or less are dispersed and adhered to the surface of the polymeric material. A method for producing a material coated with a characteristic ultrafine metal.