JPS63149383A - Production of material coated with hyperfine metal - Google Patents

Abstract

PURPOSE:To obtain a material coated with hyperfine metal excellent in electromagnetic characteristics by allowing alcohols and transition metallic carbonyl compd. to react with transition metallic salt, dispersing and sticking the produced hyperfine metal particles having a specified particle diameter or below on the surface of high polymer material. CONSTITUTION:After subjecting the surface of organic-base and inorganic-base high polymer material to oxidizing treatment with a sulfuric acidic potassium bichromate soln., it is immersed into i.e. the hydrochloric acidic aq. soln. of stannous chloride. Then transition metal is stuck on the surface by means of such a method that the high polymer material obtained after the above-mentioned treatment is immersed into the hydrochloric acidic aq. soln. of transition metallic salt of Ni and Pd, etc. Thereafter the high polymer material stuck with transition metal is brought into contact with alcohols and metallic carbonyl compd. and metallic carbonyl compd. is thermally decomposed. The temp. of this thermal decomposition is <=200 deg.C and especially it is preferably <=120 deg.C. As a result, hyperfine particles which have high- performance magnetic characteristics and <=0.1mu primary particle diameter and are connected with a straight chain are dispersed and stuck on the surface of the high polymer material.

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, fine metal particles condense 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 this problem by reacting a transition metal carbonyl compound on the surface of a polymeric material at a low temperature, and achieves this object by reacting a transition metal carbonyl compound on the surface of a polymeric material. This was done after discovering that it can be dispersed and adhered to the surface of the substrate, thereby providing excellent electromagnetic properties.

That is, the present invention aims at "contacting and reacting a transition metal salt with an alcohol and a transition metal carbonyl compound on the surface of a polymeric material to form a primary particle size of 0.1 micron (μ
) A method for producing a material coated with ultrafine metal particles, which comprises dispersing and adhering the following metal particles to the surface of a cough 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 uniformly 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, transition metal salts used in the present invention include, for example, Cu, N1
%Co5Pd5Fe and other metal salts, especially N
Salts of t sPd are preferred.

As the alcohol used in the present invention, any of aliphatic saturated alcohols, alicyclic alcohols, and aromatic alcohols can be used. Specific examples include methyl alcohol, ethyl alcohol, propyl alcohol, butyl alcohol, octyl alcohol, noryl alcohol, trimethylsilanol, and ethylene glycol.

It is desirable that these alcohols be added in a molar ratio of 0.1 to 0.0001, preferably 0.05 to 0.001, relative to the transition metal carbonyl compound. If this molar ratio exceeds 0.1, the reactants tend to aggregate, and if it is less than 0.0001, the primary particle diameter of the reactants tends to increase.

Furthermore, the transition metal carbonyl compound used in the present invention is
It is a metal carbonyl compound such as Fe5Ni, Co, W, MO% Cr. These may be used in combination.

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

First, a transition metal is attached to the surface of a polymer material,
Prior to adhesion, the surface of the polymeric material can be oxidized if necessary. This oxidation treatment is carried out by treatment with, for example, a sulfuric acid acidic potassium dichromate solution.

A transition metal can be attached to the surface by a method such as immersing this polymer material in an acidic hydrochloric acid aqueous solution of tinnous chloride and then immersing it in an acidic hydrochloric acid aqueous solution of a transition metal salt.

Next, the polymer material to which the transition metal salt is attached is brought into contact with the alcohol and the metal carbonyl compound to thermally decompose the metal carbonyl compound. The temperature during this thermal decomposition is 2
The temperature is preferably 00°C or lower, preferably 150°C or lower, particularly preferably 120°C or lower. temperature is 200℃
If the amount is exceeded, decomposed metals may precipitate on the reactor walls other than the surface of the polymer material, carbon may be produced as impurities due to side reactions, and the primary particle size of the produced metals may become larger than 0.1μ. There is a tendency to put it away.

The above reactions can also be carried out in the gas phase and in the liquid phase. When carrying out the decomposition reaction in a liquid phase, the alcohol and 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.

It is preferable to carry out this decomposition reaction in a magnetic field because linearly connected ultrafine particles having high performance magnetic properties can be obtained as shown in the later examples.

Antioxidation treatment can be performed as necessary to prevent oxidation of the produced ultrafine metal particles. An effective antioxidant for this purpose is a silane coupling agent. Specific examples of silane coupling agents include vinyltriethoxysilane, γ
- Vinyl silane compounds such as methacryloxypropyltrimethoxysilane; Amino silane compounds such as γ-aminopropyltrimethoxysilane and N-phenyl-T-aminopropyltrimethoxysilane; γ-glycidoxypropylmethyljethoxysilane There are epoxy-based silane compounds such as 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 (KzCr20t) in advance.
50 g % concentrated sulfuric acid 400+alt, water 600111
) at room temperature, and then a stannous chloride solution C3n
C1z 100 g SHCj 250 ml water if), palladium chloride solution (PdCj! t O, 5 g, concentrated hydrochloric acid 10-!, water 41), and finally immersed at 50 °C for 3
After drying for a few hours, transition metal treatment was performed.

Next, ethyl alcohol was added to a 5% by weight solution of Fe (Go) s in toluene at 0.2 mol % based on Fe (CO) s, and the above-treated PET film was immersed therein for 30 minutes at 60°C. Heated. As a result, ultrafine particles of decomposed iron were supported on the film. Next, this film was immersed in a 1% solution of γ-aminopropyltriethoxysilane in toluene and heated at 80° C. for 1 hour to prevent oxidation of the supported iron.

Observation of the surface morphology using an electron microscope revealed that ultrafine iron particles with a primary particle diameter of about 0.02 μm were supported in a network-like manner on the surface of the PET film.

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 In the decomposition reaction of Fe (Co) s in Example 1, 1,0000 in the horizontal direction with respect to the PET film
Fe(Co)s was decomposed under a magnetic field of e, and ultrafine iron particles were supported.

Next, this film was immersed in a 1% by weight solution of γ-aminopropyltriethoxysilane in toluene and heated at 80°C for 1% by weight.
The supported iron was treated to prevent oxidation by heating for a certain period of time.

Observation of the surface morphology using an electron microscope revealed that ultrafine iron particles with a primary particle diameter of about 0.02 μm were supported in a linear chain on the surface of the PET film. The magnetic properties of this product were as shown in Table 1.

Example 3 Ultrafine iron particle-supporting carbon fibers were obtained in the same manner as in Example 1, except that carbon fibers were used instead of the PET film in Example 1, which had been subjected to anti-oxidation treatment.

Electron microscopic observation of this material revealed that ultrafine iron particles with a primary particle diameter of approximately 0.03 μm were supported on the surface of the carbon fibers in a connected manner. 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.
(Co)s catalytic reaction was performed. As a result, no iron decomposition product was observed on the surface of the film.

Comparative Example 2 In Example 1, P without adding ethyl alcohol
The same procedure as in Example 1 was carried out, except that e (CO) s and the PET film were reacted, and the anti-oxidation treatment was completed.

When observed with an electron microscope, the primary particle diameter was 0.15.
It was found that ultrafine iron particles of μ were supported. Also,
The magnetic properties of this product were as shown in Table 1.

Table 1

Claims (1)

[Claims] The feature is that a transition metal salt, an alcohol, and a transition metal carbonyl compound are brought into contact with each other on the surface of a polymeric material, and reacted to cause metal particles with a primary particle diameter of 0.1μ or less to be dispersed and adhered to the surface of the polymeric material. A method of manufacturing a material coated with ultrafine metal particles.