JP2003064401A - Ni BASED POWDER HAVING EXCELLENT ANTIBACTERIAL AND MOLD PREVENTION PROPERTIES, PRODUCTION METHOD THEREFOR, AND MATERIAL RESIN AND MEMBER CONTAINING THE SAME Ni BASED POWDER AND HAVING EXCELLENT ANTIBACTERIAL AND ANTIFUNGAL PROPERTIES - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce metal powder which stably exhibits higher antibacterial and antifungal properties by further increasing the antibacterial and antifungal of Ni based powder containing hydrogen. SOLUTION: The Ni based powder having excellent antibacterial and antifungal properties is obtained by sticking a P and/or S-containing compound to the surface of Ni or Ni alloy powder in which the content of Ni in an Ni or Ni alloy part is >=20 mass%, and the content of hydrogen is 1 to 10,000 ppm. The sticking quantity of the P and/or S-containing compound is <=1% in terms of a ratio occupied in the whole of the powder, and the total content of P and/or S in the compounds is >=0.001% in terms of a ratio occupied in the whole of the powder.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a Ni or Ni alloy powder having excellent antibacterial and antifungal properties, a method for producing the same, a material containing the powder and having excellent antibacterial and antifungal properties, a resin, and a coating thereof. And a member having excellent antibacterial and antifungal properties.

[0002]

2. Description of the Related Art In recent years, in various applications such as food processing and medical fields and daily necessities, from the viewpoint of hygiene, the growth of fungi and fungi is prevented. The adoption of a metal member that has been subjected to a treatment has started to be considered. The level of antibacterial and antifungal properties required for each of these applications differs depending on the application.Because of the small amount of antibacterial and antifungal properties that can serve the purpose in order to give a good image of high hygiene, There are a variety of uses that require immediate effects and require breeding and infection prevention. Of these, for example, equipment used in hospitals and medical facilities, equipment used in the field of food manufacturing and processing, and fittings, toilets, air conditioners, refrigerators, transport machines, and transport vehicles used in those facilities are the latter. There is an increasing demand for surface-treated metal members having a high level of antibacterial and antifungal properties.

In manufacturing such a surface-treated metal member, a method of surface-treating each member, a method of subjecting a metal plate or the like to a surface treatment and then assembling it, and the like can be considered.
However, if antibacterial and antifungal properties are given to the metal powder, the range of applications and usage forms can be greatly expanded, such as when mixed with resin and applied or mixed with paint. Development of a metal powder having properties is desired.

Most of the coating type antibacterial / antifungal surface treatment agents are powders having antibacterial / antifungal properties dispersed in a film-forming matrix. Specifically, (1) ) JP-A-8-156175 and JP-A-8-274.
No. 04 and Japanese Unexamined Patent Publication No. 8-25548, etc., containing powders of metals having antibacterial and antifungal properties such as Cu and Ag, and powders of various inorganic compounds having a photocatalytic function such as TiO ₂ . A method of applying a coating film or a resin layer to a metal surface, (2) JP-A-8-53738 and JP-A-8-603.
No. 03 and JP-A-8-104952, a method of concentrating a metal having antibacterial / antifungal properties such as Cu and Ag on the surface of stainless steel, (3) JP-A-9-195061 Nos. 7,228,999, 9-157860, etc., which are disclosed in Japanese Patent Laid-Open Nos. 7-228999 and 9-157860.
And a method of forming a surface layer containing inorganic compound particles having a photocatalytic function such as a metal having antifungal properties and TiO ₂ .

As the powder used for imparting antibacterial / antifungal properties by these methods, an electrochemically noble metal component such as Cu or Ag, or an inorganic compound having a photocatalytic function is used, or those powders are used. It is produced by supporting an ion or complex on an inorganic oxide such as silica gel, zeolite or calcium phosphate.

However, since metal powders such as Cu and Ag are electrochemically noble, they are difficult to ionize, and the metal powders themselves show almost no antibacterial / fungistatic properties. In addition, even if the method of loading on an inorganic oxide or the inorganic carrier is devised, the stability of the antibacterial / antifungal powder is not compatible with the improvement of the ionization rate. It also takes 12 hours) and has almost no effect on antifungal properties.

Further, the inorganic powder having a photocatalytic function requires strong sunlight and ultraviolet rays to exert its antibacterial effect,
The number of practical parts that can secure such strong sunlight and ultraviolet rays is naturally limited.

Under these circumstances, the present inventors have been conducting research for some time, and as a part thereof, developed an antibacterial powder containing Ni as a main component and containing Co, P and the like, and previously proposed it ( Japanese Patent Laid-Open No. 2000-143422). This publication also revealed that excellent antibacterial properties can be obtained by controlling the hydrogen content in the antibacterial powder.

However, it is very difficult to control hydrogen in the powder in a stable and reliable manner. This is because the hydrogen intrusion method disclosed in the above publication, specifically, a method of electrochemically charging Ni-based powder with hydrogen, or Ni
All of the methods of exposing the system powder to a high temperature and high pressure hydrogen gas atmosphere require expensive equipment for hydrogen infiltration, and it is difficult to uniformly contain a target amount of hydrogen in the Ni system powder. Therefore, it is difficult to obtain a material in which the amount of hydrogen is stably controlled, and what is currently put into practical use is hydrogen-free Ni—Co or Ni—P powder, which is slightly inferior in antibacterial / mold resistance.

[0010]

The present inventor has been made in view of the above circumstances, and its purpose is to:
Another object of the present invention is to provide a metal powder disclosed in the above-mentioned Japanese Patent Application Laid-Open No. 2000-143422, which further enhances the antibacterial and antifungal properties and stably exhibits excellent antibacterial and antifungal properties.

[0011]

The Ni-based powder having excellent antibacterial and antifungal properties according to the present invention capable of solving the above-mentioned problems means that the Ni content in the Ni or Ni alloy portion is 20% by mass or more. , A P- and / or S-containing compound adheres to the surface of Ni or Ni alloy powder having a hydrogen content of 1 to 10,000 ppm, and the adhered amount of the P- and / or S-containing compound occupies the whole powder. 1% by mass
The following content, and the total content of P and / or S in the compound is 0.001% by mass in the ratio of the whole powder.
The gist exists where the above is.

In the above Ni-based powder of the present invention, Ni
Alternatively, the Ni content of the Ni alloy portion is preferably 50% by mass or more, more preferably 90% by mass or more, and the P and / or S-containing compound is an oxide or complex oxide of P and / or S. It is recommended that those containing one or more selected from zinc phosphate, calcium phosphate, iron phosphate and manganese phosphate are particularly preferable.

The manufacturing method according to the present invention is positioned as a manufacturing method of Ni-based powder having the above-mentioned characteristics.
Alternatively, the Ni alloy powder has an elution amount of 0.05 to 5
The gist is that it includes a treatment of immersing in an aqueous solution of 0 g / m ² / h or more for 1 to 10,000 minutes.

When 1 to 30% by mass of the above-mentioned Ni-based powder of the present invention, which has excellent antibacterial and antifungal properties, is contained in various inorganic substances, organic substances or mixtures thereof, the antibacterial and antifungal properties are excellent. A material can be obtained, which is also included in the preferred embodiment of the invention. In particular, when vinylidene fluoride resin, acrylic resin, epoxy resin, silicone resin or a mixed resin thereof is used as the organic substance, it is possible to impart antibacterial and antifungal properties to these resins. By using an antibacterial / antifungal resin for the surface coating of various inorganic or organic members, it is possible to impart excellent antibacterial / antifungal properties to these members, and the obtained antibacterial / antifungal member is also the present invention. It is included in the category of.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, Ni or Ni
The reasons for defining the Ni content and hydrogen content in the alloy powder (hereinafter referred to as Ni-based powder) are as follows.

First, the Ni-based powder exhibits antibacterial and antifungal properties because the surface of the material is adsorbed on the surface of the adsorbed water, which is present in an ordinary atmosphere of about 10 nm to 1 μm and in a high humidity atmosphere of about several tens to several 100 μm. It is considered that Ni and the like elute and bacteria and fungi, which are considered to grow in the presence of adsorbed water, come into contact with the Ni ions and die. In order to effectively exert such a sterilizing effect, it is necessary to contain Ni in an amount of 20 mass% or more in the Ni-based powder, and in order to exert the sterilizing effect more effectively, it should be contained in an amount of 50 mass% or more. desirable.

The cause of the effect of hydrogen on the antibacterial and antifungal properties is that i) hydrogen has a reducing action and N
Prevents oxidation and alteration on the surface of the i-based powder and keeps the surface of the Ni-based powder in an active state to maintain a stable elution amount of Ni. ii)
It is considered that hydrides act synergistically on the two functions of effectively altering and destroying the proteins that make up fungi and mold. In particular, the above-mentioned action ii) is considered to be extremely effective because it has an antibacterial / fungal mechanism different from the action derived from Ni and has a low possibility of producing resistant bacteria.

In order to effectively exhibit the action of hydrogen, it is necessary to contain at least 0.1 ppm or more in the Ni-based powder, and if it is less than this, a satisfactory antibacterial
Antifungal property cannot be obtained. However, the amount of hydrogen is 10,000p
If it exceeds pm and is excessively large, the toughness of the Ni-based powder becomes poor, and hydrogen cannot exist stably in the surface layer portion, and the stability of the effect is impaired. Therefore, it should be suppressed to 10,000 ppm or less. The more preferable content of hydrogen is 1
It is 0 ppm or more and 1,000 ppm or less.

The greatest feature of the present invention is that a P- and / or S-containing compound (hereinafter referred to as P, S-containing compound) is attached to the surface of the Ni-based powder as described above to stabilize a proper amount of hydrogen. In addition, the action and effect brought about by the P, S-containing compound are as follows.

That is, the inventors of the present invention have conducted extensive studies to establish a method for stably containing a large amount of hydrogen in the Ni-based powder under the known technique as described above, and as a result, It was found that the presence of the P, S-containing compound on the surface was extremely effective.

The mechanism of how hydrogen penetrates and is fixed in the Ni-based alloy has not been clarified.
When a P, S-containing compound is allowed to exist on the surface of the system powder,
It was confirmed that a large amount of hydrogen could be retained on the surface by a short hydrogenation treatment. Therefore, in producing the powder of the present invention, a P- and S-containing compound is attached to the surface of the Ni-based powder and then a hydrogen-containing treatment is performed, or a treatment that combines the attachment of the P and S-containing compound and the hydrogen-containing treatment is performed. If you give
As a result, the powder of the present invention is a new antibacterial / antifungal powder in which P- and S-containing compounds are present on the surface of the Ni-based powder and a large amount of hydrogen is contained as compared with the conventional example.

Moreover, P, which is attached to the surface of the Ni-based powder,
The S-containing compound is not treated with P and / or S in the subsequent heat treatment.
Diffuses into the Ni-based powder to cause grain boundary segregation, and as a result, also exerts an action of enhancing the elution of Ni ions from the Ni-based powder. Therefore, the elution of antibacterial metal ions into the adsorbed water during use is accelerated, which also contributes to the improvement of antibacterial and antifungal properties. However, if the above heat treatment is carried out after hydrogen is contained, the hydrogen that has been introduced may possibly be released. Therefore, it is desirable that the heat treatment be carried out before hydrogen is contained.

Further, in the case where the P-containing compound is adhered to the surface of the Ni-based powder, P becomes a reducing ion during use and is eluted into the adsorbed water, which also contributes to the improvement of the antibacterial and antifungal properties. .

The action of the P- and S-containing compound is Ni as disclosed in the above-mentioned JP-A-2000-43422.
It cannot be obtained if P is contained in the system powder.
By the way, when Ni-P alloy is used as the Ni-based powder material as described in the above publication, a sufficient amount of P can be contained in order to ensure the strength and to secure the strength of the alloy powder. In addition, the exposure of P to the surface is insufficient, so that a satisfactory antibacterial / antifungal action cannot be obtained. Moreover, the production of the Ni-P alloy requires high cost, and if the P content is high, it becomes difficult to obtain a uniform Ni-P-containing alloy.

On the other hand, as described above, the powder in which the P, S-containing compound is adhered to the surface of the Ni-based powder is easy to manufacture and the necessary amount of P or S can be easily adhered, as described later. Therefore, it is possible to inexpensively manufacture a product having stable and excellent antibacterial and antifungal effects.

The action and effect of the P, S-containing compound described above is
The area ratio of the P and S-containing compounds attached to the surface of the Ni-based powder is important in order to achieve a good balance with the antibacterial / rust-proofing effect of Ni or its alloy itself and the antibacterial / mold-proofing action of hydrogen. That is, when the area ratio of the compound is too large, it becomes difficult to effectively exhibit the antibacterial effect of Ni or its alloy and hydrogen, and when the area ratio of the compound is too small, the action of the P, S-containing compound is significant. This is because it is difficult for them to be demonstrated. In addition, the P and / or S-containing compound itself also has P and / or S in the compound.
The higher the content of, the better the antibacterial and antifungal properties.

As a practical matter, it is difficult to accurately know the area ratio of the P, S-containing compound on the surface of Ni or its alloy powder. Therefore, in the present invention, instead of the above area ratio, P,
It is recommended to adopt a method of controlling the amount of S-containing compound deposited. Specifically, the amount of P, S-containing compound in the total mass of the Ni-based powder is 0.001% by mass or more, more preferably 0.1% by mass or more in terms of P and / or S, and 1 It is preferable to control it to be not more than mass%.

Incidentally, the total amount of P and S conversion is 0.00
If it is less than 1% by mass, antibacterial effect due to the adhesion of P and S containing compounds
If the fungicidal action is insufficient, it is difficult to obtain the intended effect of the present invention. On the contrary, if the amount exceeds 1% by mass and becomes excessively large, N
The surface exposure of i or its alloy powder is likely to be insufficient, and N
This is because i's own antibacterial and antifungal effects are difficult to be effectively exerted, and the performance is insufficient as a whole.

In the present invention, the type of P, S-containing compound formed on the surface of Ni or its alloy powder is not particularly limited, and phosphorus, sulfur itself, oxides thereof, other phosphorus compounds, sulfur compounds, phosphates, etc. And sulfates, composite compounds thereof, various alloys containing P and S, and the like. Further, of course, it may be a complex compound or a mixture of a compound other than phosphorus or sulfur and a phosphorus (or sulfur) -containing compound.

However, the action and effect of P and S described above, in particular, the action of promoting penetration of hydrogen into the Ni-based powder, the action of promoting diffusion of P and S into the Ni-based powder by heat treatment, and further to the adhered water. Considering comprehensively the easiness of ionization by dissolution and the like, the oxidation products of P and S are preferable, and particularly preferable are one or more kinds of zinc phosphate, calcium phosphate, iron phosphate, manganese phosphate and the like. It is a film. By the way, these coatings are not only easy to manufacture themselves, but also easy to adhere to the surface of the Ni-based powder and easy to control the P and S contents (adhesion amount), so that the target antibacterial and protective properties can be obtained. This is because it is easy to adjust the performance according to the fungus action.

The antibacterial and antifungal powder of the present invention is a compound of P or S containing Ni or its alloy powder adhered to the surface as described above. The amount of adhesion is P or S adhered to the surface. It may be measured by dissolving only one of the compound and Ni or its alloy and leaving the other as an insoluble matter.

As a method for producing the above-mentioned antibacterial / antifungal powder, first, a Ni-based alloy having a Ni content of 20% by mass or more, preferably 50% by mass or more, and more preferably a powder consisting essentially of Ni alone. Is produced by any known method, and the powder is brought into contact with a P, S-containing compound to adhere to the surface thereof, and then heat treatment is preferably carried out at about 100 to 700 ° C. to form the P, S-containing compound on the surface. After fixing, it is desirable to carry out a treatment containing hydrogen.

There is no particular limitation on the type of other components that are allowed to be mixed in the Ni-based powder used as a raw material, and other alloying elements such as Co and oxygen, and further mixed in during Ni production. Certain known impure elements and the like are included.

There are various methods such as a wet or dry plating method, a chemical conversion treatment method, and an adsorption method as a method for adhering the P, S containing compound to the Ni-based powder, and any method is adopted in the present invention. I do not care. However, in order to easily attach a desired amount of P, S-containing compound by a short-time treatment, a method of immersing the Ni-based powder in a phosphoric acid solution or a method of surface-treating with a phosphate is a preferable method. Recommended.

Further, the method of incorporating hydrogen into the Ni-based powder to which the P, S-containing compound has been attached does not require any special method, and the existing method as described above can be adopted. the simple is the Ni-based powder, the amount of elution of the powder is 0.05g / m ² / h or more, 50g / m ² / h or less, more preferably 0.1g / m ² / h or more, 20 g /
It is a method of immersing in an aqueous solution of m ² / h or less for 1 minute or more and 10,000 minutes or less, more preferably 5 minutes or more and 2,000 minutes or less. If this method is adopted, N
A large amount of hydrogen can be uniformly contained in the i-based powder.

This hydrogen-containing treatment utilizes the generation of hydrogen that occurs as a reaction accompanying the oxidation reaction of the Ni-based powder when immersed in an aqueous solution. Most of the generated hydrogen is generated as hydrogen gas. A part penetrates into the Ni-based powder and diffuses throughout the powder. When this hydrogen-containing treatment method is adopted, the hydrogen content is almost uniquely determined by the solution composition used for the treatment, the temperature, and the immersion time. Therefore, it is easy to control the hydrogen content and, if necessary, a large amount of hydrogen is used. Can be included.

The above hydrogen generation reaction occurs along with the oxidation reaction of the Ni-based powder in the above treatment solution, but when a film is formed on the powder surface by the oxidation reaction, the above reaction is suppressed. Therefore, in order to promote the hydrogen generation reaction smoothly, it is necessary to use, as the treatment liquid, an aqueous solution having a small film formation and capable of continuously promoting the elution reaction of the Ni-based powder.

From this point of view, when the conditions of the immersion treatment for continuously and efficiently proceeding the hydrogen generation reaction were examined, the elution amount of the Ni-based powder by the immersion treatment was 0.05 to 50 g / m ² / h. , Preferably 0.1-20
Within the range of g / m ² / h, and under this condition, 1 minute or more, 1
10,000 minutes or less, more preferably 5 minutes or more, 2,000
By soaking for 0 minutes or less, the hydrogen content in the obtained Ni-based powder can be controlled within the range of 1 to 10,000 ppm.

The elution rate of the Ni-based powder during the dipping treatment can be obtained by dividing the weight loss before and after the treatment by the treatment time and the surface area of the entire powder. In addition, the surface area of the whole powder is obtained by calculating the surface area per powder from the average particle diameter of the powder, and the number of powders obtained from the mass or density / volume of each powder and the mass of the whole powder, and per powder. It may be determined by integrating the surface areas of Then, when the elution rate per mass of the Ni-based powder as a whole and the immersion time are out of the preferable ranges, the hydrogen content of the obtained Ni-based powder becomes deficient or insufficient,
The purpose of the present invention may not be met.

The components in the aqueous solution used for the above-mentioned dipping treatment are not particularly limited, but preferable ones are various acids such as H ₂ SO ₄ , HCl, HF, H ₃ PO ₄ and alkalis such as NaOH; H ₂ O ₂ , FeCl ₃ ,
Various oxidizing agents such as Fe ₂ (SO ₄ ) ₃ are exemplified. When an acid aqueous solution such as H ₂ SO ₄ , H ₃ PO ₄ , or H ₃ PO ₃ is used as a treatment liquid, P and / or S is added to the surface of the Ni-based powder.
It is also possible to use it as a treating agent for attaching the contained compound.

The average particle size and shape of the Ni-based powder used in the present invention are not particularly limited, but 0.01 is preferable in consideration of practicality as a metal powder for imparting antibacterial / fungistatic properties. -100 μm, more preferably 0.1-10
A complex shape with a particle size of μm and with irregularities on the surface enhances the dispersibility when blended into the surface treatment film and is used, as well as the elution of Ni ions during actual use. Is preferable because it can be improved.

The hydrogen-containing treated Ni-based powder and the treatment liquid may be separated by a method of filtering with a filter paper or a filter, a centrifugal separation method, a method of separating with an electromagnet, or the like. Then, in order to remove the acid or alkaline water adhering to the surface, it is desirable to wash with water or neutralize with a weak acid or weak alkali.

When heated after the above hydrogen-containing treatment,
Since the diffusion coefficient of hydrogen in the Ni-based powder is increased and the hydrogen introduced at the corner may be reduced, it is desirable to perform the drying at a low temperature near room temperature.

The present invention is constructed as described above, and Ni
The Ni-based powder having excellent antibacterial activity can be efficiently produced at low cost simply by subjecting the powder to the simple treatment as described above.

When the powder containing the antibacterial and antifungal properties is contained in an amount of 1 to 30% by mass in various known inorganic substances, organic substances or a mixture thereof, the antibacterial and antifungal properties are imparted to them. be able to. As the substance to be mixed with the antibacterial / antifungal powder, various coating resins, metal materials subjected to metal or alloy plating, anodizing treatment, ceramics, concrete, plastics, etc. can be widely applied. By compounding these substances, excellent antibacterial and antifungal properties can be imparted to all of these substances.

Specific examples of the above coating resin include alkyd resin, nitrocellulose resin, butyral resin,
Polyurethane resin, epoxy resin, tar epoxy resin, melamine resin, acrylic resin, vinyl chloride resin, silicone resin, fluorine resin, vinylidene fluoride resin, polyamide resin, polycarbonate resin, glass fiber Examples include reinforced polyester resins and the like, and an appropriate amount of the above-mentioned antibacterial and antifungal powder may be mixed therein.

Considering the wide range of applications, the dispersibility of the Ni-based powder, the adhesion between the resin and the Ni-based powder, the processability of the resin, the scratch resistance, and the like, vinylidene fluoride-based resin and acrylic resin, Epoxy resins, silicone resins and mixed resins thereof are recommended as preferable coating resin materials.

If the content of the Ni-based powder is less than 1% by mass, the effect of imparting antibacterial and antifungal properties is insufficient and it is difficult to obtain the intended level of effect in the present invention. If it is blended too much, the mechanical strength may be adversely affected, and the workability and scratch resistance may be deteriorated, depending on the type of resin to be blended. Therefore, it is desirable to adjust the blending amount of the Ni-based powder to 1% by mass or more and 30% by mass or less, more preferably 1% by mass or more and 10% by mass or less.

There are no particular restrictions on the method for coating various members using the above coating resin, but typical methods include spray coating, electrostatic coating, dip coating, powder coating,
Examples include electrodeposition coating and roll coater coating.

As the plating, for example, zinc plating, chromium plating, nickel plating, tin plating, etc. are exemplified, and the above Ni-based powder may be contained in these plating materials by a dispersion plating method or the like. As a plating method,
Wet plating methods such as electroplating and electroless plating and various vapor phase plating methods can be arbitrarily selected and applied.

Further, after the anodizing treatment, the pore portion in the porous anodizing layer is sealed with a resin or a metal salt containing the Ni-based powder, and the anodizing layer is antibacterial. -It can give mold resistance. As the metal salt used in this case, for example, an acetate salt such as nickel, cobalt, zinc, aluminum, copper, lead, etc., a nitrate salt, a sulfate salt or the like can be used. Can be used.

As the ceramic, various oxides such as silicon oxide, lead oxide, boron oxide, titania, zirconia and alumina, as well as various carbides, nitrides and borides can be used. A moldproof powder may be added. As a method of forming these ceramic layers on a metal, an alloy or other inorganic substance, a known method such as enamel or sol-gel method may be adopted.

As the concrete which can be provided with antibacterial and antifungal properties by the powder, pastes, mortars, etc., in which various cements or aggregates and water are kneaded and solidified,
Concrete, coal tar enamel, asphalt, etc. are included, and the surface of the base material may be coated with them by a lining method or a coating method.

Further, as the plastic to which the above-mentioned antibacterial and antifungal powders can be blended, vinyl chloride resin, epoxy resin, tar epoxy resin, polyolefin resin such as polyethylene and polypropylene, polyester resin, polyurethane resin, etc. Resins, acrylic resins, fluorine resins, vinylidene fluoride resins, etc. are exemplified, and by adding an appropriate amount of the above-mentioned antibacterial / antifungal powder, it is possible to impart antibacterial / fungistatic properties to the resin molding itself. In addition to being effectively used as various molding materials, it can also be used as a laminate material or a lining material for imparting antibacterial and antifungal properties.

[0055]

EXAMPLES The present invention will be described in more detail with reference to the following experimental examples. However, the present invention is not limited to the following experimental examples, and may be appropriately applied within the scope of the above and the following points. Modifications can be made and implemented, and all of them are included in the technical scope of the present invention.

Experimental Examples As examples and comparative examples, test materials were prepared under the following conditions and evaluated for antibacterial and antifungal properties.

The Ni-based powder used in the test was melted and then pulverized to have an average particle size of about 1 μm. The surface of the powder was subjected to a P, S-containing compound adhesion treatment. The adhesion treatment was performed according to the following (A) to (D).

(A) Palladium chloride: 0.01 mol /
dm ^3, ethylenediamine: 0.08 mol / dm ^3, sodium phosphinate: 0.06 mol / dm ^3, thio diglycolic acid: surface adhesion treatment of the Pd-5 mass% P using an aqueous solution containing 30 mg / dm ^3, (B) 10 mass%
Surface adhesion treatment of S oxide by immersion in Na ₂ SO ₄ solution, (C) Surface adhesion treatment of P oxide by immersion in 10 mass% H ₃ PO ₄ solution, (D) Commercial phosphate treatment solution Surface treatment treatment of zinc phosphate, iron phosphate, calcium phosphate or manganese phosphate by immersion in a treatment bath containing zinc ion, iron ion, calcium ion or manganese ion.

Next, the powder was subjected to a hydrogen-containing treatment.
The hydrogen-containing treatment was performed according to the following (E) to (F).

(E) Hydrogen-containing treatment by exposure in a hydrogen gas atmosphere at 800 ° C. and 1 atm, (F) NaCl; 50 g
/ L, HCl; 0.0001 to 17 mass%, HF; 0
Hydrogen-containing treatment by immersion in an aqueous solution containing 10% by weight.

Then, after washing with water and drying, for some of the treated powders, a commercially available 2,4,6-vinylidene fluoride copolymer and a commercially available acrylic resin were mixed in a mass ratio of 7: 3. Then, the Ni-based powder was added to the solvent-added product and dispersed for 30 minutes with a paint shaker to produce a paint.
Then, a stainless steel plate was roll coater-coated and baked and cured. Some of the treated powders were mixed and dispersed in a sol prepared from fine silica powder and CH ₃ Si (OCH ₃ ) ₃ and then dip-coated and heat-treated at 500 ° C. to obtain a 10 μm SiO ₂ film. Was formed.

The antibacterial and antifungal properties of the obtained treated powders and coated stainless steel sheets were evaluated by the following methods. The Ni, P, and S contents of each powder are confirmed by ICP emission spectroscopy after eluting each powder with nitric acid or nitric hydrofluoric acid, and the hydrogen content is measured with a temperature-increasing gas analyzer. I went.

For the evaluation of antibacterial properties, Staphylococcus aureus and Escherichia coli were used as the bacterial species, and each bacterial cell after culturing had a concentration of 2 × 10 5.
0.5 ml of the liquid adjusted to be ⁵ to 1 × 10 ⁶ (CFU / ml) was dropped on each Ni-based powder or coated stainless steel plate, and a polyethylene film was covered on the Ni-based powder or the coated stainless steel plate to make them adhere to each other.

After keeping this for 2 hours under the conditions of 35 ° C. and relative humidity of 90% or more, the viable cell count (bacterial survival rate:%) was measured by the plate dilution method, and converted per sample.
The survival rate in the test using each bacterium is averaged, and when the average survival rate is less than 5%, it is evaluated. ○ When 5% or more and less than 20% is evaluated. When it was 50% or more, it was expressed as evaluation x.

For the antifungal investigation, black koji mold was used as the fungus species, and 2.0 ml of the spore suspension was added to 400 ml of PD.
In addition to the medium, a stock culture solution was prepared. 1.0% by mass of each Ni-based powder obtained above was added to this stock solution, or the coated stainless steel plate obtained above was inoculated and cultured for 1 week. If the growth of hyphae is not observed, it is evaluated ○, if the growth of hyphae is observed, it is evaluated ◇, if spores are not formed but the hyphae cover the whole, it is evaluated △, if black spores are formed, it is evaluated ×.
Expressed as

In addition, the lowest evaluation result of the above-mentioned three kinds of evaluations was taken as the comprehensive evaluation of antibacterial and antifungal properties.

Treatment process of powder treated according to the example, amount of P, S-containing compound, amount of P, S conversion,
Table 1 collectively shows the evaluation results of the amount of hydrogen, antibacterial properties and antifungal properties. In addition, when the hydrogen-containing treatment (F) is performed, Ni
Fig. 1 shows the results of examining the effects of the immersion time and the elution amount of the system powder on the comprehensive evaluation of antibacterial and antifungal properties. Also, test N in Table 1
o. In the resin and SiO ₂ film in which 17 powders are mixed,
FIG. 2 shows the results of examining the relationship between the mixing ratio of the Ni-based powder and the comprehensive evaluation of antibacterial and antifungal properties.

[0068]

[Table 1]

As is clear from Table 1, a Ni-based powder satisfying the Ni content and hydrogen content specified in the present invention and having a predetermined amount of a compound containing at least one of P and S attached on the surface. It can be seen that has excellent antibacterial and antifungal properties. Further, as is clear from FIG. 1, when the Ni-based powder is immersed in a treatment liquid showing an appropriate elution amount with respect to the Ni-based powder for a predetermined time, the antibacterial /
Mold resistance can be imparted. As is clear from FIG. 2, resin or Si prepared by mixing the Ni-based powder in an appropriate ratio is used.
The O ₂ film has excellent antibacterial and antifungal properties.

[0070]

INDUSTRIAL APPLICABILITY The Ni-based powder of the present invention is constituted as described above, and in addition to the elution of Ni ions, the surface activation effect by the contained hydrogen and the action of the P, S-containing compound attached to the surface are exerted. Together, they show outstanding antibacterial and antifungal activity, so equipment and parts that require antibacterial and antifungal properties in various fields, including the food processing field and medical field, where antibacterial and antifungal properties are desired. It can be widely and effectively used as an additive for surface treatment. Further, by using the production method of the present invention, the Ni-based powder having the above-mentioned excellent antibacterial and antifungal properties can be easily obtained. Furthermore, by blending the Ni powder as an antibacterial / antifungal property-imparting agent into various materials, various materials can be provided with antibacterial / antifungal properties, and members having excellent antibacterial / antifungal properties can be obtained.

[Brief description of drawings]

FIG. 1 N in hydrogen-containing treatment (F) adopted in the experiment
It is a graph which shows the influence which the immersion time and the elution amount of i-type powder have on antibacterial and antifungal comprehensive evaluation.

FIG. 2 is a graph showing the relationship between the compounding ratio of the antibacterial / fungistatic powder to the resin or the SiO ₂ film and the comprehensive antibacterial / fungistatic evaluation result.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C09C 3/06 C09C 3/06 C22C 19/03 C22C 19/03 Z (72) Inventor Sadako Yamada Nishi Ward, Kobe City Takatsudai 1-5-5 Stock Company Kobe Steel Works Kobe Research Institute F-term (reference) 4J002 AB021 BD031 BD121 BD141 BE061 BG021 CC181 CD001 CF001 CF011 CG001 CK021 CL001 CP031 DA086 DG047 DH047 FB076 FD186 GB01 GC00GG0200 GQ00 4J037 AA04 AA06 CA19 CA22 CB21 EE02 EE43 FF21 4K018 AA08 BC28 BD10 KA70

Claims (8)

[Claims] 1. The Ni content of the Ni or Ni alloy portion is 2
0 mass% or more and hydrogen content of 1 to 10,000 pp
m on the surface of the Ni or Ni alloy powder, P and / or
Alternatively, the S-containing compound is attached, and the amount of the P- and / or S-containing compound attached is 1 in the ratio of the whole powder.
The content of P and / or S in the compound is 0.001 or less in the whole powder.
A Ni-based powder having excellent antibacterial and antifungal properties, which is characterized by being at least mass%. 2. The Ni content of the Ni or Ni alloy portion is 5
The Ni-based powder excellent in antibacterial and antifungal properties according to claim 1, which is 0 mass% or more. 3. The P- and / or S-containing compound is
The Ni-based powder having excellent antibacterial and antifungal properties according to claim 1 or 2, which contains an oxide or a complex oxide of P and / or S. 4. The P- and / or S-containing compound is
The Ni-based powder having excellent antibacterial / antifungal properties according to claim 1 or 2, which contains at least one selected from zinc phosphate, calcium phosphate, iron phosphate and manganese phosphate. 5. N according to any one of claims 1 to 4.
A method for producing an i-based powder, wherein Ni or Ni alloy powder has an elution amount of 0.05 to 50 g / m ² / h.
Ni having excellent antibacterial and antifungal properties, characterized by including a treatment of immersing the above aqueous solution for 1 to 10,000 minutes
A method of manufacturing powders. 6. N according to any one of claims 1 to 4.
A material having excellent antibacterial and antifungal properties, characterized in that the i-based powder is contained in an inorganic substance, an organic substance or a mixture thereof in an amount of 1 to 30% by mass. 7. The material according to claim 6, wherein the organic substance according to claim 6 is a vinylidene fluoride resin, an acrylic resin, an epoxy resin, a silicone resin, or a mixed resin thereof. 8. A member having excellent antibacterial and antifungal properties, characterized in that an inorganic member or an organic member is coated with the material according to claim 6 or 7.