JP2005350741A - Oxide film structure of iodine or iodine compound-sealed metallic material base and its forming method and applied article having the film structure - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an oxide film structure of an iodine or iodine compound-sealed metallic material base which is good in all of weatherability, appearance (color) stability, sterilizability, wear resistance, slidability, optical environmental catalyst, and colorability (coloring) and its forming method and an applied article. <P>SOLUTION: The oxide film structure is formed by using a metallic material selected from the group consisting of alloys composed mainly of Al and impregnating the micropores 3 of the oxide film 2 of the base 1 with the iodine or the iodine compound, and closing a portion or the whole of the mouth parts 3a of the micropores 3 and forming the iodine or the iodine compound 4 in a half sealed or sealed state into the micropores 3. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  INDUSTRIAL APPLICABILITY The present invention provides iodine or iodine compound-containing metal useful for applications requiring weather resistance, appearance (color) stability, bactericidal properties, antibacterial properties, abrasion resistance, slipperiness, photoenvironment catalyst, and colorability (coloring). The present invention relates to an oxide film structure of a material substrate, a method for forming the structure, and an applied article having the coating structure.

For example, there is an oxide film structure of an iodine or iodine compound-impregnated metal material base material proposed in Patent Document 1, a method for forming the structure, and an applied article having the coating structure (see FIG. 5).
In this oxide film structure, a metal material selected from the group consisting of an alloy mainly composed of any one of metals such as Al is used as a base material. It is impregnated with iodine or an iodine compound (hereinafter referred to as PVPI). And since it has bactericidal and antibacterial properties and has a large ultraviolet catalytic effect, it is suitable as an environment-resistant article, and because it has excellent wear resistance, it is also suitable for materials with high friction such as pistons. Yes.
By the way, the fine holes or fine irregularities impregnated with PVPI have a coating structure in which the mouth portion remains open and PVPI is exposed to the outside from the mouth portion.
Therefore, PVPI that is weak against moisture or the like is easily diffused, and it is confirmed that the surface of the article is discolored after about 2 hours after electrodeposition and impregnation, and lacks appearance (color) stability. This means that the weather resistance is inferior, leading to a decrease in bactericidal properties, antibacterial properties, ultraviolet catalytic effects, and abrasion resistance.
Also, when PVPI is impregnated by electrophoretic electrodeposition into fine pores or fine irregularities, film destruction is likely to occur, and when this film is destroyed, the surface of the article becomes rough and is not suitable for reprocessing. .
Since polyvinyl pyrrolidone iodine (PVPI) is dissolved in deionized water for bathing, color management at low cost is difficult.
For articles that emphasize appearance (color), it is essential to perform sealing treatment after anodizing, but stable sealing technology has not yet been established, and the manufactured article is discolored, and appearance ( It is difficult to make an article with a stable color. That is, the used sealing agent is not suitable for use because the precipitated iodine dissolves in the sealing agent.
Since PVPI has an odor, if the amount of PVPI deposited increases during the sealing process, the odor becomes stronger.
Japanese Patent No. 2932437

  The problem to be solved is at least weather-resistant, and good appearance (color) stability, bactericidal properties, antibacterial properties, abrasion resistance, slipperiness, photoenvironmental catalyst, and colorability (coloring) An object of the present invention is to provide an oxide film structure of a metal material substrate containing iodine or iodine compound, a method for forming the same, and an applied article.

In the present invention, impregnation means that PVPI is formed by immersion dyeing or electrophoretic electrodeposition in fine pores or fine irregularities.
Low-temperature sealing treatment means that a substrate with an oxide film formed is immersed in a low-temperature sealing liquid bathed with a sealing agent, and then lifted to open the pores with fine pores or fine irregularities into a film-like pore. Partially closed at the part, and semi-encapsulated in a state where the fine holes or fine irregularities are impregnated with PVPI. Such a semi-encapsulated state refers to a state where PVPI in a minute hole or minute unevenness can be evaporated and diffused from a mouth partly opened.
The high-temperature sealing treatment is to close all the fine pores or fine irregularities that are impregnated with PVPI with a film-like sealing portion and enclose the fine holes or fine irregularities in a state where PVPI is impregnated with PVPI. Point to. Such an encapsulated state refers to a state in which there is no vaporization / release of PVPI from the closed mouth.
Immersion dyeing refers to impregnation by impregnation by dyeing PVPI into fine pores or irregularities by immersing it in a liquid bathed with a dye containing at least PVPI. In this way, PVPI impregnates fine pores or fine irregularities without using electricity.
Electrophoretic electrodeposition refers to electrodeposition by electrophoresis.

In order to achieve the above-described problems, the present invention is characterized in that the oxide film structure of the iodine or iodine compound-containing metal material base material has the following configuration.
1. A metal material selected from the group consisting of Al-based alloys is used as a base material, and PVPI is impregnated into the fine pores or fine irregularities of the oxide film of the base material. The mouth part is partially closed with a film-like sealing part, and PVPI is formed in a semi-encapsulated state in the fine hole or fine unevenness.
Examples of the substrate made of an alloy mainly composed of Al in the present invention include Al—Cu, Al—Mn, Al—Si, Al—Mg, Al—Mg—Si, and Al—Zn. It is done. The oxide film is obtained by an anodic oxidation method or etching type anodic dissolution, and a film having fine holes or fine irregularities is obtained.
The iodine compound may be an inorganic compound that can impart lubricity, or may be an organic compound that is excellent in lubricity, bacteria resistance, wear resistance, environmental catalyst function, and the like. In this organic compound, a characteristic group of iodine (I) is combined with an organic compound selected from the group consisting of a chain saturated hydrocarbon, a chain unsaturated hydrocarbon, a cyclic compound, and an aromatic compound (including a heterocyclic compound). It may be an organic compound. Moreover, it is the compound which the iodine compound combined with the heterocyclic compound, Comprising: It may be selected from the group of polyvinylpyrrolidone iodine, polyvinyl phthalimide iodine, polyvinyl butyral iodine, polyvinyl formal iodine.
The film-like sealing part may be made of a sealing agent, may have PVPI in the sealing agent, or may be made of PVPI. Good.

  2. A metal material selected from the group consisting of Al-based alloys is used as a base material, and PVPI is impregnated into the fine pores or fine irregularities of the oxide film of the base material. All the mouths are closed with a film-like sealing part, and PVPI is formed in a sealed state in the fine holes or fine irregularities.

  3. In 1 or 2 described above, the film-shaped sealing portion is characterized by having iodine or iodine compound similar to iodine or iodine compound impregnated in the fine pores or fine irregularities.

And in the formation method of the oxide film of a PVPI enclosure metal material base material, it was characterized by having the following structures.
4). A metal material selected from the group consisting of Al-based alloys is used as a base material, an oxide film is provided on the base material by an oxidizing means, and PVPI is impregnated into fine pores or fine irregularities formed in the oxide film. After that, a low-temperature sealing treatment is performed to partially close the mouth portion of the fine hole or fine unevenness with a film-like sealing portion, thereby forming PVPI in a semi-encapsulated state in the fine hole or fine unevenness. .
The temperature in the low-temperature sealing liquid is less than 70 ° C. at which PVPI does not decompose, and is preferably suitable for mass production at 40 ° C.

5). Based on a metal material selected from the group consisting of alloys mainly composed of Al, the base material was provided with an oxide film by oxidation means, and PVPI was impregnated into the fine holes or fine irregularities formed in the oxide film. After that, the low-temperature sealing treatment and then the high-temperature sealing treatment are performed to close all the micropores or fine unevenness mouth portions with the film-like sealing portions, thereby forming PVPI in an encapsulated state in the micropores or fine unevennesses. And
The temperature in the low temperature sealing liquid is as described above, while the temperature in the high temperature sealing liquid is 60 to 100 ° C.

6). In the above 4 or 5, the PVPI impregnation is performed by immersion dyeing.
As the dyeing agent used in this immersion dyeing, a dyeing agent comprising PVPI, a solvent and tap water, for example, a dyeing agent comprising PVPI, an alcohol solvent and tap water, a dyeing agent comprising PVPI, N ethyl 2-pyrrolidone and tap water. And other dyeing agents. Examples of alcohol solvents include hexane, methanol, ethanol, and ethyl alcohol. N ethyl 2-pyrrolidone is suitable for mass production because it is less likely to evaporate than alcohol solvents.

  7). In the above 4 or 5, the PVPI impregnation is performed by electrophoretic electrodeposition.

8). Any one of 4 to 7 described above is characterized in that the sealing agent that forms the film-shaped sealing portion comprises a sealing agent, a solvent, and PVPI.
Examples of the sealing agent include a sealing agent mainly composed of nickel fluoride, a sealing agent mainly composed of nickel acetate, and other sealing agents. The sealing agent mainly composed of nickel fluoride and the sealing agent mainly composed of nickel acetate are well suited for color stability. The color is not stable in general steam sealing or hot water sealing. Examples of the solvent include alcohol solvents and N ethyl 2-pyrrolidone. Examples of alcohol solvents include hexane, methanol, ethanol, and ethyl alcohol. N ethyl 2-pyrrolidone is suitable for mass production because it is less likely to evaporate than alcohol solvents.

An application article having an oxide film structure of a base material of iodine or iodine compound-containing metal material has the following structure.
9. 3. The film structure according to 1 or 2 described above, wherein the film has at least weather resistance, appearance (color) stability, bactericidal property, antibacterial property, abrasion resistance, slipping property, light environmental catalyst, coloring property (coloring) ) Is intended for any of the above.
As such applied articles, various kinds of materials that have at least weather resistance, and are required to have appearance (color) stability, bactericidal properties, antibacterial properties, abrasion resistance, slipperiness, photocatalytic catalysts, and coloring properties (coloring). Product.

A. According to claim 1, PVPI that is vulnerable to moisture is semi-encapsulated in the fine pores or fine irregularities of the oxide film, so that vaporization from the mouth to the outside can be suppressed somewhat, and the weather resistance is sustained and exhibited. . And it is useful for the use for which bactericidal property, antibacterial property, and light environment catalyst are required.
B. According to claim 2, PVPI that is vulnerable to moisture is encapsulated in the fine pores or fine irregularities of the oxide film, so that vaporization from the mouth to the outside can be largely suppressed, and good weather resistance is sustained and exhibited. And it is useful for applications that require appearance (color) stability, wear resistance, slipperiness, light environmental catalyst, and colorability (coloring), and the film-like sealing part is worn away to release the sealing. And if a mouth part will be opened, PVPI will spread from a mouth part and it can exhibit about bactericidal property and antibacterial property.
C. Further, according to the third aspect, since the film-like sealing portion has PVPI, bactericidal and antibacterial properties can be obtained by the sealing portion itself. In addition, in the configuration in which the sealing portion closes the mouth portion, bactericidal and antibacterial properties until the sealing portion is released due to wear of the sealing portion and PVPI vaporizes and diffuses from the mouth portion. The sterilization and antibacterial properties can be obtained continuously.
D. According to the fourth aspect of the present invention, PVPI which is weak against moisture can be semi-encapsulated in the fine pores or fine irregularities of the oxide film, so that it can be weathered with somewhat suppressed vaporization from the mouth to the outside. And it is useful as a manufacturing method of what has bactericidal property, antibacterial property, and a light environment catalyst.
E. According to the fifth aspect, PVPI is sealed after being semi-encapsulated in the fine pores or fine irregularities of the oxide film, so that PVPI which is weak against moisture can be encapsulated while remaining in the fine pores or fine irregularities of the oxide film. In addition, it can be made to have good weather resistance in which vaporization from the mouth portion to the outside is suppressed. And it is useful as a manufacturing method of what has external appearance (color) stability, abrasion resistance, slipperiness, a light environment catalyst, coloring property (coloring), and has antibacterial property.
F. According to the sixth aspect, since it is not electrodeposition, there is little possibility of roughening the surface of the base material, and reprocessing is easy.
G. According to claim 7, the impregnation effect is further great.
H. According to the eighth aspect of the present invention, since the saturated state is created by the PVPI in the sealing agent during the sealing treatment, it is difficult to vaporize the PVPI impregnated in the fine pores of the oxide film and the sealing treatment is performed. it can.
I. According to claim 9, various products that have at least weather resistance and are further required to have appearance (color) stability, bactericidal properties, antibacterial properties, abrasion resistance, slipperiness, photoenvironmental catalyst, and colorability (coloring). Suitable for

FIG. 1 illustrates another embodiment of the oxide film structure of the iodine or iodine compound-encapsulated metal material substrate of the present invention. PVPI 4 is provided in the micropores 3 in the soft anodized film 2 on the aluminum substrate 1. Is impregnated.
The opening 3a of the micropore 3 impregnated with PVPI4 is partially sealed by the membrane-like sealing portion 5 by being sealed, so that the PVPI4 is almost enclosed in the micropore 3. It is formed in the state. The fine hole 3 has a hole diameter of 10 μm to 50 μm and a hole depth of 20 μm to 700 μm. The thickness of the film-like sealed part 5 that partially closes the mouth 3a of the fine hole 3 is about 20 μm. It is. The film-like sealing part 5 is formed by adding PVPI4 to an appropriate sealing agent.
As a result, PVPI 4 that is vulnerable to moisture is semi-encapsulated in the fine pores 3 of the alumite film 2, so that the diffusion from the mouth 3a to the outside is somewhat suppressed and weather resistance is obtained. The PVPI 4 diffusing from the film-shaped sealing portion 5 and the PVPI 4 diffusing outside through the mouth portion 3a exhibit bactericidal properties, antibacterial properties, and a light environment catalyst.

FIG. 2 exemplifies an embodiment of the oxide film structure of the base material of iodine or iodine compound-containing metal material according to the present invention. The micropores 3 in the hard anodized film 2 on the aluminum substrate 1 are impregnated with PVPI4. Has been.
The mouth 3a of the micropore 3 impregnated with the PVPI 4 is completely closed by the film-like sealing portion 5 by being sealed, and the PVPI 4 is completely enclosed in the micropore 3 It is formed. The fine hole 3 has a hole diameter of 10 μm to 50 μm and a hole depth of 20 μm to 700 μm, and the thickness of the film-like sealing part 5 that closes the mouth 3 a in the fine hole 3 is about 20 μm. . The film-like sealing part 5 is formed by adding PVPI4 to an appropriate sealing agent.
As a result, PVPI 4 that is vulnerable to moisture is sealed in the micropores 3 of the hard anodized film 2, so that diffusion from the mouth portion 3a to the outside can be suppressed, and favorable weather resistance is achieved. Further, since the mouth 3a of the fine hole 3 is closed, there is no color change, it is difficult to cause a stain, the appearance (color) is stable, and the appearance management between lots is easy. And it exhibits abrasion resistance, slipperiness, a light environment catalyst, and coloring property (coloring), and it is also obtained about bactericidal property and antibacterial property by PVPI4 diffused from the film-like sealing portion 5. Further, after the film-like sealing part 5 is worn and the mouth part 3a is opened, PVPI 4 is diffused to the outside through the mouth part 3a, and thus bactericidal and antibacterial properties are continuously exhibited. Is done.

FIG. 3 illustrates the above-described method for forming the film structure of FIG. 1 as one embodiment of the method for forming the film structure of the iodine or iodine compound-encapsulated metal material base material of the present invention.
After the aluminum substrate 1 is degreased and washed with water and pretreated, a 20% sulfuric acid aqueous solution is electrolyzed at a current concentration of 3 A / d and a bath temperature of 20 ° C. using a carbon electrode as a cathode, so that the pore diameter is 10 μm to 50 μm. Thus, a soft alumite film 2 in which fine holes 3 having a hole depth of 20 μm to 700 μm are opened is formed.
Thereafter, the aluminum substrate 1 is immersed in a dyeing solution having a bath temperature of 50 ° C., which is constructed with N-methyl-2-pyrrolidone, PVPI, and tap water, and the dyeing solution is infiltrated into the micropores 3 of the alumite film 2 to start the immersion. 10 minutes after the removal, the fine pores 3 are impregnated by staining with PVPI4.
Next, it is immersed for 25 minutes in a sealing solution having a bath temperature of 90 ° C., which is constructed with N-methyl-2-pyrrolidone, PVPI, and tap water. A part of the film-shaped sealing part 5 having a thickness is closed to be semi-opened, and then left to be naturally dried, so that PVPI 4 is semi-encapsulated in the fine holes 3.

The mixing ratio of the dyeing solution and the sealing solution is shown below.
-Mixing ratio of dyeing solution N-methyl-2-pyrrolidone 10% by weight
20% PVPI
Tap water 70% by weight
-Mixing ratio of sealing liquid N-methyl-2-pyrrolidone 10% by weight
20% PVPI
Tap water 70% by weight

After the aluminum substrate 1 is degreased and washed with water and pretreated, a 30% sulfuric acid aqueous solution is electrolyzed at a current concentration of 3 A / d and a bath temperature of −10 ° C. using a carbon electrode as a cathode, whereby a pore diameter of 10 μm to A hard anodized film 2 is formed in which fine holes 3 having a pore depth of 20 μm to 700 μm are opened at 50 μm.
Thereafter, the aluminum substrate 1 is immersed in a dyeing solution having a bath temperature of 50 ° C., which is constructed with N-methyl-2-pyrrolidone, PVPI, and tap water, and the dyeing solution is infiltrated into the micropores 3 of the alumite film 2 to start the immersion. 10 minutes after the removal, the fine pores 3 are impregnated by staining with PVPI4.
Next, steam sealing is performed at 100 ° C. for 20 minutes, and the mouth portion 3a of the micropore 3 is partially closed with a film-like sealing portion 5 having a thickness of 20 μm, and then left open. It is formed in a state in which PVPI 4 is semi-encapsulated in the fine holes 3 by natural drying treatment.

The blending ratio of the dyeing solution described above is shown below.
-Mixing ratio of dyeing solution N-methyl-2-pyrrolidone 10% by weight
20% PVPI
Tap water 70% by weight

FIG. 4 illustrates the above-described method for forming the film structure of FIG. 2 as one embodiment of the method for forming the film structure of the iodine or iodine compound-encapsulated metal material substrate of the present invention.
After the aluminum substrate 1 is degreased and washed with water and pretreated, a 30% sulfuric acid aqueous solution is electrolyzed at a current concentration of 3 Amp and a bath temperature of −10 ° C. by using a carbon electrode as a cathode, so that the pore diameter is 10 μm to 50 μm. A hard anodized film 2 in which fine holes 3 having a hole depth of 20 μm to 700 μm are opened is formed.
Thereafter, the aluminum substrate 1 is immersed in a dyeing solution having a bath temperature of 50 ° C., which is constructed with N-methyl-2-pyrrolidone, PVPI, and tap water, and the dyeing solution is infiltrated into the micropores 3 of the alumite film 2 to start the immersion. 10 minutes after the removal, the fine pores 3 are impregnated by staining with PVPI4.
Next, it is immersed for 3 minutes in a primary sealing liquid with a bath temperature of 30 ° C., which is constructed with a sealing agent mainly composed of nickel fluoride, N-methyl-2-pyrrolidone, and PVPI, and then is pulled down and cooled. Then, the mouth portion 3a of the fine hole 3 is partially closed with a film-like sealing portion 5 having a thickness of 20 μm so as to be semi-opened, and further, a sealing agent mainly composed of nickel acetate, ethanol, and PVPI. And soaked in a secondary sealing solution with a bath temperature of 80 ° C. for 10 minutes, and then pulled up and subjected to high-temperature sealing treatment, fully closed with a film-shaped sealing portion 6 having a thickness of 20 μm, and then left standing Then, it is formed in a state in which PVPI 4 is completely enclosed in the fine holes 3 by natural drying treatment.

The blending ratio of the dyeing liquid, the primary sealing liquid, and the secondary sealing liquid is shown below.
-Mixing ratio of dyeing solution N-methyl-2-pyrrolidone 10% by weight
20% PVPI
Tap water 70% by weight
-Mixing ratio of primary sealing liquid N-methyl-2-pyrrolidone 10% by weight
20% PVPI
Sealing agent based on nickel fluoride 70% by weight
・ Composition ratio of secondary sealing liquid Ethanol 10% by weight
20% PVPI
Sealing agent based on nickel acetate 70% by weight

After the aluminum substrate 1 is degreased and washed with water and pretreated, a carbon electrode is used as a cathode, and an aqueous sulfuric acid solution having a concentration of 20% is electrolyzed at a current concentration of 3 Amp and a bath temperature of 20 ° C. so that the pore diameter is 10 μm to 50 μm. A soft alumite film 2 having a fine hole 3 having a depth of 20 μm to 700 μm is formed.
Thereafter, the aluminum substrate 1 is immersed in a dyeing solution having a bath temperature of 50 ° C. that is built with ethanol, PVPI, and tap water, and the dyeing solution is infiltrated into the micropores 3 of the alumite film 2. Later, the fine pores 3 are impregnated by being pulled up and dyed with PVPI4.
Next, it is immersed for 3 minutes in a primary sealing liquid with a bath temperature of 30 ° C. which is bathed with a sealing agent mainly composed of nickel acetate, ethanol, and PVPI, and is subjected to a low-temperature sealing treatment. 3 part 3a is partially closed with a film-like sealing part 5 having a thickness of 20 μm to make it semi-open, and further, a bath with a sealing agent mainly composed of nickel acetate, ethanol and PVPI. It is immersed in a secondary sealing liquid with a bath temperature of 80 ° C. for 10 minutes, and is pulled up and subjected to high-temperature sealing treatment, fully closed with a film-shaped sealing part 6 having a thickness of 20 μm, and then left to dry naturally. By processing, PVPI 4 is completely sealed in the fine holes 3.

The blending ratio of the dyeing liquid, the primary sealing liquid, and the secondary sealing liquid is shown below.
-Mixing ratio of staining solution Ethanol 10% by weight
20% PVPI
Tap water 70% by weight
-Mixing ratio of primary sealing liquid Ethanol 10% by weight
20% PVPI
Sealing agent based on nickel acetate 70% by weight
・ Composition ratio of secondary sealing liquid Ethanol 10% by weight
20% PVPI
Sealing agent based on nickel acetate 70% by weight

After the aluminum substrate 1 is degreased and washed with water and pretreated, a carbon electrode is used as a cathode, and an aqueous sulfuric acid solution having a concentration of 20% is electrolyzed at a current concentration of 3 Amp and a bath temperature of 20 ° C. so that the pore diameter is 10 μm to 50 μm. A soft alumite film 2 having a fine hole 3 having a depth of 20 μm to 700 μm is formed.
Thereafter, the aluminum substrate 1 is immersed in a solution having a bath temperature of 50 ° C., which is constructed with N-methyl-2-pyrrolidone, PVPI and tap water, and the solution is electrodeposited at 20 VDC for 10 minutes by electrophoresis. Thus, PVPI 4 is impregnated into the fine holes 3 of the alumite film 2.
Next, it is immersed for 3 minutes in a primary sealing liquid with a bath temperature of 30 ° C., which is constructed with a sealing agent mainly composed of nickel fluoride, N-methyl-2-pyrrolidone, and PVPI, and then is pulled down and cooled. Then, the mouth portion 3a of the fine hole 3 is partially closed with a film-like sealing portion 5 having a thickness of 20 μm so as to be semi-opened, and further, a sealing agent mainly composed of nickel acetate, ethanol, and PVPI. And soaked in a secondary sealing solution with a bath temperature of 80 ° C. for 10 minutes, and then pulled up and subjected to high-temperature sealing treatment, fully closed with a film-shaped sealing portion 6 having a thickness of 20 μm, and then left standing Then, it is formed in a state in which PVPI 4 is completely enclosed in the fine holes 3 by natural drying treatment.

The blending ratio of the above-described solution, primary sealing liquid, and secondary sealing liquid is shown below.
-Mixing ratio of dyeing solution N-methyl-2-pyrrolidone 10% by weight
20% PVPI
Tap water 70% by weight
-Mixing ratio of primary sealing liquid N-methyl-2-pyrrolidone 10% by weight
20% PVPI
Sealing agent based on nickel fluoride 70% by weight
・ Composition ratio of secondary sealing liquid Ethanol 10% by weight
20% PVPI
Sealing agent based on nickel acetate 70% by weight

Comparative Example 1

  After the aluminum substrate 1 is degreased and washed with water and pretreated, a carbon electrode is used as a cathode, and an aqueous sulfuric acid solution having a concentration of 20% is electrolyzed at a current concentration of 3 Amp and a bath temperature of 20 ° C. so that the pore diameter is 10 μm to 50 μm. A soft anodized film 2 in which fine holes 3 having a depth of 20 μm to 700 μm were opened was formed.

Comparative Example 2

  After the aluminum substrate 1 is degreased and washed with water and pretreated, a 30% sulfuric acid aqueous solution is electrolyzed at a current concentration of 3 Amp and a bath temperature of −10 ° C. by using a carbon electrode as a cathode, so that the pore diameter is 10 μm to 50 μm. A hard alumite film 2 in which fine holes 3 having a hole depth of 20 μm to 700 μm were opened was formed.

  FIG. 5 shows the antibacterial properties of the above-described Example 4 and Comparative Example 1 of the present invention. In Example 4, the amount was 50000 cells at the start of measurement of E. coli but decreased to less than 100 cells after 1 hour, Thereafter, it was kept below 100 cells. On the other hand, in the thing of the comparative example 1, it decreased only from 510000 cells at the time of a measurement start to 460000 cells, and it was the same numerical value after that.

  FIG. 6 shows the friction coefficient at a load of 10 N of the above-described Example 3 and Comparative Example 2 of the present invention. On the other hand, in the comparative example 2, it became about 0.6 to 0.7 after 10 m, and the friction coefficient showed a tendency to increase in proportion to the distance. Table 1 shows the test data of the coefficient of friction.

Sectional drawing which illustrates one Embodiment in the oxide film structure of the iodine or iodine compound enclosure metal material base material of this invention. Sectional drawing which illustrates another 1 form of implementation in the oxide film structure of the iodine or iodine compound enclosure metal material base material of this invention. The flowchart which illustrates one form of implementation in the formation method of the oxide film structure of the iodine or iodine compound enclosure metal material base material of this invention. The flowchart which illustrates other 1 form of implementation in the formation method of the oxide film structure of the iodine or iodine compound enclosure metal material base material of this invention. The graph which shows the antibacterial property of the thing of Example 4 and the comparative example 1 in this invention. The graph which shows the friction coefficient of the thing of Example 3 and the comparative example 2 in this invention. The flowchart in the formation method of the oxide film structure of the conventional iodine or iodine compound impregnation metal material base material.

Explanation of symbols

1 Aluminum substrate (base material)
2 Anodized film (oxide film)
3 Micropore 3a Mouth 4 PVPI (Iodine or iodine compound)
5 Film-like sealing part

Claims (9)

  It is based on a metal material selected from the group consisting of alloys mainly composed of Al, and impregnated with iodine or an iodine compound in the fine pores or fine irregularities of the oxide film of the base material, Iodine or iodine compound-containing metal material base material, wherein the mouth of the fine irregularities is partially closed with a film-shaped sealing portion, and iodine or iodine compound is formed in a semi-encapsulated state in the fine holes or fine irregularities Oxide film structure.   It is based on a metal material selected from the group consisting of alloys mainly composed of Al, and impregnated with iodine or an iodine compound in the fine pores or fine irregularities of the oxide film of the base material, Oxidation of iodine or iodine compound-containing metal material base material, characterized in that all mouths of fine irregularities are closed with a film-like sealing part, and iodine or iodine compound is formed in an enclosed state in the fine holes or fine irregularities Film structure.   3. The iodine or iodine compound-containing metal according to claim 1, wherein the film-shaped sealing portion has iodine or an iodine compound similar to iodine or an iodine compound impregnated in the fine pores or fine irregularities. The oxide film structure of the material substrate.   A metal material selected from the group consisting of an alloy mainly composed of Al is used as a base material, an oxide film is provided on the base material by an oxidizing means, and iodine or an iodine compound is formed in the fine pores or fine irregularities formed in the oxide film. After impregnating with a low-temperature sealing treatment, the micropores or fine irregularities are partially closed with a film-shaped sealing portion to form iodine or iodine compound in a semi-encapsulated state in the fine pores or fine irregularities A method for forming an oxide film on an iodine or iodine compound-containing metal material base material, comprising:   Based on a metal material selected from the group consisting of alloys mainly composed of Al, an oxide film is provided on the base material by oxidation means, and iodine or an iodine compound is formed in the fine pores or fine irregularities formed in the oxide film. After impregnation, low-temperature sealing treatment and then high-temperature sealing treatment are performed, and all the micropores or fine irregularities are closed with a film-like sealing portion, so that iodine or iodine compound is enclosed in the fine pores or fine irregularities. A method for forming an oxide film on an iodine or iodine compound encapsulated metal material base material, characterized in that:   6. The method for forming an oxide film on a base material for iodine or iodine compound-containing metal material according to claim 4 or 5, wherein the impregnation with iodine or iodine compound is performed by immersion dyeing.   6. The method for forming an oxide film on an iodine or iodine compound-containing metal material substrate according to claim 4 or 5, wherein the impregnation of iodine or an iodine compound is performed by electrophoretic electrodeposition.   The iodine or iodine compound-containing metal according to any one of claims 4 to 7, wherein the sealing agent for forming the film-like sealing portion comprises a sealing agent, a solvent, and iodine or an iodine compound. A method for forming an oxide film on a material substrate.   The film structure according to any one of 1 to 3 described above, wherein the film has at least weather resistance, appearance (color) stability, bactericidal property, antibacterial property, abrasion resistance, slipping property, light environment catalyst, An applied article having an oxide film structure of iodine or an iodine compound-containing metal material base material, which is intended for either coloring (coloring).

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