CN114075648A

CN114075648A - White antibacterial member, method for producing white antibacterial member, and timepiece including white antibacterial member

Info

Publication number: CN114075648A
Application number: CN202110892000.7A
Authority: CN
Inventors: 高崎康太郎
Original assignee: Citizen Watch Co Ltd
Current assignee: Citizen Watch Co Ltd
Priority date: 2020-08-20
Filing date: 2021-08-04
Publication date: 2022-02-22
Also published as: JP2022035078A

Abstract

The invention provides a white antibacterial member which has excellent antibacterial property and excellent decorative property. The white antibacterial member has a base material and a white antibacterial film provided on the base material, wherein the white antibacterial film contains a metal M1 and a metal M2, the metal M1 is at least 1 selected from Pt, Pd and Rh, the metal M2 is Cu, Ag or Ni, when the metal M2 is Cu or Ni, the metal M2 is contained in the white antibacterial film in an amount of 4.15 at% or more, and when the metal M2 is Ag, the metal M2 is contained in the white antibacterial film in an amount of 2.49 at% or more.

Description

White antibacterial member, method for producing white antibacterial member, and timepiece including white antibacterial member

Technical Field

The present invention relates to a white antibacterial member, a method for manufacturing the white antibacterial member, and a timepiece including the white antibacterial member.

Background

Patent document 1 describes an antibacterial alloy coating composition applied to the surface of a device to plate an antibacterial alloy coating on the surface of the device. Specifically, the antibacterial alloy coating composition comprises an antibacterial material selected from the group consisting of copper, silver and a mixture thereof, wherein the antibacterial material has an atomic content of 1.7 to 26.8% of the total content, and an alloy comprising at least 4 or more metal elements selected from the group consisting of iron, cobalt, chromium, nickel, aluminum, vanadium and titanium and at least one non-metal element selected from the group consisting of boron, oxygen and nitrogen.

Patent document 1: japanese patent application laid-open No. 2010-156035

Disclosure of Invention

However, the antibacterial alloy coating layer obtained from the antibacterial alloy coating composition of patent document 1 does not show a white color excellent in decorativeness.

Accordingly, an object of the present invention is to provide a white antibacterial member which has excellent antibacterial properties and exhibits a white color with excellent decorative properties.

The white antibacterial member of the present invention comprises a base material and a white antibacterial film provided on the base material, wherein the white antibacterial film comprises a metal M1 and a metal M2, the metal M1 is at least 1 selected from Pt, Pd and Rh, and the metal M2 is at least 1 selected from Cu, Ag and Ni. When the metal M2 is Cu or Ni, the metal M2 is contained in an amount of 4.15 at% or more in the white antibacterial film, and when the metal M2 is Ag, the metal M2 is contained in an amount of 2.49 at% or more in the white antibacterial film.

The white antibacterial member of the present invention has excellent antibacterial properties and exhibits a white color with excellent decorative properties.

Drawings

Fig. 1 is a diagram illustrating a white antimicrobial member according to an embodiment.

Fig. 2 is a diagram for specifically explaining a modification of the white antimicrobial member according to the embodiment.

Fig. 3 is a diagram for specifically explaining a modification of the white antimicrobial member according to the embodiment.

Fig. 4 is a diagram for specifically explaining a modification of the white antimicrobial member according to the embodiment.

FIG. 5 is a graph showing the results of X-ray diffraction of the white antibacterial member produced in example 1 and the Pt white member produced in comparative example 1-1.

Fig. 6 is a graph showing the results of X-ray diffraction of the white antibacterial member produced in example 2 and the Pt white member produced in comparative example 2-1.

FIG. 7 is a graph showing the change in hardness when the amount of introduced nitrogen gas was changed with the amount of Ar gas being constant at 105sccm in a MoNbCr film.

FIG. 8 is a graph showing the change in luminance when the amount of introduced nitrogen gas was changed with the amount of Ar gas being constant at 105sccm in a MoNbCr film.

Fig. 9 is a photograph of a non-processed test piece after an antibacterial activity test by staphylococcus aureus.

FIG. 10 is a photograph of a non-processed test piece after the antibacterial activity test by Escherichia coli.

Fig. 11 is a photograph of the antibacterial processed test piece after the antibacterial activity test by staphylococcus aureus.

FIG. 12 is a photograph of the antibacterial processed test piece after the antibacterial activity test by Escherichia coli.

Description of the symbols

100 white antibacterial member

10 base material

11 cured layer

12 bonding layer

13 inclined sealing layer

14 inclined layer of coloring

20 white antibacterial coating

Detailed Description

The mode (embodiment) for carrying out the present invention will be described in detail. The present invention is not limited to the contents described in the following embodiments. The constituent elements described below include elements that can be easily conceived by those skilled in the art, and substantially the same elements. The following configurations can be combined as appropriate. Various omissions, substitutions, and changes in the configuration may be made without departing from the spirit of the invention.

< white antibacterial part >

Fig. 1 is a diagram illustrating a white antimicrobial member according to an embodiment. As shown in the schematic cross-sectional view of fig. 1, the white antimicrobial member 100 has a base material 10 and a white antimicrobial coating 20 provided on the base material 10.

The substrate 10 is formed of metal, ceramic, or plastic. Examples of the metal (including alloy) include stainless steel, titanium alloy, copper alloy, tungsten, and high-carbon chromium bearing steel (SUJ 2). These metals may be used alone in 1 kind, or may be used in combination in 2 or more kinds. The shape of the base material is not limited.

The white antibacterial coating film 20 contains a metal M1 of at least 1 selected from Pt, Pd and Rh and a metal M2 of at least 1 selected from Cu, Ag and Ni. Here, when the metal M2 is Cu or Ni, the metal M2 is contained in an amount of 4.15 at% or more in the white antibacterial film, and when the metal M2 is Ag, the metal M2 is contained in an amount of 2.49 at% or more in the white antibacterial film. The white antibacterial member of the embodiment includes the coating metal M2 in a specific amount, and therefore has excellent antibacterial properties. In addition, since the metal M1 and the metal M2 are included, white color excellent in decorativeness is displayed.

On the other hand, patent document 1 describes an antibacterial alloy coating layer, but does not describe a color tone. As described above, the conventional techniques have a problem that a white antibacterial member having high decorativeness and antibacterial properties cannot be provided. In contrast, as described above, the white antimicrobial member according to the embodiment has a specific white antimicrobial coating, and therefore, these problems can be solved.

Specific combinations of the metals M1 and M2 include M1 ═ Pt, M2 ═ Cu; m1 ═ Pt, M2 ═ Ag; m1 ═ Pt, M2 ═ Ni; m1 ═ Pd, M2 ═ Cu; m1 ═ Pd, M2 ═ Ag; m1 ═ Pd, M2 ═ Ni; m1 ═ Rh, M2 ═ Cu; m1 ═ Rh, M2 ═ Ag; m1 ═ Rh, M2 ═ Ni, and the like.

Among these, when the metal M1 is Pt and the metal M2 is Cu, the composition range showing antibacterial properties and corrosion resistance is wide, and the metal M1 is preferable from the viewpoint of mass production stability. In other words, in production, even if there is an error or variation in the composition of the coating film, a coating film having desired characteristics can be obtained, which is preferable. In addition, when the metal M1 is Pt and the metal M2 is Ag, a small amount of Ag exhibits antibacterial properties, and therefore, it is preferable. When the metal M1 is Pt and the metal M2 is Ni, since Ni itself has high corrosion resistance, the composition range showing antibacterial properties and corrosion resistance is wide, and this is preferable from the viewpoint of mass production stability. However, the decorative member that comes into contact with the skin is not preferable from the viewpoint of Ni allergy. From the viewpoint of cost and mass productivity, Cu is most preferably selected as the antibacterial material.

When the metal M1 is Pt and the metal M2 is Cu or Ni, it is preferable that Pt (metal M1) is contained in an amount of 29.72 at% to 95.85 at% and Cu or Ni (metal M2) is contained in an amount of 4.15 at% to 70.28 at% in the white antibacterial film. The total of the amount of the metal M1 and the amount of the metal M2 was 100 at%.

If Cu or Ni is contained in an amount of 4.15 at% or more, the antibacterial property of the white antibacterial member is more excellent. More specifically, such a white antibacterial member is used in a state of being covered by "JIS Z2801: 2012 antibacterial processing-antibacterial test method and antibacterial effect ", the antibacterial activity value is usually 2.0 or more. Further, if Cu or Ni is contained in an amount of 70.28 at% or less, the corrosion resistance of the white antimicrobial member is also excellent.

In addition, if Pt is contained in an amount of 29.72 at% or more, the white antibacterial member shows a white color more excellent in decorativeness. More specifically, such white antimicrobial components are typically a in the CIE Lab color space display^*Is-2.0 to 2.0, b^*Is-4.50 to 4.50. Further, such white antimicrobial components are typically L in the CIE Lab color space display^*Is 80.00 or more. It should be noted that if a^*When it exceeds 3, red color tends to appear, and if a is present^*When the color is less than-3, green color tends to be observed. In addition, if b^*When the average molecular weight is more than 5, the color tends to be yellowish, and when b is more than 5^*When the color is less than-5, a blue color tends to be perceived. In addition, L can be said to be^*The higher, the closer to white (silver). Here, in the present specification, L^*、a^*、b^*Is to the surface of a substrateThe value measured for the white antibacterial coating.

That is, if Pt and Cu or Ni are contained in the above amounts, the antibacterial property of the white antibacterial member is more excellent, and white color with more excellent decorative property is displayed, and further, corrosion resistance is also excellent.

In addition, in the case where the metal M1 is Pd or Rh and the metal M2 is Cu or Ni, similarly to the case where the metal M1 is Pt, it is preferable that Pd or Rh (metal M1) is contained in an amount of 29.72 at% to 95.85 at% or less and Cu or Ni (metal M2) is contained in an amount of 4.15 at% to 70.28 at% or less.

When the metal M1 is Pt and the metal M2 is Ag, the white antibacterial coating preferably contains Pt (metal M1) in an amount of 67.13 at% to 97.51 at% and Ag (metal M2) in an amount of 2.49 at% to 32.87 at%. The total of the amount of the metal M1 and the amount of the metal M2 was 100 at%.

When Ag is contained in an amount of 2.49 at% or more, the antibacterial property of the white antibacterial member is more excellent. More specifically, such a white antibacterial member is used in a state of being covered by "JIS Z2801: 2012 antibacterial processing-antibacterial property test method and antibacterial effect "the antibacterial activity value is usually 2.0 or more. Further, if Ag is contained in an amount of 32.87 at% or less, the corrosion resistance of the white antimicrobial member is also excellent.

In addition, if Pt is contained in an amount of 67.13 at% or more, the white antibacterial member shows a white color more excellent in decorativeness. More specifically, such white antimicrobial components are typically a in the CIE Lab color space display^*Is-2.0 to 2.0, b^*Is-4.50 to 4.50. Further, such white antimicrobial components are typically L in the CIE Lab color space display^*Is 80.00 or more.

That is, if Pt and Ag are contained in the above amounts, the antibacterial property of the white antibacterial member is more excellent, and white color with more excellent decorative property is displayed, and further, corrosion resistance is also excellent.

In addition, in the case where the metal M1 is Pd or Rh and the metal M2 is Ag, similarly to the case where the metal M1 is Pt, it is preferable that Pd or Rh (metal M1) is contained in an amount of 67.13 at% to 97.51 at%, and Ag (metal M2) is contained in an amount of 2.49 at% to 32.87 at% or less.

Here, the amounts of metal M1 and metal M2 of the white antibacterial coating can be determined by ESCA (X-ray photoelectron spectroscopy), EDX (energy dispersive X-ray spectroscopy) or EPMA (electron probe microanalyzer). Among these, it is preferable to obtain the value by EDX (energy dispersive X-ray spectrometry).

The thickness of the white antibacterial coating 20 is preferably 10nm to 1000 nm. If the thickness of the white antibacterial film is less than 10nm, the antibacterial property and the decorative property may not be sufficiently exhibited. Further, if the thickness of the white antibacterial film exceeds 1000nm, the scratch resistance and the cost property may be inferior.

In addition, the white antibacterial member of the embodiment preferably has a film hardness of HV1000 or more. Here, in the present specification, the film hardness refers to a value measured for a white antibacterial film formed on a substrate. As described above, the white antibacterial member of the embodiment has sufficient hardness and is excellent in scratch resistance and abrasion resistance.

The white antimicrobial member according to the embodiment may further include an intermediate layer between the base material and the white antimicrobial coating.

The intermediate layer may be a cured layer. Fig. 2 is a diagram for specifically explaining a modification of the white antimicrobial member according to the embodiment. As shown in fig. 2, the white antimicrobial member 100 may be further provided with a cured layer 11 between the substrate 10 and the white antimicrobial coating 20. Such a white antimicrobial member 100 has sufficient hardness and is excellent in scratch resistance and abrasion resistance.

The cured layer 11 has a higher hardness than the white antibacterial coating 20. The scratch resistance is determined approximately by the product of the thickness of the coating, the degree of adhesion of the coating, and the hardness of the coating. If the cured layer 11 is provided, the hardness of the entire film is increased, and a thick film can be formed. As a result, the scratch resistance of the white antibacterial member can be improved. The cured layer 11 is not particularly limited as long as it has a hardness (for example, 1000HV or more) higher than that of the white antibacterial film 20.

The solidified layer 11 contains, for example, a metal M1' of at least 1 selected from Ti, Cr, Zr, Nb, Mo, Hf, Ta, and W, and carbon, nitrogen, or both as non-metallic elements, and is appropriately selected depending on the appearance color and the use environment of the coating film. Since the cured layer 11 is white, the appearance can be maintained even when the white antibacterial film 20 is peeled off. Specifically, TiC is preferably used.

Alternatively, the solidified layer 11 contains at least 1 metal M1 'selected from Ti, Cr, Zr, Nb, Mo, Hf, Ta, and W, at least 1 metal M2' selected from Cu, Ag, and Ni, and carbon, nitrogen, or both as non-metallic elements, which are appropriately selected depending on the appearance color and the use environment of the coating film. Since the cured layer 11 is white, the appearance can be maintained even when the white antibacterial film 20 is peeled off. Further, the cured layer 11 containing the metal M2' has an antibacterial property, and therefore has an advantage that the antibacterial property can be maintained even when the white antibacterial film 20 is peeled off. The cured layer 11 containing the metal M2' that is the same as the metal M2 of the white antibacterial film 20 formed on the cured layer 11 is also preferable in terms of high adhesion and ease of production. Specifically, TiCuC and TiAgC are preferably used.

The thickness of the cured layer 11 is preferably 100nm to 3000 nm.

Examples of the intermediate layer include an adhesion layer, an inclined adhesion layer, and a colored inclined layer. Fig. 3 and 4 are views for specifically explaining a modification of the white antimicrobial member according to the embodiment. As shown in fig. 3, the white antimicrobial member 100 may be provided with an adhesion layer 12 and a cured layer 11 in this order between the base material 10 and the white antimicrobial film 20. The cured layer 11 is as described above. If the adhesive layer 12 is provided, the adhesion between the base material 10 and the layer formed on the adhesive layer 12 is improved, and a thick coating film can be formed. As a result, the white antibacterial member can contribute to improvement in scratch resistance and abrasion resistance. Examples of the adhesion layer 12 include a Ti film and a Cr film. The adhesion layer 12 containing the same metal as the metal constituting the base material 10 or the metal constituting the layer formed on the adhesion layer 12 is also preferable in terms of obtaining a high adhesion degree and ease of production. For example, when the substrate 10 contains Ti, a Ti coating is preferably used. When the substrate 10 includes high-carbon chromium bearing steel (SUJ2), a Cr coating is preferably used. The adhesion layer 12 may contain a metal other than Ti (e.g., Mo, Nb, Cu, etc.) as long as it contains Ti or Cr. The adhesion layer 12 may be a low-grade oxide film. In addition, when the adhesion layer 12 contains at least one element of carbon and nitrogen in addition to Ti, the film formed on the base material 10 can be easily removed. That is, for example, the white antibacterial member 100 is immersed in a solution such as nitric acid, dilute nitric acid, or fluoronitric acid for a predetermined time period, which does not damage the surface of the base material 10, whereby the adhesive layer 12 is dissolved, and the layer formed on the adhesive layer 12 is peeled off. Therefore, the coating film formed on the substrate 10 can be removed without damaging the surface of the substrate 10.

As shown in fig. 4, the white antimicrobial member 100 may be provided with an adhesion layer 12, an inclined adhesion layer 13, a cured layer 11, and a colored inclined layer 14 in this order between the base material 10 and the white antimicrobial film 20. The adhesion layer 12 and the cured layer 11 are as described above. If the inclined adhesion layer 13 is provided, stress strain generated between the base material 10 and the white antibacterial film 20 can be relaxed, the adhesion degree between the base material 10 and the white antibacterial film 20 becomes high, and generation of cracks and peeling are suppressed. As a result, the white antibacterial member can contribute to improvement in scratch resistance and abrasion resistance. The oblique adhesion layer 13 contains, for example, a metal M1' of at least 1 selected from Ti, Cr, Zr, Nb, Mo, Hf, Ta, and W, and carbon, nitrogen, or both as non-metal elements. In addition, the amount of carbon, nitrogen, or both in the oblique adhesion layer 13 generally increases as it goes away from the substrate 10 in a direction perpendicular to the surface of the substrate 10 on which the white antibacterial coating 20 is provided. If the colored inclined layer 14 is provided, stress is gradually reduced from the cured layer 11, stress strain is relaxed, and the occurrence of scratches and cracks can be reduced. Further, since the brightness is increased toward the white antibacterial film 20, the difference in color from the white antibacterial film 20 is reduced, and the decorative member is free from a feeling of discomfort in actual use even if the white antibacterial film 20 is peeled off, for example. The coloring-gradient layer 14 contains a metal M1' of at least 1 kind selected from Ti, Cr, Zr, Nb, Mo, Hf, Ta, and W, and carbon, nitrogen, or both as non-metal elements. In addition, the amount of carbon, nitrogen, or both in the oblique adhesion layer 13 generally decreases as it moves away from the substrate 10 in a direction perpendicular to the surface of the substrate 10 on which the white antimicrobial coating 20 is provided.

In the white antibacterial member of the embodiment and the white antibacterial film 20 of the modified example thereof, in order to make the color tone more desirable, the metal M1 in the white antibacterial film 20 may be changed as it is separated from the substrate 10 in a direction perpendicular to the surface of the substrate 10 on which the white antibacterial film 20 is provided. Of course, it may not be changed. The amounts of the metals M1 and M2 in the entire white antibacterial coating 20 are preferably within the above-described preferred ranges for the entire white antibacterial coating 20.

Any of the white antibacterial members has the above-described white antibacterial coating, and therefore has excellent antibacterial properties. In addition, white color excellent in decorativeness is displayed.

Method for producing white antibacterial member

The method of manufacturing the white antimicrobial member according to the embodiment is the method of manufacturing the white antimicrobial member. That is, the method for producing a white antimicrobial member according to the embodiment includes a step of providing a white antimicrobial coating on a base material (white antimicrobial coating forming step). Here, the white antibacterial coating contains metal M1 of at least 1 selected from Pt, Pd and Rh and metal M2 of at least 1 selected from Cu, Ag and Ni. When the metal M2 is Cu or Ni, the metal M2 is contained in an amount of 4.15 at% or more in the white antibacterial film, and when the metal M2 is Ag, the metal M2 is contained in an amount of 2.49 at% or more in the white antibacterial film.

The white antibacterial coating forming step is specifically performed by a sputtering method or an arc method. The sputtering method is a method in which a high voltage of direct current or alternating current is applied between a base material and a target composed of constituent atoms of a coating film while introducing an inert gas (for example, Ar) into a chamber evacuated to vacuum, and the inert gas such as Ar after ionization is caused to collide with the target, thereby forming a target substance to be splashed on the base material.

In the white antibacterial film forming step, the target (raw material metal) is a sintered body or a molten body containing, for example, metal M1 of at least 1 selected from Pt, Pd, and Rh and metal M2 of at least 1 selected from Cu, Ag, and Ni.

In the white antibacterial coating forming step, the film is formed under different conditions depending on the production apparatus and the target composition used, for example, under the condition that the inert gas (for example, Ar) is 100 to 200 sccm.

Further, the kind and amount of the metal element in the white antibacterial coating and the thickness of the white antibacterial coating can be controlled by adjusting the kind and ratio of the target constituent atoms, the sputtering time, the sputtering output, and the bias voltage applied to the substrate side. In addition, the adhesiveness, film hardness, and color tone of the white antimicrobial member can be controlled.

The white antimicrobial member may further include an intermediate layer as described above. These layers may be laminated by an intermediate layer forming step following the white antibacterial coating forming step described above. The kind, amount, thickness, and the like of the metal element in the intermediate layer can be controlled by adjusting the kind and proportion of the target constituent atoms, sputtering time, sputtering output, bias voltage applied to the substrate side, and the like.

For example, the case of forming the solidified layer is performed by a reactive sputtering method. In the reactive sputtering method, a reaction gas is introduced in a small amount together with an inert gas, and a coating film (solidified layer) of a reaction compound of target constituent atoms and a nonmetallic element constituting the reaction gas can be formed on a substrate. When the non-metal element is carbon, a carbon atom-containing gas such as methane gas or acetylene gas can be used as the reaction gas.

The solidified layer is formed under different conditions depending on the manufacturing apparatus and the target composition used, for example, a carbide film, a nitride film, or a carbonitride film (solidified layer) is formed by introducing 5 to 150sccm of a gas containing carbon atoms, nitrogen gas, or a gas containing both of these gases under the condition that the inert gas is 100 to 200 sccm. If the amount of gas is in the above range, the amount of carbon and nitrogen in the cured layer can be adjusted to a preferable range.

The reactive sputtering method is highly controllable in film quality and film thickness, and can be easily automated. Further, since the energy of the sputtered atoms is high, heating of the substrate for improving the adhesion is not necessary, and the coating film can be formed even on a substrate such as plastic having a low melting point. In addition, since the method is a method of forming a target substance which is splashed on a base material, a film can be formed even with a high-melting-point material, and the material can be freely selected.

Further, the kind and amount of the metal element in the solidified layer, the amounts of carbon and nitrogen, and the thickness of the solidified layer can be controlled by adjusting the kind and ratio of the target constituent atoms, the selection and amount of the reaction gas, the sputtering time, the sputtering output, and the bias voltage applied to the substrate side. In addition, the adhesiveness, film hardness, and color tone of the white antimicrobial member can be controlled.

For example, the oblique adhesion layer and the colored oblique layer may be formed by a reactive sputtering method or an arc method. The amount of the reaction gas may be appropriately changed in the inclined adhesion layer and the coloring inclined layer in which the amounts of carbon and nitrogen change as they are separated from the base material. Further, the adjustment of the gas amount may be performed using an automatically controlled mass flow controller.

Clock & watch & lt

The timepiece of the embodiment includes the above white antibacterial member. The white antibacterial member is not particularly limited as long as it is a component of a timepiece, and examples thereof include a case, a back cover, a band, and a buckle. The timepiece according to the embodiment may be any one of a photo-electric timepiece, a thermal-electric timepiece, a radio wave receiving type automatic correction timepiece, a mechanical timepiece, and a general electronic timepiece, or may be any one of a wristwatch, a wall clock, and a table clock. Such a timepiece can be manufactured by a known method using the above-described white antibacterial member. Any of the timepieces has the above-described white antibacterial coating, and therefore has excellent antibacterial properties. In addition, white color excellent in decorativeness is displayed.

The white antibacterial member according to the embodiment can be applied to a timepiece or the like. The white antibacterial member of the embodiment may be included in medical instruments such as scissors, forceps, and scalpels; beauty treatment devices such as scissors and razors; building hardware such as door handles, locks, hinges and the like; decorative parts such as glasses and jewelry; cooking utensils such as scissors and tongs; beer suppliers, hooks, and other daily necessities; a combination of; sports goods, electric appliances and the like. Any of the products has the above-mentioned white antibacterial coating film and therefore has excellent antibacterial properties. In addition, white color excellent in decorativeness is displayed.

The white antibacterial member according to the embodiment can be used for manufacturing a timepiece or a product other than a timepiece according to the embodiment by a known method.

As described above, the present invention relates to the following.

[ 1] A white antimicrobial member comprising a base material and a white antimicrobial coating provided on the base material, wherein the white antimicrobial coating comprises at least 1 metal M1 selected from Pt, Pd and Rh and at least 1 metal M2 selected from Cu, Ag and Ni, and wherein when the metal M2 is Cu or Ni, the metal M2 is contained in the white antimicrobial coating at 4.15 at% or more, and when the metal M2 is Ag, the metal M2 is contained in the white antimicrobial coating at 2.49 at% or more.

The white antibacterial member of the above [ 1] is excellent in antibacterial property and exhibits a white color excellent in decorativeness.

The white antibacterial member according to [ 1], wherein the metal M1 is Pt, the metal M2 is Cu or Ni, and the metal M1 is contained in the white antibacterial film in an amount of 29.72 at% to 95.85 at% or less and the metal M2 is contained in an amount of 4.15 at% to 70.28 at%.

The white antibacterial member according to [ 1], wherein the metal M1 is Pt, the metal M2 is Ag, and the metal M1 is contained in an amount of 67.13 at% to 97.51 at% and the metal M2 is contained in an amount of 2.49 at% to 32.87 at% in the white antibacterial film.

The above-mentioned white antibacterial member of [ 2] or [ 3] is more excellent in antibacterial property, and exhibits a white color more excellent in decorative property, and further is excellent in corrosion resistance.

[ 4] the white antibacterial member according to any one of [ 1] to [ 3], wherein the white antibacterial film is L in a Lab color space display^*Is 80.00 or more, a^*Is-2.0 to 2.0, b^*Is-4.50 to 4.50.

The above white antibacterial member of [ 4] exhibits a white color more excellent in decorativeness.

The white antibacterial member according to any one of [ 1] to [ 4], wherein a cured layer is further provided between the base material and the white antibacterial film.

The white antibacterial member of [ 5] above has sufficient hardness and is excellent in scratch resistance and abrasion resistance.

A timepiece comprising the white antibacterial member according to any one of [ 1] to [ 5 ].

The timepiece of [ 6] is excellent in antibacterial property and exhibits a white color excellent in decorative property.

A method for producing a white antimicrobial member, comprising a step of providing a white antimicrobial film on a substrate, wherein the white antimicrobial film contains at least 1 metal M1 selected from Pt, Pd and Rh and at least 1 metal M2 selected from Cu, Ag and Ni, and wherein when the metal M2 is Cu or Ni, the metal M2 is contained in the white antimicrobial film in an amount of 4.15 at% or more, and when the metal M2 is Ag, the metal M2 is contained in the white antimicrobial film in an amount of 2.49 at% or more.

According to the method for producing a white antibacterial member of the above [ 7 ], a white antibacterial member excellent in antibacterial property and excellent in decorativeness can be obtained.

[ examples ]

The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

< example 1 >

[ example 1-1 ]

A white antimicrobial component 100 shown in fig. 1 was produced. As the sputtering target, a sputtering target containing Pt96 at% and Cu4 at% was used, and as the base material 10, a base material made of Ti was used. A white antibacterial member 100 (Table 1) was obtained by introducing argon gas of 105sccm by a sputtering method to sputter a PtCu alloy target and forming a white antibacterial film 20 having a thickness of about 200nm on a substrate 10.

Examples 1-2 to 1-13

In examples 1-2 to 1-13, a white antimicrobial member 100 was obtained in the same manner as in example 1-1, except that sputtering targets having different Pt and Cu contents were used as shown in table 1.

Comparative examples 1 to 1

In comparative example 1-1, a Pt white member was obtained in the same manner as in example 1-1, except that Pt was used as a sputtering target as shown in table 1.

Comparative examples 1 and 2

In comparative example 1-2, white members were obtained in the same manner as in example 1-1, except that sputtering targets having different Pt and Cu contents were used as shown in table 1.

Table 1 shows the evaluation results of the amount of metal element in the film of the white antibacterial member obtained above, antibacterial property, color tone, and corrosion resistance. A thin film containing only Pt but not Cu was also shown as comparative example 1-1. As is clear from table 1, when the Cu content in the thin film is 4.15 at% or more, the film has antibacterial properties according to the antibacterial test shown in JIS.

It is understood that the antibacterial property is exhibited when the Cu content is 4.15 at% or more, but as the Cu content increases, a of the color tone is observed^*And b^*The increase in the corrosion resistance of examples 1 to 12 and examples 1 to 13 was also reduced because the pink color of Cu began to appear slightly. From the above results, it is considered that the preferable Cu amount in the thin film is 4.15 at% to 70.28 at% for a white antibacterial member which is excellent in antibacterial property, corrosion resistance and further excellent in decorativeness.

[ Table 1]

FIG. 5 is a graph showing the results of X-ray diffraction of the white antibacterial member produced in example 1 and the Pt white member produced in comparative example 1-1. Specifically, FIG. 5 shows the results of X-ray diffraction of the Pt white member produced in comparative example 1-1 and the white antibacterial members produced in examples 1-1, 1-4, 1-9, 1-10, 1-11, 1-12, and 1-13.

The Pt white member produced in comparative example 1-1 is a Pt crystal itself having a face-centered cubic structure with a crystal peak on the [1, 1, 1] plane (near 39.9 degrees), [2, 0, 0] plane (near 46.4 degrees), [2, 2, 0] plane (near 67.7 degrees), and a slightly visible crystal peak on the [3, 1, 1] plane (near 81.7 degrees). When the amount of Cu increases in the thin film, the respective crystal peaks move to the high angle side and approach the [1, 1, 1] plane (near 43.1 degrees), [2, 0, 0] plane (near 50.4 degrees), [2, 2, 0] plane (near 73.6 degrees), and [3, 1, 1] plane (near 89.1 degrees) of the crystal structure of Cu. It is known that the crystal state is variously changed depending on the content of Cu.

Specifically, in the crystal structures of examples 1-1 and 1-4, in addition to the crystal structure of Pt, it was confirmed that the crystal phase of CuPt7 was contained in a larger amount in examples 1-4 in which the amount of Cu was large. In the crystal structures of examples 1 to 9 and examples 1 to 10, the crystal phases of CuPt7 and CuPt were confirmed, showing that the more the amount of Cu contained, the more the CuPt crystal phase contained. In the crystal structures of examples 1 to 11, the crystal structures of CuPt, Cu3Pt, and CuPt7 were confirmed. In the crystal structures of examples 1 to 12 and examples 1 to 13, crystal phases of Cu3Pt and Cu were confirmed, showing that the more the amount of Cu contained, the more the Cu crystal phase contained. If the Cu ratio in the Pt film increases, the crystal phase having a high Cu ratio increases as Pt crystal → Pt crystal + CuPt7 crystal → CuPt7 crystal + CuPt crystal → CuPt crystal + Cu3Pt crystal → Cu3Pt crystal + Cu crystal → Cu crystal. It is presumed that the corrosion resistance is high even in the case of the Cu70.28at% Pt29.72at% film containing 70 at% Cu (examples 1 to 11) because Pt-containing crystals such as Cu3Pt, CuPt and CuPt7 were formed.

< example 2 >

[ example 2-1 ]

A white antimicrobial component 100 shown in fig. 1 was produced. As the sputtering target, a sputtering target containing Pt98 at% and Ag2 at% was used, and as the base material 10, a base material made of Ti was used. A PtAg alloy target was sputtered by introducing 105sccm of argon gas by a sputtering method to form a white antibacterial film 20 having a thickness of about 200nm on the substrate 10, thereby obtaining a white antibacterial member 100 (Table 2).

[ examples 2-2 to 2-8 ]

In examples 2-2 to 2-8, a white antimicrobial member 100 was obtained in the same manner as in example 2-1, except that sputtering targets having different Pt and Ag contents were used as shown in table 2.

Comparative example 2-1

In comparative example 2-1, a Pt white member was obtained in the same manner as in example 2-1, except that Pt was used as a sputtering target as shown in table 2.

Comparative examples 2-2 and 2-3

In comparative examples 2-2 and 2-3, white members were obtained in the same manner as in example 2-1, except that sputtering targets having different contents of Pt and Ag were used as shown in Table 2.

Table 2 shows the evaluation results of the amount of metal element in the film of the white antibacterial member obtained above, antibacterial property, color tone, and corrosion resistance. The thin film of comparative example 2-1 containing only Pt but not Ag is also shown. As is clear from Table 2, when the Ag content in the film is 2.49 at% or more, the film has antibacterial properties according to the antibacterial test shown in JIS.

It is found that the antibacterial property is exhibited when the Ag content is 2.49 at% or more, but the hue b is found as the Ag content increases^*In examples 2-6 to 2-8, b^*Increased with a yellow color and reduced corrosion resistance. From the above results, it is found that the preferable amount of Ag in the film is 2.49 at% to 32.87 at% for a white antibacterial member having excellent antibacterial properties, corrosion resistance, and further excellent decorative properties.

[ Table 2]

Fig. 6 is a graph showing the results of X-ray diffraction of the white antibacterial member produced in example 2 and the Pt white member produced in comparative example 2-1. Specifically, FIG. 6 is a graph showing the results of X-ray diffraction of the Pt white member produced in comparative example 2-1 and the white antibacterial members produced in examples 2-1, 2-2, 2-3, 2-4, 2-5, 2-6, 2-7 and 2-8.

The Pt white member produced in comparative example 2-1 is a Pt crystal itself having a face-centered cubic structure with a crystal peak on the [1, 1, 1] plane (near 39.9 degrees), [2, 0, 0] plane (near 46.4 degrees), [2, 2, 0] plane (near 67.7 degrees), and [3, 1, 1] plane (near 81.7 degrees). When the amount of Ag in the film increases, the respective crystal peaks shift to the low angle side, and the crystal peaks are observed near the [1, 1, 1] plane (around 38.4 degrees), [2, 0, 0] plane (around 44.6 degrees), [2, 2, 0] plane (around 64.91 degrees), and [3, 1, 1] plane (around 77.99 degrees) of the crystal structure of Ag, and at the [2, 2, 2] plane (around 82.18 degrees). It is known that the crystal state changes in many ways depending on the content of Ag.

Specifically, in the crystal structure of example 2-1, in addition to the crystal structure of Pt, a slightly AgPt3 crystal phase was confirmed. In example 2-2, a crystalline layer of AgPt was observed in addition to the Pt crystalline layer and the AgPt3 crystalline layer. In examples 2-3 to 2-5, the AgPt crystal layer was observed, and the amount of the AgPt crystal phase tended to increase as the Ag content increased. In examples 2-6 to 2-8, the AgPt crystal layer and the Ag crystal layer were observed, and the amount of the Ag crystal phase tended to increase with the increase in the Ag content. If the ratio of Ag in the Pt film increases, the crystal phase with a high ratio of Ag increases as Pt crystal → Pt crystal + AgPt3 crystal → AgPt3 crystal + AgPt crystal → AgPt crystal + Ag crystal → Ag crystal. As a result of the crystal measurement, it was found that the conditions under which Ag crystals were observed, specifically, corrosion resistance and color tone were not satisfied in examples 2 to 6, 2 to 7, and 2 to 8, and a correlation with the evaluation of corrosion resistance was obtained.

< example 3 >

[ example 3-1 ]

A white antimicrobial member 100 shown in fig. 2 was produced. As the sputtering target, targets made of Ti were disposed on target 1 and target 2, and a molten target of Pt96 at% Cu4 at% was used for target 3. As the substrate 10, a substrate made of Ti was used. Argon gas of 105sccm and methane gas of 10sccm were introduced by a sputtering method to form a solidified layer 11 (thickness 900nm) made of TiC. Subsequently, argon gas of 105sccm was introduced and a molten target of Pt96 at% Cu4 at% was sputtered to form a white antibacterial coating film 20 having a thickness of about 10nm on the solidified layer 11, thereby obtaining a white antibacterial member 100.

By forming the cured layer as in example 3-1, the hardness of the white antimicrobial member 100 was dramatically improved, and the scratch resistance (root mean square roughness) and the abrasion resistance were significantly improved. Table 3 shows a comparison between example 3-1 and example 1-1. It is understood that the white antimicrobial member 100 has a hardness and scratch resistance of 5 times or more. The amounts of the components in the white antibacterial coating 20 of example 3-1 were the same as in example 1-1.

When scratch resistance and abrasion resistance are required, the thickness of the white antibacterial coating 20 is preferably 10nm to 50 nm. When the film thickness is less than 10nm, the antibacterial activity may not be sufficiently exhibited. When the film thickness exceeds 50nm, the hardness of the entire white antimicrobial member is lowered, and therefore, the scratch resistance may be poor. By setting the thickness of the PtCu alloy film to about 10nm as in example 3-1, a white antibacterial member having excellent antibacterial properties, corrosion resistance, scratch resistance, and color tone can be produced.

[ Table 3]

< example 4 >

[ example 4-1 ]

A white antimicrobial member 100 shown in fig. 3 was produced. As the sputtering target, targets made of Ti were disposed on target 1 and target 2, and a molten target of Pt96 at% Cu4 at% was used for target 3. As the substrate 10, a substrate made of SUS316L was used. Argon gas of 105sccm was introduced by a sputtering method to form the adhesion layer 12 (thickness 100nm) made of Ti. Then, argon gas of 105sccm and methane gas of 10sccm were introduced to form a solidified layer 11 (thickness 900nm) made of TiC. Subsequently, argon gas of 105sccm was introduced and a molten target of Pt96 at% Cu4 at% was sputtered to form a white antibacterial coating film 20 having a thickness of about 10nm on the solidified layer 11, thereby obtaining a white antibacterial member 100.

When the composition of the substrate and the cured layer is different as in example 4-1, an adhesion layer may be provided. In example 4-1, since SUS316L was used as the substrate, if a cured layer was formed directly on the substrate, there was a case where the scratch resistance was significantly reduced due to peeling caused by a reduction in adhesion force and generation of cracks caused by stress strain. The scratch resistance is determined by the product of the hardness of the wear-resistant layer, the film thickness of the wear-resistant layer, and the degree of adhesion to the substrate, and therefore, when different types of materials are laminated, the adhesion to the substrate is important.

Table 4 shows the results of measuring the hardness, scratch resistance, corrosion resistance, color tone and antibacterial property of example 4-1 and example 1-1. The hardness and scratch resistance were significantly improved as compared with those of example 1-1. The amounts of the components in the white antibacterial coating 20 of example 4-1 were the same as in example 1-1.

When scratch resistance and abrasion resistance are required, the thickness of the white antibacterial coating 20 is preferably 10nm to 50 nm. When the film thickness is less than 10nm, the antibacterial activity may not be sufficiently exhibited. When the film thickness exceeds 50nm, the hardness of the entire white antimicrobial member is lowered, and therefore, the scratch resistance may be poor. By setting the thickness of the PtCu alloy film to about 10nm as in example 4-1, a white antibacterial member having excellent antibacterial properties, corrosion resistance, scratch resistance, and color tone can be produced.

[ Table 4]

< example 5 >

[ example 5-1 ]

A white antimicrobial member 100 shown in fig. 4 was produced. As the sputtering target, targets composed of Mo60 wt% Nb30 wt% Cr10 wt% were disposed in target 1 and target 2, and a molten target of Pt96 at% Cu4 at% was used in target 3. As the substrate 10, a substrate made of Ti was used. Fig. 7 and 8 are graphs showing the change in hardness and the change in luminance of a MoNbCr film, respectively, when the amount of introduced nitrogen gas was changed while the amount of Ar gas was kept constant at 105 sccm. The film hardness has a certain peak value according to the nitrogen introduction amount, and the luminance gradually decreases according to the nitrogen introduction amount. The sealing layer 12 of the white antimicrobial member 100 was formed by introducing 3sccm of oxygen gas under the condition of the nitrogen introduction amount of 0sccm in fig. 7 and 8. In this way, a MoNbCr lower oxide film (thickness 0.1 μm) was formed. By forming a MoNbCr lower oxide film, adhesion to a substrate is increased as compared with a MoNbCr alloy film, and scratch resistance can be improved. The oblique adhesion layer 13 was formed by increasing the amount of nitrogen gas introduced in FIGS. 7 and 8 from 0sccm to 30sccm, which showed the maximum hardness, while introducing 3sccm of oxygen gas. In this manner, a nitride film (thickness 0.2 μm) of a MoNbCr alloy was formed. The cured layer 11 was formed under the condition that the nitrogen gas introduction amount showing the maximum hardness was 30 sccm. In this manner, a nitride film (thickness 1.6 μm) of a MoNbCr alloy was formed. The upper inclined layer 14 is formed by reducing the nitrogen introduction amount 30sccm showing the maximum hardness in fig. 7 and 8 to 0sccm in an inclined manner. A nitride film of MoNbCr alloy (thickness 0.2 μm) was formed in this manner. The white antibacterial coating 20 was formed on the upper color gradient layer 14 by introducing argon gas of 105sccm and sputtering a Pt96 at% Cu4 at% molten target. The thickness of the white antibacterial coating 20 is about 20 nm. In this manner, the white antibacterial member 100 is obtained.

If the oblique adhesion layer 13 is provided as in example 5-1, there is no clear interface between the adhesion layer and the wear-resistant layer, and therefore integration with the base material 10 is achieved. By providing the inclined adhesion layer, the adhesion between the adhesion layer and the wear-resistant layer can be sufficiently ensured, and the film stress rises obliquely. This can provide an effect of suppressing the occurrence of cracks and peeling due to stress strain, improve scratch resistance and wear resistance, and form a wear-resistant layer having high film hardness in a thick film. Since the scratch resistance is determined by the product of the hardness of the wear-resistant layer, the film thickness of the wear-resistant layer, and the degree of adhesion to the base material, the scratch resistance can be improved by improving the adhesion to the base material.

The color-sloped layer 14 of the white antibacterial member 100 of example 5-1 was formed by reducing the nitrogen gas content in a sloped manner so that L was^*The rise in brightness is performed obliquely so as to approach the brightness of the white antibacterial coating 20. By providing the colored inclined layer, even if the white antibacterial coating becomes thin due to scratches and abrasion, the coating is not noticeable in an actual use environment and can be used without giving an uncomfortable feeling. Further, since the amount of nitrogen contained in the colored oblique layer gradually decreases from the solidified layer, there is no clear interface, and the crack is suppressed and the adhesion is realizedThe improvement also contributes to the scratch resistance.

It is easy to produce a film in which Mo, Nb, and Cr are alloyed, and the hardness, brightness, corrosion resistance, and adhesion of the film can be freely controlled. The nitride, carbide, oxide, oxynitride, oxycarbide, carbonitride, oxycarbonitride of these alloys can be easily produced by adjusting the reactive gas, and can be changed according to the required characteristics. Further, since Mo and Cr have very high adhesion to the substrate, a MoNbCr alloy film can be formed very thickly and is easily improved in scratch resistance.

Table 5 shows the results of measuring the hardness, scratch resistance, corrosion resistance, color tone and antibacterial property of example 5-1 and example 1-1. Compared with examples 1-1, 3-1 and 4-1, the hardness and scratch resistance were significantly improved. The amounts of the components in the white antibacterial coating 20 of example 5-1 were the same as in example 1-1.

When scratch resistance and abrasion resistance are required, the thickness of the white antibacterial coating 20 is preferably 10nm to 50 nm. When the film thickness is less than 10nm, the antibacterial activity may not be sufficiently exhibited. When the film thickness exceeds 50nm, the hardness of the entire white antimicrobial member is lowered, and therefore, the scratch resistance may be poor. By setting the thickness of the PtCu alloy film to about 10nm as in example 5-1, a white antibacterial member having excellent antibacterial properties, corrosion resistance, scratch resistance, and color tone can be produced.

[ Table 5]

< example 6 >

[ example 6-1 ]

A white antimicrobial member 100 shown in fig. 3 was produced. As the sputtering target, targets composed of Ti80 wt% Cu20 wt% were disposed in target 1 and target 2, and a molten target of Pt96 at% Cu4 at% was used in target 3. As the substrate 10, a substrate made of SUS316L was used. Argon gas of 105sccm was introduced by a sputtering method to form the adhesion layer 12 (thickness 100nm) made of TiCu. Then, argon gas of 105sccm and methane gas of 12sccm were introduced to prepare a solidified layer 11 (thickness 900nm) composed of TiCuC. Subsequently, argon gas of 105sccm was introduced and a molten target of Pt96 at% Cu4 at% was sputtered to form a white antibacterial coating film 20 having a thickness of about 20nm on the solidified layer 11, thereby obtaining a white antibacterial member 100.

As in example 6-1, when the composition of the substrate and the cured layer is different, an adhesion layer may be provided. In example 6-1, since SUS316L was used as the substrate, if a cured layer was formed directly on the substrate, there was a case where the scratch resistance was significantly reduced due to peeling caused by a reduction in adhesion force and generation of cracks caused by stress strain. The scratch resistance is determined by the product of the hardness of the wear-resistant layer, the film thickness of the wear-resistant layer, and the degree of adhesion to the substrate, and therefore, when different types of materials are laminated, the adhesion to the substrate is important.

The TiCuC layer in the hard layer 11 also exhibits antibacterial properties by itself, by containing 16.28 at% Cu in the film. Therefore, even if the white antibacterial film 20 as the outermost layer is completely removed, the antibacterial property can be maintained. By forming a white antibacterial coating film 20, L on the hard layer 11^*The white antibacterial member with high brightness can be manufactured.

Table 6 shows the results of measuring the hardness, scratch resistance, corrosion resistance, color tone, and antibacterial property of example 6-1 and hard layer 11. The hardness and scratch resistance are significantly improved as compared with the hard layer 11. The amounts of the components in the white antibacterial coating 20 of example 6-1 were the same as in example 1-1.

[ Table 6]

In examples 1 and 3 to 6, the same results as those obtained in examples 1 and 3 to 6 were obtained in both cases where Pd or Rh was used instead of Pt and where Ni was used instead of Cu. In example 2, the same results as those obtained in example 2 were obtained using Pd or Rh instead of Pt.

< method of measurement >

[ elemental quantity ]

The amounts of the respective elements in the white antibacterial coating were measured by EDX (energy dispersive X-ray spectroscopy). The acceleration voltage of incident electrons is set to 15.0kV to 50.0kV, and the sample is quantitatively analyzed from the energy value of the obtained spectrum by detecting characteristic X-rays emitted from the sample by a semiconductor detector and performing energy spectroscopy. In obtaining the quantitative values of the respective element amounts, correction is performed in consideration of differences between the standard sample and the unknown sample in scattering of incident electrons by the sample, absorption of X-rays emitted from the sample, and fluorescence excitation (ZAF correction method).

[ antibacterial Properties ]

The antibacterial property test was carried out in accordance with "JIS Z801: 2012 antibacterial processing-antibacterial property test method-antibacterial effect ".

1) Preparation of test piece

The antibacterial processing test piece (sample, i.e., the white antibacterial member produced in the example and the white member produced in the comparative example) was cleaned by ethanol washing, air-dried sufficiently, and then used for the test. The film and the non-processed test piece were used by cutting a polyethylene film and performing EOG sterilization.

2) Preparation of test bacterial solution

The test bacteria (staphylococcus aureus (NBRC12732) and escherichia coli (NBRC3972)) are prepared by inoculating the preserved bacteria to a common agar culture medium for culture, and suspending the preserved bacteria in 1/500 common meat soup after 18-20 hours after passage on the next day.

3) Inoculation and culture of test bacteria

The test piece was inoculated with 0.2mL of test bacterial suspension, covered with a membrane (20X 40mm rectangle), and then cultured at 35 ℃ and 90% or more relative humidity for 24 hours.

4) Washing of test bacteria and determination of viable count

The non-processed test piece immediately after inoculation of the test bacterial liquid was washed with 10mL of SCDLP medium (antimicrobial inactivation medium), and the viable cell count was investigated by agar plate culture. The viable cell count was similarly measured for the non-processed test piece and the antibacterial processed test piece after 24-hour culture. The viable cell count was measured by the agar plate culture method (agar plate mix release method). The washing solution and the 10-fold dilution series thereof were dispensed into a petri dish, and a standard agar medium was added thereto and mixed. After the agar solidified, the petri dish was inverted and incubated at 35 ℃ for 40-48 hours. After the culture, the number of viable bacteria (colonies) was measured, and the number of viable bacteria was not calculated.

Here, fig. 9 is a photograph of a non-processed test piece after an antibacterial property test by staphylococcus aureus. FIG. 10 is a photograph of a non-processed test piece after the antibacterial activity test by Escherichia coli. On the other hand, fig. 11 is a photograph of the antibacterial processed test piece after the antibacterial activity test by staphylococcus aureus. FIG. 12 is a photograph of the antibacterial processed test piece after the antibacterial activity test by Escherichia coli. These specifically show the petri dish when measuring viable count (colonies). In addition, FIG. 11 and FIG. 12 are photographs after a test using the antibacterial processing test piece of example 1-1.

5) Determination of test establishment conditions

1. The following equation holds for the logarithmic value of viable cell count immediately after inoculation of the non-processed test piece.

(Lmax－Lmin)/Lmean≤0.2

Lmax: maximum value of log number of viable bacteria

Lmin: minimum value of log number of viable bacteria

Lmean: average value of log of viable count of 3 test pieces

2. The average viable cell count of the non-processed test piece immediately after inoculation was 6.2X 10³～2.5×10⁴Per cm²Within the range of (1).

3. In the case of using the membrane as the non-processed test piece, 3 values of viable cell count after 24 hours were all 6.2X 10²Per cm²The above.

The above determination is performed, and the result satisfies the test establishment condition.

6) Calculation and determination of antimicrobial Activity value

Antibacterial activity value: r ═ Ut-U0) - (At-U0 ═ Ut-At

U0: average value of logarithmic value of viable cell count immediately after inoculation of non-processed test piece

Ut: average value of logarithmic value of viable cell count of non-processed test piece after 24 hours

At: average value of logarithmic values of viable cell count of antibacterial processed test piece after 24 hours

"having antibacterial effect" is defined as that the viable count of the test bacteria after 24 hours on the product is 1% or less (antibacterial activity value 2.0 or more) of the viable count on the non-processed product. The judgment criteria were O when the antimicrobial activity value was 2.0 or more and X when the antimicrobial activity value was less than 2.0.

[ film thickness ]

The simple thickness of the white antibacterial coating was measured as follows: the masked Si wafer was introduced into a film deposition apparatus together with a substrate, the mask was removed after film deposition, and the step difference between the masked portion and the unmasked portion was measured to measure the film thickness.

[ tone ]

The color tone of the white antibacterial member was measured based on L using a Spectra Magic NX (light source D65) manufactured by KONICAMINOLTA^*a^*b^*L of the chromaticity diagram^*a^*b^*And evaluated.

[ Corrosion resistance ]

The corrosion resistance of the white antibacterial member was evaluated by the CASS test and the artificial sweat test. The CASS test was conducted in accordance with JIS-H8502, and the atmosphere sprayed with a solution obtained by adding sodium chloride to an acetic acid-based sodium chloride solution and chlorinating the solution was set for 48 hours, and the peeling and discoloration of the white antibacterial coating were observed to evaluate the corrosion resistance. The composition was evaluated to be good when no peeling or discoloration was observed, and evaluated to be "poor" when peeling or discoloration was observed.

The artificial sweat test was conducted in accordance with ISO12870, and the evaluation of corrosion resistance was conducted by placing a liquid (artificial sweat) obtained by mixing sodium chloride and lactic acid in an atmosphere of aeration at 55 ℃ for 48 hours and observing the discoloration of the white antibacterial coating. The color was evaluated as good, slightly, and not as good.

[ Crystal Structure ]

The crystallinity was measured by using an X-ray diffraction apparatus (manufactured by RIGAKU, product name SmartLab). The measurement was performed under the following conditions.

Overall qualitative analysis conditions X-ray output: 40kV, 30mA, scanning axis: 2 θ/θ, scanning range: 5-120 °, 0.02 step length, cable-stayed slit: 5deg, long side restriction slit: 15 mm.

Fractional qualitative analysis condition X-ray output: 40kV, 30mA, scanning axis: 2 θ/θ, scan range: 5-120 °, 0.02 step length, cable-stayed slit: 2.5deg, long side restriction slit: 15 mm.

[ scratch resistance test method ]

The scratch resistance test is a test in which a sandpaper in which alumina particles are uniformly dispersed is brought into contact with a test sample with a certain weight, and a scratch is generated by wiping the sample for a certain number of times. The surface roughness of the scratched test sample was measured by scanning the surface in a direction perpendicular to the direction of scratching, and the root mean square roughness was used as an evaluation of scratch resistance. The scratch resistance can be evaluated numerically because the larger the amount of scratch generation, the deeper the depth of the scratch and the larger the value of the root mean square roughness, and conversely, the smaller the amount of scratch generation, the shallower the depth of the scratch and the smaller the value of the root mean square roughness.

[ method of measuring film hardness ]

The film hardness was measured by using a micro indentation hardness tester (H100 manufactured by FISCHER). The probe was held at a load of 5mN for 10 seconds using a Vickers indenter, and then unloaded, and the film hardness was calculated from the depth of the inserted Vickers indenter.

Claims

1. A white antibacterial member having a base material and a white antibacterial film provided on the base material,

the white antibacterial capsule comprises a metal M1 and a metal M2, the metal M1 is at least 1 selected from Pt, Pd and Rh, the metal M2 is Cu, Ag or Ni,

when the metal M2 is Cu or Ni, the metal M2 is contained in the white antibacterial coating in an amount of 4.15 at% or more,

when the metal M2 is Ag, the metal M2 is contained in the white antibacterial film in an amount of 2.49 at% or more.

2. The white antimicrobial member according to claim 1, wherein said metal M1 is Pt, said metal M2 is Cu or Ni, and said metal M1 is contained in said white antimicrobial coating in an amount of 29.72 at% to 95.85 at%, and said metal M2 is contained in an amount of 4.15 at% to 70.28 at%.

3. The white antibacterial member according to claim 1, wherein the metal M1 is Pt, the metal M2 is Ag, and the metal M1 is contained in the white antibacterial coating film in an amount of 67.13 at% to 97.51 at%, and the metal M2 is contained in an amount of 2.49 at% to 32.87 at%.

4. The white antimicrobial component of any one of claims 1 to 3, wherein said white antimicrobial coating L in Lab color space display^*Is 80.00 or more, a^*Is-2.0 to 2.0, b^*Is-4.50 to 4.50.

5. The white antimicrobial member according to any one of claims 1 to 4, wherein a cured layer is further provided between said base material and said white antimicrobial coating.

6. A timepiece comprising the white antibacterial member according to any one of claims 1 to 5.

7. A method for producing a white antibacterial member, comprising a step of providing a white antibacterial coating on a substrate,

the white antibacterial capsule comprises a metal M1 and a metal M2, wherein the metal M1 is at least 1 selected from Pt, Pd and Rh, the metal M2 is at least 1 selected from Cu, Ag and Ni,