Antimicrobial member

Antibacterial parts technology field

[0001] The present invention relates to an antibacterial component having excellent antibacterial properties and flexibility.

[0002] Furthermore, the present invention relates to an antibacterial component having low cost and excellent antibacterial properties and durability.

[0003] And, the present invention relates to a transparent antibacterial member having excellent transmittance of visible light and excellent antibacterial property.

This application is based on Patent Application No. 2020-057131 filed in Japan on March 27, 2020, Patent Application No. 2020-109482 filed in Japan on June 25, 2020, and Patent Application No. 2020-109482 filed in Japan on July 7, 2020 The patent application No. 2020116807 claims its priority, and the content thereof is incorporated herein by reference.

Background technique

In general, daily utensils such as tables, chairs, shelves, handrails, door handles, etc. used in medical institutions, public facilities, and research facilities with strict hygiene management (such as food, cosmetics, pharmaceuticals, etc.) Since the possibility of contact with many people is specified, it is also expected to have antibacterial properties from the viewpoint of preventing infectious diseases and preventing the spread of viruses or bacteria.

Here, as the material that imparts antibacterial properties to the surfaces of daily utensils such as tables, chairs, shelves, or various products such as armrests and door handles, for example, the antibacterial film (anti-disease) shown in Patent Documents 1 and 2 is proposed. toxic film).

[0007] In Patent Document 1, an antibacterial film in which an antibacterial metal thin film (eg copper, silver, copper alloy, silver alloy) is formed on the surface of a flexible polymer film substrate is proposed.

[0008] Patent Document 2 proposes an antiviral film in which metal particles composed of Cu and Pd are dispersed in an island shape on a film serving as a base material.

Patent Document 1: Japanese Patent Laid-Open No. 2010-247450 (A)

Patent Document 2: Japanese Patent Laid-Open No. 2018-134753 (A)

[0011] However, in the antibacterial films disclosed in Patent Documents 1 and 2, a resin film is used as the base material, and moisture from the resin material constituting the base material may hinder the adhesion between the base material and the metal thin film. Therefore, when the antibacterial film is bent, there is a possibility that the base material and the metal thin film are peeled off, or cracks may occur in the base material or the metal thin film.

[0012] The present invention is accomplished on the background of the above-mentioned situation, and an object thereof is to provide an antibacterial component that is excellent in antibacterial property and flexibility and can be used stably.

[0013] Furthermore, in the antibacterial films disclosed in Patent Documents 1 and 2, a metal is arranged on the outermost surface.

[0014] Here, as described above, the metal layer formed on the surface of the antibacterial member is composed of copper, silver, palladium, etc., and the manufacturing cost is relatively large. In addition, when the thickness of the metal layer is thick, the weight increases, and in order to support the portion, the thickness of the film needs to be increased to ensure rigidity. Therefore, it is required to form the metal layer thin.

[0015] However, when the metal layer of the outermost surface layer is formed into a thin film, there are problems such as metal agglomeration, discoloration, poor appearance, and greatly reduced durability.

[0016] The present invention is accomplished on the background of the above-mentioned situation, and its object is to provide an antibacterial component with low cost, excellent antibacterial properties and excellent durability.

And, in the antibacterial film disclosed in the patent document 1,2, be arranged with metal on the outermost surface, therefore there is metallic luster, the surface of the various products of the configuration of this antibacterial film can not be visually recognized, there is appearance Sexual decline problem.

[0018] In addition, when the metal layer of the outermost surface layer is formed into a thin film, depending on the use environment, the metal may aggregate and cause discoloration, resulting in poor appearance.

[0019] The present invention is completed with the above-mentioned situation as a background, and its object is to provide a kind of antibacterial property and excellent transmittance of visible light, can suppress the generation of poor appearance, and can stably use the transparent antibacterial component.

SUMMARY OF THE INVENTION

In order to solve this problem, the antibacterial component of a mode of the present invention (hereinafter referred to as "the antibacterial component of the present invention") is characterized in that, there is: substrate; base layer, film-forming on this substrate; and copper layer, It is formed on the surface of the base layer on the opposite side of the substrate and arranged on the outermost surface layer, the copper layer is made of copper or a copper alloy, the base layer is made of a metal oxide, and the base plate is made of flexible material. It is composed of flexible resin material or flexible glass material.

[0021] In the antibacterial component of this structure, since the outermost surface layer is provided with a copper layer formed of copper or a copper alloy, the antibacterial property is excellent.

Also, when the substrate is made of a flexible resin material, a base layer formed of a metal oxide is disposed between the substrate and the copper layer, so that the water flow from the flexible resin material constituting the substrate can be suppressed. The copper layer side moves to ensure the adhesion between the substrate and the copper layer. Therefore, even when the antibacterial member of the present invention is bent, the peeling of the substrate and the copper layer or the occurrence of cracks can be suppressed, and stable use can be achieved. Furthermore, even if the substrate is made of a flexible glass material, since the base layer formed of a metal oxide is disposed between the substrate and the copper layer, the adhesion between the substrate and the copper layer can be ensured. Therefore, even when the antibacterial member of the present invention is bent, the peeling of the substrate and the copper layer or the occurrence of cracks can be suppressed, and stable use can be achieved.

[0023] In addition, the copper layer may be composed of copper or a copper alloy, and an oxide film may be formed on the surface thereof.

[0024] And, in the antibacterial component of the present invention, the thickness of the copper layer is preferably below 5um.

[0025] In this case, since the thickness of the copper layer is suppressed as described above, the occurrence of cracks in the copper layer during bending can be suppressed, and peeling from the base layer can be suppressed, and the bendability can be further improved.

[0026] And, in the antibacterial component of the present invention, the thickness of the copper layer can be 35nm or less.

[0027] In the antibacterial member of this structure, since the outermost surface layer is provided with a copper layer formed of copper or a copper alloy, the antibacterial property is excellent. In addition, since the thickness of the copper layer is set to be 35 nm or less, the manufacturing cost can be kept at a relatively low level.

Then, since a base layer formed of a metal oxide is formed between the substrate and the copper layer, even if the thickness of the copper layer is 35 nm or less, the copper aggregation of the copper layer can be suppressed, and the occurrence of poor appearance can be suppressed, Excellent durability.

[0029] In addition, the copper layer may be formed of copper or a copper alloy, and an oxide film may be formed on the surface of the copper layer.

[0030] And, in the antibacterial component of the present invention, the substrate may be a transparent substrate, and the metal oxide may be a metal oxide that transmits visible light.

[0031] In the transparent antibacterial member of this structure, since the outermost surface layer is configured with a copper layer formed of copper or a copper alloy, the antibacterial property is excellent.

In addition, since a base layer made of a metal oxide that transmits visible light is formed on the transparent substrate, the thickness of the copper layer formed on the surface of the base layer on the opposite side of the transparent substrate is set to 35 nm or less, the visible light transmittance is excellent, the surfaces of various products on which the transparent antibacterial member is arranged can be visually recognized, and the appearance is excellent.

Then, although the thickness of the copper layer is thinly formed to be 35 nm or less, since the base layer composed of the metal oxide is formed between the transparent substrate and the copper layer, the copper aggregation of the copper layer can be suppressed, and the Products with poor appearance

raw, excellent durability.

Here, in the antibacterial component of the present invention, after preferably implementing 100 times the bending test that radius of curvature is 6mm, can not observe crack.

In this case, because also does not produce crack under the situation that implements bending test as above, therefore can to the surface close-fitting configuration of the product of various shapes, can give antibacterial property to the surface of product.

[0036] Moreover, in the antibacterial component of the present invention, the thickness of the base layer is preferably 500 nm or less.

[0037] In this case, since the thickness of the base layer is suppressed as described above, the occurrence of cracks in the base layer during bending can be suppressed, and the bendability can be further improved.

[0038] And, in the antibacterial component of the present invention, the thickness of the base layer is preferably 100 nm or less.

[0039] In this case, since the thickness of the base layer formed of the metal oxide is limited to 100 nm or less, the manufacturing cost can be kept lower.

[0040] And, in the transparent antibacterial component of the present invention, the thickness of the base layer is preferably below 50nm.

[0041] In this case, the visible light transmittance of the base layer can be fully ensured, and the surfaces of various products that configure the transparent antibacterial member can be fully visually recognized.

[0042] And, in the antibacterial component of the present invention, the thickness of the substrate is preferably below 500um.

[0043] In this case, since the thickness of the substrate is suppressed as described above, the flexibility of the substrate itself can be ensured, and the flexibility can be further improved.

And, in the antibacterial part of the present invention, the described metal oxide that preferably constitutes described base layer comprises selected from In oxide, Sn oxide, Zn oxide, Nb oxide, Ti oxide, Al oxide any one or two or more of compounds, Ga oxides, W oxides, Mo oxides, Si oxides, Zr oxides, Ta oxides, Y oxides, Ge oxides, Cu oxides, and Ag oxides .

In this case, since the base layer is composed of the above-mentioned metal oxide, the movement of moisture from the resin material constituting the substrate to the copper layer side is reliably suppressed, and the adhesion between the substrate and the copper layer can be further improved , and can further improve the flexibility.

And, in antibacterial part of the present invention, preferably described copper layer is made up of copper alloy, and this copper alloy comprises a kind of selected from Zn, Sn, Ni, Al, Si and Mn more than 0.1 mass % in total or two or more, and the Cu content is set to 45% by mass or more.

[0047] In this case, since the Cu content of the copper layer is set to 45 mass % or more, the antibacterial properties can be sufficiently ensured. In addition, since the copper layer contains 0.1 mass % or more in total of one or more selected from the group consisting of Zn, Sn, Ni, Al, Si, and Mn, discoloration of the copper layer can be suppressed.

And, in the antibacterial part of the present invention, preferably the surface layer of described copper layer is formed with Cu oxide film, CuO and Cu in this Cu oxide film₂Molar ratio of O CuO/Cu₂O is CuO/Cu₂O<1.

In this case, in the Cu oxide film formed on the surface layer of the copper layer, Cu₂The O content is larger than the CuO content, and the antibacterial properties can be sufficiently ensured.

[0050] Furthermore, in the antibacterial member of the present invention, it is preferable that an adhesive layer is provided on the surface of the substrate opposite to the base layer.

[0051] In this case, by using the adhesive layer, the antibacterial member can be easily arranged on the surface of various products.

[0052] Furthermore, in the antibacterial component of the present invention, it is preferable that the substrate is made of glass or resin.

[0053] In this case, a relatively large antibacterial member can be produced relatively easily at low cost.

Here, in the antibacterial part of the present invention, the transmittance to the light of wavelength 550nm in the lamination direction is preferably more than 5%.

In this case, because the transmittance to the light of wavelength 550nm is set as more than 5% in lamination direction, therefore can fully visually recognize the surface of the various products of this antibacterial component configuration, can improve appearance reliably sex.

[0056] According to the present invention, it is possible to provide an antibacterial member that is excellent in antibacterial properties and flexibility and can be used stably.

[0057] And, according to the present invention, can provide a kind of low cost and excellent antibacterial properties, and excellent antibacterial parts durability.

And, according to the present invention, can provide a kind of antibacterial property and the transmittance of visible light excellent, and can suppress the generation of poor appearance, and the transparent antibacterial component that can use stably.

Description of drawings

1 is an explanatory diagram showing an example of an antibacterial member according to an embodiment of the present invention.

[0060] FIG. 2A is an explanatory diagram of a test method for evaluating bendability in Examples.

[0061] FIG. 2B is an explanatory diagram of a test method for evaluating bendability in Examples.

[0062] FIG. 2c is an explanatory diagram of a test method for evaluating bendability in Examples.

3 is an explanatory diagram showing an example of an antibacterial member according to an embodiment of the present invention.

4 is an explanatory diagram showing an example of a transparent antibacterial member according to an embodiment of the present invention.

Detailed ways

[0065] [First Embodiment]

[0066] Hereinafter, the antibacterial member of the first embodiment of the present invention will be described.

[0067] The antibacterial member 110 of this embodiment is a member that is disposed on the surfaces of daily utensils such as tables, chairs, and shelves, or various products such as armrests and door handles, thereby imparting antibacterial properties to the surfaces of various products.

As shown in FIG. 1 , the antibacterial component 110 of the present embodiment includes a base layer 112 disposed on one side of the substrate 111 (the upper surface in FIG. 1 ) and a base layer 112 that is stacked on the base layer 112 opposite to the substrate 111. side copper layer 113 on the face side.

[0069] In this embodiment, as shown in FIG. 1 , an adhesive layer 115 is formed on the surface of the substrate 111 opposite to the base layer 112.

[0070] Here, since the antibacterial member 110 of the present embodiment has excellent flexibility, it can be closely arranged on the surfaces of products of various shapes.

[0071] Specifically, in the antibacterial member 110 of the present embodiment, it is preferable that cracks are not observed after 100 bending tests with a radius of curvature of 6 mm.

[0072] The substrate 111 is a substrate supporting the base layer 112 and the copper layer 113, and in this embodiment, it is made of a flexible resin material excellent in flexibility.

[0073] As the flexible resin material constituting the substrate 111, for example, polyethylene phthalate (PET), polyolefin (PO), acrylic, polyvinyl chloride, etc. can be mentioned.

[0074] Here, in this embodiment, in order to further ensure the flexibility of the antibacterial member 110, the thickness of the substrate 111 is preferably below 500um, more preferably below 400um, and further preferably below 300um. On the other hand, in order to secure the rigidity of the substrate 111 , the thickness of the substrate 111 is preferably 10 μm or more, more preferably 25 μm or more, and further preferably 50 μm or more.

[0075] The base layer 112 is composed of a metal oxide that transmits visible light. The base layer 112 serves to suppress the

The barrier layer for gas components and moisture to reach the copper layer 113 acts as a barrier, and has an effect of suppressing the peeling phenomenon at the interface. In addition, a metal oxide is arranged as the base layer 112 between the substrate 111 and the copper layer 113 , whereby the interface energy between the copper layer 113 (Cu) and the base layer 112 (metal oxide) is lowered, and it is possible to suppress the concentration of the copper layer 113 The effect of Cu agglomeration.

[0076] The metal oxide constituting the base layer 112 preferably contains a metal oxide selected from the group consisting of In oxide, Sn oxide, Zn oxide, Nb oxide, Ti oxide, Al oxide, Ga oxide, W oxide, Mo Any one or two or more of oxides, Si oxides, Zr oxides, Ta oxides, Y oxides, Ge oxides, Cu oxides, and Ag oxides.

Specifically, can enumerate In-Sn oxide, Al-Zn oxide, In-Zn oxide, Zn-Sn oxide, Zn-SnAl oxide, Ga-Zn oxide, Zn-Y oxide compound, Ga-Zn-Y oxide, In-Ga-Zn oxide, etc.

[0078] Here, in this embodiment, in order to further ensure the flexibility of the antibacterial member 110, the thickness of the base layer 112 is preferably 500 nm or less, more preferably 400 nm or less, and further preferably 300 nm or less. On the other hand, in order to further exert the function and effect as a barrier layer, the thickness of the base layer 112 is preferably 2 nm or more, more preferably 5 nm or more, and still more preferably 10 nm or more.

[0079] The copper layer 113 is composed of copper or a copper alloy. Here, copper or copper alloys are known to have antibacterial effects (including bacteriostatic effects). Infections caused by various bacteria and viruses can be prevented by using copper alloys with antibacterial properties (bacteriostatic effect) in parts that many people touch.

[0080] Here, in this embodiment, in order to further ensure the flexibility of the antibacterial member 110, the thickness of the copper layer 113 is preferably 5um or less, more preferably 4um or less, and more preferably 3um or less. On the other hand, in order to sufficiently secure antibacterial properties, the thickness of the copper layer 113 is preferably 5 nm or more, more preferably 10 nm or more, and still more preferably 15 nm or more.

[0081] In this embodiment, the copper layer 113 may be composed of a copper alloy containing a total of 0.1 mass % or more of one or two selected from the group consisting of Zn, Sn, Ni, Al, Si and Mn above, and the Cu content is set to 45% by mass or more.

By including one or two or more selected from Zn, Sn, Ni, Al, Si and Mn in a total of 0.1 mass% or more, the uniformity or durability of the copper layer 113 during film formation can be greatly improved Wait. In addition, in order to fully exhibit this effect, the total content of one or more selected from Zn, Sn, Ni, Al, Si, and Mn is more preferably 0.2 mass % or more, and further preferably 0.3 mass % above.

[0083] Furthermore, when the Cu content is 45% by mass or more, the antibacterial properties based on Cu can be sufficiently ensured. In addition, the lower limit of the Cu content is more preferably 47.5 mass % or more, and further preferably 50 mass % or more.

[0084] Furthermore, in the present embodiment, a Cu oxide film may be formed on the outermost surface of the copper layer 113. On the outermost surface of the copper layer 113, CuO and Cu₂Molar ratio of O CuO/Cu₂O is preferably CuO/Cu₂O<1. That is, it is preferable to use Cu₂The O content is more than the CuO content. by making Cu₂The O content is larger than the CuO content, and the antibacterial properties can be sufficiently ensured.

In addition, CuO and Cu₂Molar ratio of O CuO/Cu₂O is more preferably less than 0.9, more preferably less than 0.8.

[0086] Hereinafter, the manufacturing method of the antibacterial member 110 involved in the present embodiment will be described.

[0087] First, the substrate 111 on which the adhesive layer 115 is formed is prepared.

[0088] Next, the base layer 112 is formed on one surface (the surface opposite to the adhesive layer 115) of the substrate 111 by a sputtering method. In this case, it is preferable to use a sputtering target having a composition corresponding to the oxide constituting the base layer 112 . For example, an oxide sputtering target made of a metal oxide constituting the base layer 112 may be used, or a metal sputtering target of a metal oxide constituting the base layer 112 may be used, and oxygen may be introduced to apply the reactive sputtering method . In addition, it is preferable to select and use DC (direct current) sputtering, RF (high frequency) sputtering, MF secondary frequency) sputtering, AC (alternating current) sputtering, etc. as appropriate in consideration of the electrical conductivity of the sputtering target and the like.

[0089] Next, a copper layer 113 is formed on the formed base layer 112 by a sputtering method. At this time, a sputtering target having a composition corresponding to copper or copper alloy constituting the copper layer 113 is used. At this time, the sputtering conditions are appropriately adjusted so that the thickness of the copper layer 113 becomes

specified thickness. In addition, at the time of sputtering, the film thickness at the time of film formation for a predetermined time was measured with a step difference meter (DEKTAK-XT) to measure the sputtering rate, and the film formation time was adjusted according to the value to form a film. until it reaches the target film thickness.

[0090] Through the above procedures, the antibacterial component 110 of the present embodiment can be manufactured.

[0091] According to the antibacterial member 110 of the present embodiment adopting the above-mentioned structure, since the copper layer 113 formed of copper or a copper alloy is disposed on the outermost surface layer, the antibacterial property is excellent.

In addition, the substrate 111 is composed of a flexible resin material, and the base layer 112 formed of a metal oxide is arranged between the substrate 111 and the copper layer 113, so that moisture from the flexible resin material constituting the substrate 111 can be suppressed. By moving to the copper layer 113 side, the adhesion between the substrate 111 and the copper layer 113 can be ensured. Therefore, even when the antibacterial member 110 of the present embodiment is bent, peeling of the substrate 111 and the copper layer 113 can be suppressed, and stable use is possible.

In addition, in the case where the substrate is made of a flexible glass material, also because a base layer formed of a metal oxide is arranged between the substrate and the copper layer, the adhesion between the substrate and the copper layer can be ensured sex. Therefore, even when the antibacterial member of the present invention is bent, peeling of the substrate and the copper layer and generation of cracks can be suppressed, and stable use can be achieved.

In addition, in this embodiment, when no cracks are observed after 100 times of bending tests with a radius of curvature of 6 mm, the surfaces of products of various shapes can be arranged in close contact with the surfaces of the products. Provides antibacterial properties.

[0095] Moreover, in the present embodiment, when the thickness of the copper layer 113 is below 5um or the thickness of the base layer 112 is below 500nm or the thickness of the substrate 111 is below 500um, the flexibility of the antibacterial component 110 can be further improved.

Furthermore, in this embodiment, when the copper layer 113 is composed of a copper alloy, and the copper alloy contains a total of 0.1 mass % or more selected from Zn, Sn, Ni, Al, Si and Mn in one or two. When the Cu content is 45 mass % or more, the antibacterial property can be sufficiently ensured, the durability of the copper layer 113 can be improved, and the occurrence of discoloration can be suppressed.

[0097] In this embodiment, when a Cu oxide film is formed on the surface layer of the copper layer 113, and the CuO and Cu in the Cu oxide film₂Molar ratio of O CuO/Cu₂O is CuO/Cu₂When O<1, Cu₂The O content is more than the CuO content, and the antibacterial properties can be sufficiently ensured.

Furthermore, in the present embodiment, when the adhesive layer 115 is provided on the surface of the substrate 111 on the opposite side to the base layer, the adhesive layer 115 can be easily placed on the surface of various products using the adhesive layer 115 Antimicrobial component 110 .

[0099] The embodiments of the present invention have been described above, but the present invention is not limited thereto, and changes can be appropriately made without departing from the technical idea of the present invention.

[0100] For example, in the present embodiment, an example where the adhesive layer is formed has been described, but the adhesive layer may not be formed.

[0101] In addition, the copper or copper alloy constituting the copper layer is not limited to the copper or copper alloy described in the embodiment, and various copper alloys can be used. For example, a copper alloy in which Sn, Ni, Al, Pb, Mn, Si, P, etc. are added to brass mainly composed of Cu and Zn may be used. Also in this case, it is preferable to set the Cu content to 45 mass % or more.

[0102] [Second Embodiment]

[0103] Hereinafter, the antibacterial member of the second embodiment of the present invention will be described.

[0104] The antibacterial member of the present embodiment is a member that imparts antibacterial properties to the surface of various products by being disposed on the surfaces of daily utensils such as tables, chairs, and shelves, or on the surfaces of various products such as armrests and door handles.

As shown in FIG. 3, the antibacterial component 210 of the present embodiment has a base layer 212 disposed on one side of the substrate 211 (the upper surface in FIG. 3) and a base layer 212 opposite to the substrate 211 stacked on the base layer 212. side copper layer 213 on the face side.

[0106] In the present embodiment, as shown in FIG. 3 , an adhesive layer 215 is formed on the surface of the substrate 211 opposite to the base layer 212.

[0107] The substrate 211 is a substrate supporting the base layer 212 and the copper layer 213. In this embodiment, it is preferable to consist of a glass material, a resin material, or the like.

[0108] Here, as the resin material constituting the substrate 211, for example, polyethylene phthalate (PET), polyolefin (PO), acrylic, polyvinyl chloride, and the like can be mentioned. When the substrate 211 formed of these resin materials is used, the antibacterial member 210 can be bent. In particular, when the thickness of the substrate 211 formed of a resin material is 300 μm or less, the flexibility can be further ensured.

[0109] In addition, when the substrate 211 is made of a glass material, flexibility can be obtained by setting the thickness to 200 μm or less.

[0110] The base layer 212 is composed of a metal oxide. Between the substrate 211 and the copper layer 213 , a metal oxide is arranged as the base layer 212 , thereby reducing the interface energy between the copper layer 213 (Cu) and the base layer 212 (metal oxide), and suppressing Cu in the copper layer 213 the effect of agglomeration. In addition, the base layer 212 functions as a barrier layer that prevents gas components and moisture from the substrate 211 from reaching the copper layer 213, and has an effect of suppressing the peeling phenomenon at the interface.

[0111] Here, as the metal oxide constituting the base layer 212, it is preferable to include a metal oxide selected from the group consisting of In oxide, Sn oxide, Zn oxide, Nb oxide, Ti oxide, Al oxide, Ga oxide, and W oxide. Any one or two or more of compounds, Mo oxides, Si oxides, Zr oxides, Ta oxides, Y oxides, Ge oxides, Cu oxides, and Ag oxides.

Specifically, can enumerate In-Sn oxide, Al-Zn oxide, In-Zn oxide, Zn-Sn oxide, Zn-SnAl oxide, Ga-Zn oxide, Zn-Y oxide compound, Ga-Zn-Y oxide, In-Ga-Zn oxide, etc.

[0113] Furthermore, in order to reduce the manufacturing cost, the upper limit of the thickness of the base layer 212 is preferably 100 nm or less, and more preferably 50 nm or less.

[0114] On the other hand, in order to fully exert the effect as the base layer 212, the lower limit of the thickness of the base layer 212 is preferably 5 nm or more, more preferably 8 nm or more, and more preferably 10 nm or more.

[0115] The copper layer 213 is composed of copper or a copper alloy. Here, copper or copper alloys are known to have antibacterial effects (including bacteriostatic effects). Infections by various bacteria and viruses can be prevented by using copper alloys having antibacterial properties (bacteriostatic effect) for parts that are not particularly touched by many people.

[0116] Here, if the thickness of the copper layer 213 is thicker than 30 nm, the antibacterial property will not be further improved, and the manufacturing cost will be increased, and the weight will be increased. Therefore, in this embodiment, the upper limit of the thickness of the copper layer 213 is made 30 nm or less. In addition, the upper limit of the thickness of the copper layer 213 is preferably 27 nm or less, and more preferably 25 nm or less.

[0117] On the other hand, if the thickness of the copper layer 213 is too thin, the proportion of the surface in the volume of the copper layer 213 is relatively high, the energy becomes unstable, the copper tends to agglomerate, and the durability may decrease. sex. Therefore, the lower limit of the thickness of the copper layer 213 is preferably 2 nm or more, more preferably 5 nm or more, and further preferably 10 nm or more.

In addition, in this embodiment, the copper layer 213 may be composed of a copper alloy containing one or two selected from Zn, Sn, Ni, Al, Si and Mn in a total of 0.1 mass % or more. above, and the Cu content is set to 45% by mass or more.

By including a total of 0.1 mass % or more selected from Zn, Sn, Ni, Al, Si and Mn in one or two or more, the uniformity or durability of the copper layer 213 during film formation can be greatly improved Wait. In addition, in order to fully exhibit this effect, the total content of one or more selected from Zn, Sn, Ni, Al, Si, and Mn is more preferably 0.2 mass % or more, and further preferably 0.3 mass % above.

[0120] Also, when the Cu content is 45% by mass or more, the antibacterial properties based on Cu can be sufficiently ensured. In addition, the lower limit of the Cu content is more preferably 47.5 mass % or more, and further preferably 50 mass % or more.

[0121] Furthermore, in this embodiment, a Cu oxide film may be formed on the outermost surface of the copper layer 213. in the copper layer

The outermost surface of 213, CuO and Cu₂Molar ratio of O CuO/Cu₂O is preferably CuO/Cu₂O<1. That is, it is preferable to use Cu₂The O content is more than the CuO content. by making Cu₂The O content is larger than the CuO content, and the antibacterial properties can be sufficiently ensured.

In addition, CuO and Cu₂Molar ratio of O CuO/Cu₂O is more preferably less than 0.9, more preferably less than 0.8.

[0123] Hereinafter, the manufacturing method of the antibacterial member 210 according to the present embodiment will be described.

[0124] First, the substrate 211 on which the adhesive layer 215 is formed is prepared.

[0125] Next, the base layer 212 is formed on one surface of the substrate 211 (the surface on the opposite side to the adhesive layer 215) by a sputtering method. In this case, it is preferable to use a sputtering target having a composition corresponding to the oxide constituting the base layer 212 . For example, an oxide sputtering target formed of a metal oxide constituting the base layer 212 may be used, or a reactive sputtering method may be applied by introducing oxygen using a metal sputtering target of a metal oxide constituting the base layer 212 . In addition, it is preferable to select and use DC (direct current) sputtering, RF (high frequency) sputtering, MF secondary frequency) sputtering, AC (alternating current) sputtering, etc. as appropriate in consideration of the electrical conductivity of the sputtering target and the like.

[0126] Next, a copper layer 213 is formed on the formed base layer 212 by a sputtering method. At this time, a sputtering target having a composition corresponding to Cu or Cu alloy constituting the copper layer 213 is used. At this time, the sputtering conditions are appropriately adjusted so that the thickness of the copper layer 213 becomes a predetermined thickness. In addition, at the time of sputtering, the film thickness at the time of film formation for a predetermined time was measured with a step difference meter (DEKTAK-XT) to measure the sputtering rate, and the film formation time was adjusted according to the value to form a film until it reaches the target film thickness.

[0127] Through the above procedures, the antibacterial component 210 of the present embodiment can be manufactured.

[0128] According to the antibacterial member 210 of the present embodiment adopting the above-mentioned structure, since the copper layer 213 formed of copper or a copper alloy is disposed on the outermost surface layer, the antibacterial property is excellent.

[0129] Furthermore, since the thickness of the copper layer 213 is set to be 30 nm or less, the manufacturing cost can be kept at a relatively low level.

Then, although the thickness of the copper layer 213 is thinly formed to be 30 nm or less, since the base layer 212 made of metal oxide is formed between the substrate 211 and the copper layer 213, the copper in the copper layer 213 can be suppressed. Agglomeration can suppress the occurrence of poor appearance, and is excellent in durability.

[0131] In the present embodiment, when the thickness of the base layer 212 is 100 nm or less, the manufacturing cost can be kept lower.

[0132] Furthermore, in this embodiment, when the metal oxide constituting the base layer 212 contains a metal oxide selected from the group consisting of In oxide, Sn oxide, Zn oxide, Nb oxide, Ti oxide, Al oxide, and Ga oxide , W oxides, Mo oxides, Si oxides, Zr oxides, Ta oxides, y oxides, Ge oxides, Cu oxides, and Ag oxides. Aggregation of copper in the copper layer 213 can further suppress the occurrence of poor appearance, and can further improve durability.

Also, in the present embodiment, when the copper layer 213 is composed of one or two or more selected from Zn, Sn, Ni, Al, Si and Mn in a total of 0.1 mass % or more and the Cu content is set to When the copper alloy content is 45 mass % or more, the antibacterial properties can be sufficiently ensured, the durability of the copper layer 213 can be further improved, and the occurrence of discoloration can be suppressed.

[0134] Furthermore, in the present embodiment, when the substrate 211 is made of glass or resin, a relatively large antibacterial member 210 can be produced relatively easily at low cost.

[0135] In this embodiment, when a Cu oxide film is formed on the surface layer of the copper layer 213, and the CuO and Cu in the Cu oxide film₂Molar ratio of O CuO/Cu₂O is CuO/Cu₂When O<1, Cu₂The O content is more than the CuO content, and the antibacterial properties can be sufficiently ensured.

[0136] Furthermore, in this embodiment, when the surface of the substrate 211 opposite to the base layer is provided with an adhesive layer

At 215, the antibacterial member 210 can be easily deployed on the surface of various articles using the adhesive layer 215.

[0137] The embodiments of the present invention have been described above, but the present invention is not limited thereto, and changes can be appropriately made without departing from the technical idea of the present invention.

[0138] For example, in the present embodiment, an example where the adhesive layer is formed has been described, but the adhesive layer may not be formed.

[0139] In addition, the copper or copper alloy constituting the copper layer is not limited to the copper or copper alloy described in the embodiment, and various copper alloys can be used. For example, a copper alloy in which Sn, Ni, Al, Pb, Mn, Si, P, etc. are added to brass mainly composed of Cu and Zn may be used. Also in this case, it is preferable to set the Cu content to 45 mass % or more.

[Third Embodiment]

[0141] Hereinafter, the transparent antibacterial member of the third embodiment of the present invention will be described.

[0142] The transparent antibacterial member of the present embodiment is, for example, a member that is disposed on the surfaces of daily utensils such as tables, chairs, and shelves, or various products such as armrests and door handles, thereby imparting antibacterial properties to the surfaces of various products.

As shown in Figure 4, the transparent antibacterial component 310 of the present embodiment has the base layer 312 that is arranged on one side of the transparent substrate 311 (the upper surface in Figure 4) and the transparent substrate 311 that is laminated on the base layer 312. The copper layer 313 on the opposite side.

[0144] In this embodiment, as shown in FIG. 4 , an adhesive layer 315 is formed on the surface of the transparent substrate 311 on the opposite side to the base layer 312.

[0145] The transparent substrate 311 is preferably made of a material having a high transmittance of visible light, such as a glass material or a resin material.

[0146] Here, as the resin material constituting the transparent substrate 311, for example, polyethylene phthalate (PET), polyolefin (PO), acrylic, polyvinyl chloride, etc. can be mentioned. When the transparent substrate 311 formed of these resin materials is used, the transparent substrate 311 can be bent. In particular, when the thickness of the transparent substrate 311 formed of a resin material is 300 μm or less, the flexibility can be further ensured.

[0147] Furthermore, when the transparent substrate 311 is made of a glass material, flexibility can be obtained by setting the thickness to 200 μm or less.

[0148] In addition, the lower limit of the thickness of the transparent substrate 311 is not particularly limited, but from the viewpoint of ensuring rigidity, it is preferably 10 μm or more, and more preferably 20 μm or more.

[0149] The base layer 312 is composed of a metal oxide that transmits visible light. Between the transparent substrate 311 and the copper layer 313 , a metal oxide is arranged as the base layer 312 , whereby the interface energy between the copper layer 313 (Cu) and the base layer 312 (metal oxide) is lowered, and the copper layer 313 is suppressed in The effect of Cu agglomeration. In addition, the base layer 312 functions as a barrier layer that prevents gas components and moisture from the transparent substrate 311 from reaching the copper layer 313, and has an effect of suppressing the peeling phenomenon at the interface.

[0150] Here, as the metal oxide constituting the base layer 312, it is preferable to include a metal oxide selected from the group consisting of In oxide, Sn oxide, Zn oxide, Nb oxide, Ti oxide, Al oxide, Ga oxide, and W oxide. Any one or two or more of compounds, Mo oxides, Si oxides, Zr oxides, Ta oxides, Y oxides, Ge oxides, Cu oxides, and Ag oxides.

Specifically, can enumerate In-Sn oxide, Al-Zn oxide, In-Zn oxide, Zn-Sn oxide, Zn-SnAl oxide, Ga-Zn oxide, Zn-Y oxide compound, Ga-Zn-Y oxide, In-Ga-Zn oxide, etc.

[0152] These metal oxides are excellent in visible light transmittance.

[0153] In the base layer 312, in order to sufficiently ensure the transmittance of visible light, the upper limit of the thickness of the base layer 312 is preferably 100 nm or less, and more preferably 50 nm or less.

[0154] On the other hand, in order to fully exert the effect as the base layer 312, the lower limit of the thickness of the base layer 312 is preferably 3 nm or more, more preferably 4 nm or more, and more preferably 5 nm or more.

[0155] The copper layer 313 is composed of copper or a copper alloy. Here, copper or copper alloys are known to have antibacterial effects (including bacteriostatic effects). Infections caused by various bacteria and viruses can be prevented by using copper alloys with antibacterial properties (bacteriostatic effect) for parts that are touched by unspecified many people.

[0156] Here, in this embodiment, the upper limit of the thickness of the copper layer 313 is set to 35 nm or less. Thereby, the transmittance of visible light in the copper layer 313 can be ensured. In addition, in order to further secure the transmittance of visible light in the copper layer 313, the upper limit of the thickness of the copper layer 313 is preferably 30 nm or less, and more preferably 25 nm or less.

[0157] On the other hand, if the thickness of the copper layer 313 is too thin, the proportion of the surface in the volume of the copper layer 313 is relatively high, the energy becomes unstable, the copper tends to agglomerate, and the durability may decrease. sex. Therefore, the lower limit of the thickness of the copper layer 313 is preferably 2 nm or more, more preferably 3 nm or more, and further preferably 4 nm or more.

In addition, in this embodiment, the copper layer 313 may be composed of a copper alloy containing one or two selected from Zn, Sn, Ni, Al, Si and Mn in a total of 0.1 mass % or more. above, and the Cu content is set to 45% by mass or more.

By including a total of 0.1 mass % or more selected from Zn, Sn, Ni, Al, Si and Mn in one or two or more, the uniformity or durability of the copper layer 313 during film formation can be greatly improved Wait. In addition, in order to fully exhibit this effect, the total content of one or more selected from Zn, Sn, Ni, Al, Si, and Mn is more preferably 0.2 mass % or more, and further preferably 0.3 mass % above.

[0160] Also, when the Cu content is 45% by mass or more, the antibacterial properties based on Cu can be sufficiently ensured. In addition, the lower limit of the Cu content is more preferably 47.5 mass % or more, and further preferably 50 mass % or more.

[0161] Furthermore, in the present embodiment, a Cu oxide film may be formed on the outermost surface of the copper layer 313. On the outermost surface of the copper layer 313, CuO and Cu₂Molar ratio of O CuO/Cu₂O is preferably CuO/Cu₂O<1. That is, it is preferable to use Cu₂The O content is more than the CuO content. by making Cu₂The O content is larger than the CuO content, and the antibacterial properties can be sufficiently ensured.

In addition, CuO and Cu₂Molar ratio of O CuO/Cu₂O is more preferably less than 0.9, more preferably less than 0.8.

Then, in the transparent antibacterial member 310 of the present embodiment, the transmittance to the light of wavelength 550nm in the lamination direction is preferably more than 5%.

In addition, in the transparent antibacterial component 310 of the present embodiment, the transmittance to the light of wavelength 550nm in the lamination direction is preferably more than 7%, more preferably more than 10%.

[0165] Below, the manufacturing method of the transparent antibacterial member 310 involved in this embodiment will be described.

[0166] First, the transparent substrate 311 on which the adhesive layer 315 is formed is prepared.

[0167] Next, the base layer 312 is formed on one surface (the surface opposite to the adhesive layer 315) of the transparent substrate 311 by a sputtering method. In this case, it is preferable to use a sputtering target having a composition corresponding to the oxide constituting the base layer 312 . For example, an oxide sputtering target formed of a metal oxide constituting the base layer 312 may be used, or a reactive sputtering method may be applied by introducing oxygen by using a metal sputtering target of a metal oxide constituting the base layer 312 . In addition, DC (direct current) sputtering, RF (high frequency) sputtering, MF (intermediate frequency) sputtering, AC (alternating current) sputtering, etc. are preferably selected and used in consideration of the conductivity of the sputtering target and the like.

[0168] Next, a copper layer 313 is formed on the formed base layer 312 by a sputtering method. At this time, a sputtering target having a composition corresponding to Cu or Cu alloy constituting the copper layer 313 is used. At this time, the sputtering conditions are appropriately adjusted so that the thickness of the copper layer 313 becomes a predetermined thickness. In addition, at the time of sputtering, the film thickness at the time of film formation for a predetermined time was measured with a step difference meter (DEKTAK-XT) to measure the sputtering rate, and the film formation time was adjusted according to the value to form a film until it reaches the target film thickness.

[0169] Through the above procedures, the transparent antibacterial member 310 of the present embodiment can be manufactured.

[0170] According to the transparent antibacterial member 310 of the present embodiment adopting the above-mentioned structure, since the copper layer 313 formed of copper or a copper alloy is disposed on the outermost surface layer, the antibacterial property is excellent.

In addition, on the transparent substrate 311, a base layer 312 composed of a metal oxide that transmits visible light is formed, and the thickness of the copper layer 313 is set to 35 nm or less, so the transmittance of visible light is excellent, and the transparent configuration can be visually recognized. The surfaces of various products of the antibacterial member 310 are excellent in appearance.

Then, although the thickness of the copper layer 313 is formed as thin as 35 nm or less, since the base layer 312 made of metal oxide is formed between the transparent substrate 311 and the copper layer 313, the copper layer 313 can be suppressed. Copper aggregates, and it is possible to suppress the occurrence of poor appearance.

In the present embodiment, when the transmittance to the light of wavelength 550nm in the lamination direction is more than 5%, the surface of the various products that configure this transparent antibacterial component 310 can therefore be fully visually recognized, and can be reliably Improve appearance.

[0174] Furthermore, in this embodiment, when the metal oxide constituting the base layer 312 contains a metal oxide selected from the group consisting of In oxide, Sn oxide, Zn oxide, Nb oxide, Ti oxide, Al oxide, and Ga oxide , W oxides, Mo oxides, Si oxides, Zr oxides, Ta oxides, y oxides, Ge oxides, Cu oxides, and Ag oxides, any one or two or more of them can be sufficiently ensured The visible light transmittance of the base layer 312 can be sufficiently visually recognized on the surfaces of various products on which the transparent antibacterial member 310 is arranged.

And, in the present embodiment, when the thickness of base layer 312 is set as below 50nm, can fully ensure the transmittance of the visible light of base layer 312, can fully visually identify the various configurations of this transparent antibacterial component 310 surface of the product.

Furthermore, in the present embodiment, when the copper layer 313 is composed of a copper alloy, and the copper alloy contains a total of 0.1 mass % or more selected from Zn, Sn, Ni, Al, Si and Mn one or both When the Cu content is 45 mass % or more, the antibacterial property can be sufficiently ensured, the durability of the copper layer 313 can be improved, and the occurrence of discoloration can be suppressed.

[0177] In this embodiment, when a Cu oxide film is formed on the surface layer of the copper layer 313, and CuO and Cu in the Cu oxide film₂Molar ratio of O CuO/Cu₂O is CuO/Cu₂When O<1, Cu₂The O content is more than the CuO content, and the antibacterial properties can be sufficiently ensured.

Also, in this embodiment, when the adhesive layer 315 is provided on the surface of the transparent substrate 311 on the opposite side to the base layer, the adhesive layer 315 can be easily used on the surfaces of various products The antibacterial component 310 is configured.

[0179] The embodiments of the present invention have been described above, but the present invention is not limited thereto, and changes can be appropriately made without departing from the technical idea of the present invention.

[0180] For example, in the present embodiment, the case where the adhesive layer is formed has been described as an example, but the adhesive layer may not be formed.

[0181] In addition, the copper or copper alloy constituting the copper layer is not limited to the copper or copper alloy described in the embodiment, and various copper alloys can be used. For example, a copper alloy in which Sn, Ni, Al, Pb, Mn, Si, P, etc. are added to brass mainly composed of Cu and Zn may be used. Also in this case, it is preferable to set the Cu content to 45 mass % or more.

Example

[First Embodiment]

[0184] Hereinafter, the results of confirmation experiments performed to confirm the effects of the present invention will be described.

[0185] The sputtering target used for forming the copper layer was produced by the procedure shown below.

First, a Cu raw material with a purity of 99.9 mass % or more and a purity of 99 mass % are weighed so as to have a predetermined composition.

% or more of metal raw materials are used as raw materials. Next, in a smelting furnace, the Cu raw material is smelted in a high vacuum or an inert gas atmosphere, and a predetermined content of the metal raw material is added to the obtained molten metal. After that, it is smelted in a vacuum or an inert gas atmosphere to produce a smelted cast ingot. After cold-rolling the obtained ingot, heat treatment for 2 hours at 600° C. is applied in the atmosphere, followed by machining to form a disk shape with a diameter of 152.4 mm and a thickness of 6 mm, and a copper layer is formed. sputtering target.

[0187] As the sputtering target used for forming the base layer, the sputtering targets described in Table 1 and Table 2, which were purchased from High Purity Chemical Co., Ltd. (High Touch Chemical Co., Ltd.), were used.

After these sputtering targets are welded on the back plate made of oxygen-free copper, this is installed in the DC magnetron sputtering device, and the DC magnetron sputtering device is exhausted to 5 × 10 using the vacuum exhaust device. -⁵After Pa or less, Ar gas was introduced to generate plasma between the cleaned substrates shown in Tables 1 and 2 arranged in parallel with the target and the above-mentioned target, thereby forming a base layer and a copper layer. The film-forming conditions of the base layer and the film-forming conditions of the copper layer are shown below.

Film-forming conditions of v base layer >>

Gas used: Ar+2 vol% oxygen

Air pressure: 0.67Pa

Sputtering power: DC 300W

Distance between target/substrate: 70mm

Film-forming conditions of v copper layer >>

Ultimate vacuum degree: 5*10 "⁵Below Pa

Gas used: Ar

Air pressure: 0.67Pa

Sputtering power: DC 200W

Distance between target/substrate: 70mm

[0200] For the antibacterial components obtained as described above, the following items were evaluated.

(Component composition of sputtering target for forming copper layer)

[0202] The sample for analysis was collected from the sputtering target on which the copper layer was formed, and the components were measured by ICP emission spectrometry. In addition, it was confirmed that the composition of the sputtering target for forming the copper layer and the copper layer to be formed match.

In addition, as the "other" composition in the table, Pb, Mg, Zr, Te, Cr, Fe, Co, P, etc. can be used.

(Film thickness measurement)

[0205] The thickness of the base layer and the copper layer was confirmed by observing the cross section of the base layer and the copper layer with a transmission electron microscope (TEM), and it was confirmed that the film was formed with the same thickness as the target value. In the production of a sample for TEM observation, for example, a cross section polisher (CP) or a focused ion beam (FIB) can be used.

(flexibility)

For the antibacterial component, under the environment of temperature 30 °C, relative humidity 90%, after keeping 24 hours, be 6mm with the radius of curvature, each carry out 100 bending tests alternately, observe the antibacterial component after the test, confirm peeling off And whether there is peeling (crack) inside.

Specifically, as shown in Figure 2A, the antibacterial component 110 is sandwiched between a pair of clamping bodies 120a erected on the seat 120b of the jig 120 for the bending test, as shown in Figure 2B and Figure 2c , perform 100 bends on the left and one on the right. In addition, the tip ends of the pair of holding bodies 120a are each formed in a cross-sectional arc shape with a curvature radius of 6 mm. That is, the test was performed by attaching the antibacterial member 110 to the tip of the clamp body 120a with a curvature radius of 6 mm.

For the presence or absence of cracks, five tests were performed, and the case where cracks were observed five times from the substrate side was "C", and the case where cracks were observed one to four times was "B", and none was observed. The case to the crack is "A".

(Evaluation of Antibacterial Activity)

[0211] Regarding the antibacterial activity, the antibacterial activity of copper and copper alloys formed on the surface of the sputtering target was evaluated as its characteristic.

The surface of the target used for sputtering was polished with sandpaper #1000 to expose the new surface, and then the surface oxidation state was adjusted to obtain a sample. As the reference material, a stainless steel plate without copper content was used. Then, according to JIS Z 2801, predetermined Staphylococcus aureus was inoculated on the surface of each test piece, and the number of viable cells (cfu) after 30 minutes was quantified. It was carried out with N=3, and the quantitative viable count was used to obtain the reduction rate of bacteria obtained from the following formula. When the reduction rate of bacteria exceeded 2, it was evaluated as "A", and when the reduction rate of bacteria exceeded 0 and less than 2 It was evaluated as "B" when the reduction rate of bacteria was 0 or less, and it was evaluated as "C".

Bacterial reduction rate=-log (viable bacterial count (cfu) of test piece after two hours/initial inoculated bacterial count (cfu))

(Existence form of oxide on surface)

[0215] A sample equivalent to that of the sputtering target was prepared, heat-treated in a redox atmosphere, and the morphology of the oxide present on the surface was changed as shown in Table 3. Thus, the surface oxides of CuO and Cu are changed₂The ratio of O to determine its antibacterial activity. The state of the surface oxide was determined by XPS (X-ray Photoelectron Spectroscopy) analysis.

[Table 1]

[0217]

[0218]

<td colspan="2" rowspan="3"></td><td colspan="2">substrate</td><td colspan="2">basal layer</td><td colspan="9">copper layer</td><td colspan="2">Comment on overseas Chinese</td>

<td rowspan="2">material</td><td rowspan="2">Thickness (μ in)</td><td rowspan="2">material</td><td rowspan="2">Thickness (nm)</td><td colspan="8">Composition (mass %)</td><td rowspan="2">Thickness Cnm)</td><td rowspan="2">bendability</td><td rowspan="2">seedling resistance</td>

<td>Cu</td><td>Zn</td><td>Sn</td><td>Ni</td><td>Si</td><td>Al</td><td>Mn</td><td>other</td>

<td></td><td>A1</td><td>PET</td><td>50</td><td>[n-Sn oxide</td><td>L5</td><td>90</td><td>10</td><td></td><td></td><td></td><td>-</td><td></td><td></td><td>120</td><td>A</td><td>A</td>

<td></td><td>Λ2</td><td>PET</td><td>100</td><td>Sn oxide</td><td>L5</td><td>70</td><td>30</td><td></td><td></td><td></td><td>-</td><td></td><td></td><td>160</td><td>Λ</td><td>Λ</td>

<td></td><td>A3</td><td>PET</td><td>150</td><td>Zn oxide</td><td>20</td><td>75.9</td><td>21</td><td>-</td><td>-</td><td>3</td><td>-</td><td>-</td><td>0J</td><td>160</td><td>A</td><td>A</td>

<td></td><td>A4</td><td>PET</td><td>200</td><td>Nb oxide</td><td>30</td><td>54</td><td>35</td><td>-</td><td>1 I</td><td>-</td><td>-</td><td>-</td><td>-</td><td>240</td><td>A</td><td>A</td>

<td></td><td>A5</td><td>PET</td><td>200</td><td>Ti oxidized intestine</td><td>45</td><td>70</td><td>27</td><td>1</td><td>2</td><td>-</td><td>-</td><td>-</td><td>-</td><td>ιοαο</td><td>A</td><td>A</td>

<td></td><td>A6</td><td>PP</td><td>50</td><td>Al oxide</td><td>35</td><td>90</td><td>-</td><td>-</td><td>10</td><td>-</td><td>-</td><td>-</td><td>-</td><td>420</td><td>A</td><td>A</td>

<td></td><td>A7</td><td>PP</td><td>100</td><td>Ga oxide</td><td>L0</td><td>75</td><td>25</td><td></td><td></td><td></td><td>-</td><td></td><td></td><td>180</td><td>A</td><td>A</td>

<td rowspan="2">Book</td><td>A8</td><td>FP</td><td>150</td><td>Si oxide</td><td>20</td><td>99.8</td><td></td><td></td><td>-</td><td></td><td></td><td></td><td>0.2</td><td>320</td><td>A</td><td>A</td>

<td>A9</td><td>PP</td><td>300</td><td>Mo oxide</td><td>5</td><td>54</td><td>35</td><td>-</td><td>11</td><td>-</td><td>-</td><td>-</td><td>-</td><td>420</td><td>B</td><td>A</td>

<td>send</td><td>A10</td><td>PP</td><td>500</td><td>Si oxide</td><td>500</td><td>95</td><td></td><td></td><td>-</td><td></td><td></td><td></td><td>5</td><td>180</td><td>B</td><td>A</td>

<td rowspan="2">clear example</td><td>A11</td><td>PO</td><td>50</td><td>Zr oxide</td><td>20</td><td>65</td><td>35</td><td></td><td></td><td></td><td>-</td><td></td><td></td><td>160</td><td>A</td><td>A</td>

<td>A12</td><td>PO</td><td>100</td><td>Ta oxide</td><td>45</td><td>80</td><td>-</td><td>-</td><td>20</td><td>-</td><td>-</td><td>-</td><td>-</td><td>4500</td><td>A</td><td>A</td>

<td></td><td>A13</td><td>PO</td><td>150</td><td>Y oxide</td><td>35</td><td>90</td><td>-</td><td>10</td><td>-</td><td>-</td><td>-</td><td>-</td><td>-</td><td>180</td><td>A</td><td>A</td>

<td></td><td>A14</td><td>PO</td><td>150</td><td>Ge oxide</td><td>5</td><td>62</td><td>31</td><td>-</td><td>-</td><td>L</td><td>3</td><td>3</td><td>-</td><td>280</td><td>B</td><td>A</td>

<td></td><td>Λ15</td><td>PO</td><td>200</td><td>Cu oxide</td><td>30</td><td>55</td><td>34</td><td>-</td><td>11</td><td>-</td><td>-</td><td>-</td><td>-</td><td>120</td><td>A</td><td>A</td>

<td></td><td>Λ16</td><td>PVC</td><td>50</td><td>Ag oxide</td><td>45</td><td>80</td><td>-</td><td>-</td><td>20</td><td>-</td><td>-</td><td>-</td><td>-</td><td>100</td><td>A</td><td>A</td>

<td></td><td>Λ17</td><td>PVC</td><td>100</td><td>In oxide</td><td>40</td><td>85</td><td>-</td><td>-</td><td>15</td><td>-</td><td>-</td><td>-</td><td>-</td><td>60</td><td>A</td><td>A</td>

<td></td><td>A18</td><td>PVC</td><td>150</td><td>Zn oxide</td><td>50</td><td>100</td><td></td><td></td><td></td><td>-</td><td></td><td></td><td></td><td>120</td><td>A</td><td>A</td>

<td></td><td>AI9</td><td>PVC</td><td>200</td><td>A1 oxide</td><td>50</td><td>4g</td><td>36</td><td>-</td><td>9</td><td>-</td><td>-</td><td>6</td><td>-</td><td></td><td>A</td><td>A</td>

<td></td><td>A20</td><td>PVC</td><td>200</td><td>Ga oxide</td><td>35</td><td>99.7</td><td></td><td></td><td>-</td><td></td><td></td><td></td><td>0,3</td><td>300</td><td>A</td><td>Λ</td>

[Table 2]

[0219]

[0220]

[0221]

<td rowspan="3"></td><td colspan="2">substrate</td><td colspan="2">basal layer</td><td colspan="9">copper layer</td><td colspan="2">Evaluation</td>

<td rowspan="2">material</td><td rowspan="2">Thickness (μm)</td><td rowspan="2">material</td><td rowspan="2">Thickness (ηιτι)</td><td colspan="8">Composition (mass %)</td><td rowspan="2">Shore degree (nm)</td><td rowspan="2">bendability</td><td rowspan="2">Antibacterial</td>

<td>Cu</td><td>Zn</td><td>Sn</td><td>Νί</td><td>Si</td><td>Al</td><td>Mn</td><td>other</td>

<td>Λ21</td><td>acrylic acid</td><td>50</td><td>Cu oxide</td><td>40</td><td>85</td><td>15</td><td></td><td></td><td></td><td>-</td><td></td><td></td><td>360</td><td>Λ</td><td>A</td>

<td>A22</td><td>Propionate</td><td>100</td><td>Nb oxide</td><td>35</td><td>99</td><td>-</td><td>-</td><td>-</td><td>-</td><td>1</td><td>-</td><td>-</td><td>160</td><td>A</td><td>A</td>

<td>A23</td><td>Propionic acid</td><td>150</td><td>Ti oxide</td><td>15</td><td>95</td><td>-</td><td>5</td><td>-</td><td>-</td><td>-</td><td>-</td><td>-</td><td>2000</td><td>A</td><td>A</td>

<td>Ben A24</td><td>acrylic acid</td><td>150</td><td>hl oxide</td><td>50</td><td>85</td><td>-</td><td>-</td><td>15</td><td>-</td><td>-</td><td>-</td><td>-</td><td>40</td><td>A</td><td>A</td>

<td>Send A25</td><td>Propionate</td><td>300</td><td>Cu oxide</td><td>10</td><td>90</td><td>5</td><td>5</td><td>-</td><td>-</td><td>-</td><td>-</td><td>-</td><td>140</td><td>B</td><td>A</td>

<td>Ming A26</td><td>Polyimide</td><td>50</td><td>Sn oxidizes I</td><td>200</td><td>60</td><td>-</td><td>-</td><td>40</td><td>-</td><td>-</td><td>-</td><td>-</td><td>360</td><td>A</td><td>A</td>

<td>Example A27</td><td>Polyimide</td><td>150</td><td>In oxide</td><td>35</td><td>95</td><td>5</td><td></td><td></td><td></td><td>-</td><td></td><td></td><td>180</td><td>A</td><td>A</td>

<td></td><td>Polyimide</td><td>150</td><td>Zn oxide</td><td>40</td><td>inn</td><td></td><td></td><td></td><td>-</td><td></td><td></td><td></td><td>220</td><td>A</td><td>A</td>

<td>A29</td><td>Polyimide</td><td>150</td><td>W oxide</td><td>10</td><td>54</td><td>34</td><td>-</td><td>L2</td><td>-</td><td>-</td><td>-</td><td>-</td><td>80</td><td>A</td><td>A</td>

<td>A30</td><td>Polyimide</td><td>200</td><td>Si oxide</td><td>20</td><td>90</td><td>-</td><td>-</td><td>L0</td><td>-</td><td>-</td><td>-</td><td>-</td><td>180</td><td>A</td><td>A</td>

<td>Comparative example AI</td><td>PET</td><td>200</td><td>-</td><td>-</td><td>100</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>1000</td><td>C</td><td>A</td>

[table 3]

<td colspan="2" rowspan="3"></td><td colspan="2">substrate</td><td colspan="2">basal layer</td><td colspan="9">copper layer</td><td colspan="2">Surface XPS Analysis</td>

<td rowspan="2">material</td><td rowspan="2">Thickness (μm)</td><td rowspan="2">material</td><td rowspan="2">Thickness (nm)</td><td colspan="8">Composition (mass %)</td><td rowspan="2">Thickness (nm)</td><td rowspan="2">CuO/Cu₂O</td><td rowspan="2">Antibacterial</td>

<td>Cu</td><td>Zn</td><td>Sn</td><td>Ni</td><td>Si</td><td>Al</td><td>Mn</td><td>other</td>

<td rowspan="2">Example of the present invention</td><td>A28</td><td>polyimide</td><td>150</td><td>Zn oxide</td><td>40</td><td>100</td><td></td><td></td><td></td><td>-</td><td></td><td></td><td></td><td>220</td><td>&lt;1</td><td>A</td>

<td>A31</td><td>Polyimide</td><td>150</td><td>Zn oxide</td><td>40</td><td>100</td><td></td><td></td><td></td><td>-</td><td></td><td></td><td></td><td>220</td><td>2</td><td>B</td>

Comparative example in which a copper layer with a thickness of 1000 nm was directly formed on a substrate (PET resin substrate) without forming a base layer

In A1, it is presumed that the flexibility is C because the moisture from the substrate moves to the copper layer side, thereby reducing the adhesiveness between the substrate and the copper layer.

On the other hand, in Examples A1-A30 of the present invention in which a base layer formed of a metal oxide was formed between a substrate formed of a flexible resin material and a copper layer, the flexibility was "A to B and, In the copper layers of the compositions shown in Tables 1 and 2, the reduction rate of bacteria exceeded 2, and was evaluated as "A".

Furthermore, as shown in Table 3, in Example A28 of the present invention in which the molar ratio CuO/CLO of CuO to CLO in the Cu oxide film formed on the surface layer of the copper layer was less than 1, compared with the Cu oxide film in the Cu oxide film In Example A31 of the present invention, in which the molar ratio CuO/CLO of CuO and Clo was 1 or more, it was confirmed that the antibacterial property was improved.

[0225] Confirmed from the above content, according to the present invention, a kind of antibacterial property and excellent flexibility can be provided, and the antibacterial component that can be used stably can be provided.

[Second Embodiment]

[0227] Hereinafter, the results of confirmation experiments performed in order to confirm the effects of the present invention will be described.

[0228] The sputtering target used for forming the copper layer was produced by the procedure shown below.

[0229] First, a Cu raw material with a purity of 99.9 mass % or more and a metal raw material with a purity of 99 mass % or more are weighed as raw materials so as to have a predetermined composition. Next, in a smelting furnace, the Cu raw material is smelted in a high vacuum or an inert gas atmosphere, and a predetermined content of the metal raw material is added to the obtained molten metal. After that, it is smelted in a vacuum or an inert gas atmosphere to produce a smelted ingot. After cold-rolling the obtained ingot, heat treatment is performed, for example, at 600° C. for 2 hours in the atmosphere, followed by machining to produce a disc shape having a diameter of 152.4 mm and a thickness of 6 mm to produce copper. layer of sputtering target.

[0230] As the sputtering target used for forming the base layer, the sputtering targets described in Tables 4 and 5 purchased from High Purity Chemical Co., Ltd. were used.

After these sputtering targets are welded on the back plate made of oxygen-free copper, this is installed in the DC magnetron sputtering device, and the DC magnetron sputtering device is exhausted to 5 × 10 using the vacuum exhaust device. -⁵After Pa or less, Ar gas was introduced to generate plasma between the cleaned substrates shown in Tables 4 and 5 arranged in parallel with the target and the above-mentioned target, thereby forming a base layer and a copper layer. The film-forming conditions of the base layer and the film-forming conditions of the copper layer are shown below.

The film forming conditions of v base layer &gt;&gt;

Gas used: Ar+2 vol% oxygen

Air pressure: 0.67Pa

Sputtering power: DC 300W

Distance between target/substrate: 70mm

Film-forming conditions of v copper layer &gt;&gt;

Ultimate vacuum degree: 5*10 "⁵Below Pa

Gas used: Ar

Air pressure: 0.67Pa

Sputtering power: DC 200W

Distance between target/substrate: 70mm

[0243] For the antibacterial parts obtained as described above, the following items were evaluated.

(Component composition of sputtering target for forming copper layer)

[0245] The sample for analysis was collected from the sputtering target on which the copper layer was formed, and the components were measured by ICP emission spectrometry. In addition, it was confirmed that the composition of the sputtering target for forming the copper layer and the copper layer to be formed match.

In addition, as the "other" composition in the table, Pb, Mg, Zr, Te, Cr, Fe, Co, P, etc. can be used.

(Film Thickness Measurement)

[0248] The thickness of the base layer and the copper layer was confirmed by observing the cross section of the base layer and the copper layer with a transmission electron microscope (TEM), and it was confirmed that the film was formed with the same thickness as the target value. In the production of a sample for TEM observation, for example, a cross section polisher (CP) or a focused ion beam (FIB) can be used.

(durability test)

For the antibacterial component, as a constant temperature and humidity test, it was kept for 250 hours under an environment of temperature 60° C. and humidity 90%, and the color tone change on the appearance of the surface after the test was confirmed. The color tone change was judged with the naked eye. When the discolored part in the 40 mm×40 mm size sample covered the entire surface, it was evaluated as "D", when the discolored part was half or less, it was evaluated as "B", and when no discolored part was found, it was evaluated as "A".

(Evaluation of Antibacterial Activity)

[0252] Regarding the antibacterial activity, the antibacterial activity of copper and copper alloys formed on the surface of the sputtering target was evaluated as its characteristic.

[0253] The surface of the target used for sputtering was polished with sandpaper #1000 to expose the new surface, and then the surface oxidation state was adjusted to obtain a sample. Then, according to JIS Z 2801, predetermined Staphylococcus aureus was inoculated on the surface of each test piece, and the number of viable cells (cfu) after two hours was quantified. N=3, and using the quantitative number of viable cells, the reduction rate of bacteria obtained from the following formula was obtained. When the reduction rate of bacteria exceeded 2, it was evaluated as "A", and when the reduction rate of bacteria exceeded 0 and less than 2 It was evaluated as "B" when the reduction rate of bacteria was 0 or less, and it was evaluated as "C".

[0254] Bacteria reduction rate=Tog (viable bacterial count (cfu) of test piece after two hours/initial inoculated bacterial count (cfu)) [0255] (existing form of oxide on the surface)

[0256] A sample equivalent to that of the sputtering target was prepared, heat-treated in a redox atmosphere, and the morphology of the oxide present on the surface was changed as shown in Table 6. Thus, the ratio of CuO to C%o of the surface oxide was changed, and the antibacterial activity was measured. The state of the surface oxide was determined by XPS analysis.

[Table 4]

<td rowspan="3"></td><td colspan="2">substrate</td><td colspan="2">basal layer</td><td colspan="9">copper layer</td><td colspan="2">Evaluation</td>

<td rowspan="2">material</td><td rowspan="2">Thickness (U m)</td><td rowspan="2">material</td><td rowspan="2">Thickness (nm)</td><td colspan="8">Composition (mass %)</td><td rowspan="2">Thickness (nm)</td><td rowspan="2">Durability</td><td rowspan="2">Antibacterial</td>

<td>Cu</td><td>Zn</td><td>Sn</td><td>Ni</td><td>Si</td><td>Al</td><td>Mn</td><td>other</td>

<td>B1</td><td>PET</td><td>50</td><td>In-Sn oxide</td><td>40</td><td>90</td><td>10</td><td></td><td></td><td></td><td>-</td><td></td><td></td><td>12</td><td>B</td><td>A</td>

<td>B2</td><td>PET</td><td>100</td><td>Sn oxide</td><td>25</td><td>70</td><td>3 n</td><td></td><td></td><td></td><td>-</td><td></td><td></td><td>24</td><td>A</td><td>A</td>

<td>B3</td><td>?ET</td><td>300</td><td>Zn oxide</td><td>20</td><td>75.9</td><td>21</td><td>-</td><td>-</td><td>3</td><td>-</td><td>-</td><td>0J</td><td>24</td><td>A</td><td>A</td>

<td>B4</td><td>PP</td><td>50</td><td>Nb oxide</td><td>30</td><td>54</td><td>35</td><td>-</td><td>11</td><td>-</td><td></td><td>-</td><td>-</td><td>4</td><td>B</td><td>A</td>

<td>B5</td><td>PP</td><td>100</td><td>Ti oxide</td><td>50</td><td>70</td><td>27</td><td>1</td><td>2</td><td>-</td><td>-</td><td>-</td><td>-</td><td>27</td><td>A</td><td>A</td>

<td>B6</td><td>PP</td><td>300</td><td>A1 oxide</td><td>45</td><td>90</td><td>-</td><td>-</td><td>10</td><td>-</td><td>-</td><td>-</td><td>-</td><td>L3</td><td>A</td><td>A</td>

<td>B7</td><td>PO</td><td>50</td><td>Ga oxide</td><td>15</td><td>75</td><td>25</td><td></td><td></td><td></td><td>-</td><td></td><td></td><td>7</td><td>B</td><td>A</td>

<td>B8</td><td>PO</td><td>100</td><td>W oxide</td><td>75</td><td>99.8</td><td></td><td></td><td>-</td><td></td><td></td><td></td><td>ON</td><td>27</td><td>Λ</td><td>Λ</td>

<td>Ben B9</td><td>PO</td><td>300</td><td>Mo oxide</td><td>15</td><td>54</td><td>35</td><td>-</td><td>1 1</td><td>-</td><td>-</td><td>-</td><td>-</td><td>11</td><td>B</td><td>A</td>

<td>send BLO</td><td>PVC</td><td>50</td><td>Si oxide</td><td>15</td><td>95</td><td></td><td></td><td>-</td><td></td><td></td><td></td><td>5</td><td>24</td><td>A</td><td>A</td>

<td>Ming B 11</td><td>PVC</td><td>100</td><td>Zr oxide</td><td>20</td><td>65</td><td>35</td><td></td><td></td><td></td><td>-</td><td></td><td></td><td>9</td><td>B</td><td>A</td>

<td>Example B12</td><td>PVC</td><td>300</td><td>Ta oxide</td><td>15</td><td>80</td><td>-</td><td>-</td><td>20</td><td>-</td><td>-</td><td>-</td><td>-</td><td>21</td><td>A</td><td>A</td>

<td>BL3</td><td>acrylic acid</td><td>50</td><td>Y oxide</td><td>6</td><td>90</td><td>-</td><td>10</td><td>-</td><td>-</td><td>-</td><td>-</td><td>-</td><td>L7</td><td>A</td><td>A</td>

<td>B14</td><td>acrylic acid</td><td>inn</td><td>Ge oxide</td><td>50</td><td>62</td><td>31</td><td>-</td><td>-</td><td>[</td><td>3</td><td>3</td><td>-</td><td>24</td><td>A</td><td>A</td>

<td>BL5</td><td>acrylic acid</td><td>300</td><td>Cu oxygenate</td><td>50</td><td>40</td><td>35</td><td>-</td><td>13</td><td>-</td><td>-</td><td>-</td><td>6</td><td>L5</td><td>A</td><td>A</td>

<td>BL6</td><td>Polyimide</td><td>50</td><td>Ag oxidized intestine</td><td>45</td><td>80</td><td>-</td><td>-</td><td>20</td><td>-</td><td>-</td><td>-</td><td>-</td><td>8</td><td>B</td><td>A</td>

<td>B17</td><td>Polyimide</td><td>100</td><td>E oxide</td><td>40</td><td>X5</td><td>-</td><td>-</td><td>15</td><td>-</td><td>-</td><td>-</td><td>-</td><td>26</td><td>A</td><td>A</td>

<td>BL8</td><td>Polyimide</td><td>300</td><td>Zn oxide</td><td>45</td><td>100</td><td></td><td></td><td></td><td>-</td><td></td><td></td><td></td><td>6</td><td>B</td><td>A</td>

<td>BL9</td><td>Glass</td><td>100</td><td>A1 oxide</td><td>50</td><td>49</td><td>36</td><td>-</td><td>9</td><td>-</td><td>-</td><td>6</td><td>-</td><td>26</td><td>Λ</td><td>A</td>

<td>B20</td><td>Glass</td><td>500</td><td>Ga oxide</td><td>40</td><td>99.7</td><td></td><td></td><td>-</td><td></td><td></td><td></td><td>S3</td><td>21</td><td>A</td><td>A</td>

[Table 5]

<td rowspan="3"></td><td colspan="2">substrate</td><td colspan="2">basal layer</td><td colspan="9">copper layer</td><td colspan="2"></td>

<td rowspan="2">material</td><td rowspan="2">Sharpness (μm)</td><td rowspan="2">material</td><td rowspan="2">Thickness Cnm)</td><td colspan="8">Composition (mass %)</td><td rowspan="2">Thickness (nm)</td><td rowspan="2">Durability</td><td rowspan="2">Antibacterial</td>

<td>Cn</td><td>Zn</td><td>Sn</td><td>Ni</td><td>Si</td><td>Al</td><td>Mn</td><td>other</td>

<td>B2L</td><td>Propionate</td><td>1000</td><td>Cu oxide</td><td>L5</td><td>S5</td><td>15</td><td></td><td></td><td></td><td>-</td><td></td><td></td><td>9</td><td>B</td><td>Λ</td>

<td>B22</td><td>Propionate</td><td>50</td><td>Nb oxide</td><td>50</td><td>99</td><td>-</td><td>-</td><td>-</td><td>-</td><td>1</td><td>-</td><td>-</td><td>11</td><td>B</td><td>A</td>

<td>B23</td><td>Acrylic acid</td><td>100</td><td>Ti oxide</td><td>40</td><td>95</td><td>-</td><td>5</td><td>-</td><td>-</td><td>-</td><td>-</td><td>-</td><td>IL</td><td>A</td><td>Λ</td>

<td>Ben B24</td><td>Propionate</td><td>500</td><td>In oxide</td><td>9</td><td>85</td><td>-</td><td>-</td><td>15</td><td>-</td><td>-</td><td>-</td><td>-</td><td>7</td><td>B</td><td>A</td>

<td>send B25</td><td>Propionate</td><td>100</td><td>Cu oxide</td><td>20</td><td>90</td><td>5</td><td>5</td><td>-</td><td>-</td><td>-</td><td>-</td><td>-</td><td>17</td><td>A</td><td>Λ</td>

<td>Ming B26</td><td>glass width</td><td>500</td><td>Sn oxide</td><td>30</td><td>60</td><td>-</td><td>-</td><td>40</td><td>-</td><td>-</td><td>-</td><td>-</td><td>8</td><td>B</td><td>Λ</td>

<td>Example B27</td><td>broken glass</td><td>1000</td><td>In oxide</td><td>40</td><td>95</td><td>5</td><td></td><td></td><td></td><td>-</td><td></td><td></td><td>15</td><td>A</td><td>A</td>

<td>B28</td><td>Glass</td><td>100</td><td>Zn oxide</td><td>50</td><td>L00</td><td></td><td></td><td></td><td>-</td><td></td><td></td><td></td><td>L6</td><td>B</td><td>A</td>

<td>B29</td><td>Glass</td><td>500</td><td>W oxide</td><td>45</td><td>54</td><td>34</td><td>-</td><td>12</td><td>-</td><td>-</td><td>-</td><td>-</td><td>18</td><td>A</td><td>A</td>

<td>B30</td><td>broken glass</td><td>ιοοΰ</td><td>Si oxide</td><td>35</td><td>90</td><td>-</td><td>-</td><td>10</td><td>-</td><td>-</td><td>-</td><td>-</td><td>9</td><td>B</td><td>Λ</td>

<td>Comparative Example B1</td><td>Po Li</td><td>1000</td><td>-</td><td>-</td><td>L00</td><td></td><td></td><td></td><td>-</td><td></td><td></td><td></td><td>LO</td><td>D</td><td>Λ</td>

[Table 6]

<td colspan="2" rowspan="3"></td><td colspan="2">transparent substrate</td><td colspan="2">basal layer</td><td colspan="9">copper layer</td><td>Surface XPS Analysis</td><td></td>

<td rowspan="2">material</td><td rowspan="2">Thickness (H m)</td><td rowspan="2">material</td><td rowspan="2">Thickness (nm)</td><td colspan="8">Composition (mass %)</td><td rowspan="2">Thickness (nm)</td><td rowspan="2">CuO/Cu₂O</td><td rowspan="2">Antibacterial</td>

<td>Cu</td><td>Zn</td><td>Sn</td><td>Ni</td><td>Si</td><td>Al</td><td>Mn</td><td>other</td>

<td rowspan="2">Example of the present invention</td><td>Β28</td><td>Glass</td><td>100</td><td>Zn oxide</td><td>50</td><td>100</td><td></td><td></td><td></td><td>-</td><td></td><td></td><td></td><td>16</td><td>&lt;1</td><td>Λ.</td>

<td>Β31</td><td>Glass</td><td>100</td><td>Zn oxide</td><td>50</td><td>100</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>16</td><td>2</td><td>Beta</td>

[0263] In Comparative Example B1 in which the base layer was not formed and a copper layer with a thickness of 10 nm was directly formed on the substrate (glass substrate), the durability was "D". It is presumed that the occurrence of aggregation of the copper layer could not be suppressed.

[0264] On the other hand, in Examples B1-B30 of the present invention in which a base layer formed of a metal oxide was formed between the substrate and the copper layer, and the thickness of the copper layer was 30 nm or less, the durability was excellent.

[0265] And, in the copper layer of the composition shown in the table, the reduction rate of bacteria is more than 2, are all evaluated as "A".

Furthermore, as shown in Table 6, in Example B28 of the present invention in which the molar ratio CuO/CLO of CuO and CLO in the Cu oxide film formed on the surface layer of the copper layer was less than 1, compared with the CuO in the Cu oxide film In Example B31 of the present invention, in which the molar ratio CuO/CLO of CuO and Clo was 1 or more, the improvement of the antibacterial property was confirmed.

[0267] Confirmed from the above content, according to the present invention example, a kind of low cost and excellent antibacterial property can be provided, and the antibacterial part with excellent durability.

[Third Embodiment]

[0269] Hereinafter, the results of confirmation experiments performed in order to confirm the effects of the present invention will be described.

[0270] The sputtering target used for forming the copper layer was produced by the procedure shown below.

First, a Cu raw material having a purity of 99.9 mass % or more and a purity of 99 mass % are weighed so as to have a predetermined composition.

% or more of metal raw materials are used as raw materials. Next, in a smelting furnace, the Cu raw material is smelted in a high vacuum or an inert gas atmosphere, and a predetermined content of the metal raw material is added to the obtained molten metal. After that, it is smelted in a vacuum or an inert gas atmosphere to produce a smelted ingot. After cold-rolling the obtained ingot, heat treatment is performed, for example, at 600° C. for 2 hours in the atmosphere, and then by machining, it is formed into a disk shape having a size of 152.4 mm in diameter and 6 mm in thickness, and copper is formed. layer of sputtering target.

[0272] As the sputtering target used for forming the base layer, the sputtering targets described in Tables 7 and 8, which were purchased from High Purity Chemical Co., Ltd., were used.

After these sputtering targets are welded on the back plate made of oxygen-free copper, this is installed in a DC magnetron sputtering device, and the DC magnetron sputtering device is exhausted to 5 × 10 using a vacuum exhaust device. -⁵After Pa or less, Ar gas was introduced to generate plasma between the cleaned transparent substrates shown in Tables 7 and 8 arranged in parallel with the target and the target, thereby forming a base layer and a copper layer. The film-forming conditions of the base layer and the film-forming conditions of the copper layer are shown below.

The film-forming conditions of v base layer &gt;&gt;

Gas used: Ar+2 vol% oxygen

Air pressure: 0.67Pa

Sputtering power: DC 300W

Distance between target/substrate: 70mm

Film-forming conditions of v copper layer &gt;&gt;

[0280] Ultimate vacuum: 5×10 "⁵Below Pa

Gas used: Ar

Air pressure: 0.67Pa

Sputtering power: DC 200W

Distance between target/substrate: 70mm

[0285] For the transparent antibacterial parts obtained as described above, the following items were evaluated.

(Component composition of sputtering target for forming copper layer)

[0287] The sample for analysis was collected from the sputtering target on which the copper layer was formed, and the components were measured by ICP emission spectrometry. In addition, it was confirmed that the composition of the sputtering target for forming the copper layer and the copper layer to be formed match.

In addition, as "other" composition in the table, can use Pb, Mg, Zr, Te, Cr, Fe, Co etc.

(Film Thickness Measurement)

[0290] The thickness of the base layer and the copper layer was confirmed by observing the cross section of the base layer and the copper layer with a transmission electron microscope (TEM), and it was confirmed that the film was formed with the same thickness as the target value. In the production of a sample for TEM observation, for example, a cross section polisher (CP) or a focused ion beam (FIB) can be used.

(transmittance)

[0292] The transmittance of the lamination direction of the transparent antibacterial component is measured using a spectrophotometer (U-4100 of Hitachi High-tech Co., Ltd. The average value of transmittance from wavelength 530nm to 550nm is described in the table. In addition, at the time of measurement, since the glass substrate was used as a measurement base line, the value described in the table is the relative transmittance when the transmittance of the glass substrate is taken as 100.

(durability test)

[0294] For the transparent antibacterial component, as a constant temperature and humidity test, the temperature was kept at 60° C. and a humidity of 90% for 250 hours, and the change in color tone on the appearance of the surface after the test was confirmed. The color tone change was judged with the naked eye. when

In a sample with a size of 40 mm × 40 mm, the discolored part was evaluated as "D", when the discolored part was more than half, it was evaluated as "C", when the discolored part was less than half, it was evaluated as "B", and when no discoloration was observed The department was rated as "A".

(Evaluation of antibacterial activity)

[0296] Regarding the antibacterial activity, the antibacterial activity of copper and copper alloys formed on the sputtering target on the surface was evaluated as its characteristic.

[0297] The surface of the target used for sputtering was ground with sandpaper #1000 to expose the new surface, and used as a sample. Then, according to JIS Z 2801, predetermined Staphylococcus aureus was inoculated on the surface of each test piece, and the number of viable cells (cfu) after two hours was quantified. Implemented with N=3, using the quantitative number of viable cells, the reduction rate of bacteria obtained from the following formula was obtained. When the reduction rate of bacteria exceeded 2, it was evaluated as "A", and when the reduction rate of bacteria did not exceed 2, it was evaluated. as "C".

[0298] Bacteria reduction rate=Tog (viable bacterial count (cfu) of the test piece after two hours/initial inoculated bacterial count (cfu)) [0299] [Table 7]

<td colspan="2" rowspan="3"></td><td colspan="2">transparent substrate</td><td colspan="2">basal layer</td><td colspan="9">copper layer</td><td colspan="3">Evaluation</td>

<td rowspan="2">material</td><td rowspan="2">Thickness (μm)</td><td rowspan="2">material</td><td rowspan="2">Thickness Cnm)</td><td colspan="8">Composition (mass %)</td><td rowspan="2">Thickness (nm)</td><td rowspan="2">Transmittance (%)</td><td rowspan="2">Durability</td><td rowspan="2">Antibacterial</td>

<td>Cu</td><td>Zn</td><td>Sn</td><td>Ni</td><td>Si</td><td>Al</td><td>Mn</td><td>other</td>

<td></td><td>CI</td><td>PET</td><td>50</td><td>In-Sn oxide</td><td>20</td><td>90</td><td>10</td><td></td><td></td><td></td><td>-</td><td></td><td></td><td>5</td><td>4H</td><td>B</td><td>A</td>

<td></td><td>C2</td><td>PET</td><td>50</td><td>Sn oxide</td><td>35</td><td>70</td><td>30</td><td></td><td></td><td></td><td>-</td><td></td><td></td><td>10</td><td>56</td><td>B</td><td>A</td>

<td></td><td>C3</td><td>PET</td><td>100</td><td>Zn oxide</td><td>25</td><td>75.9</td><td>21</td><td>-</td><td>-</td><td>3</td><td>-</td><td>-</td><td>OJ</td><td>19</td><td>30</td><td>B</td><td>A</td>

<td></td><td>C4</td><td>PET</td><td>100</td><td>Nb oxide</td><td>45</td><td>54</td><td>35</td><td>-</td><td>11</td><td>-</td><td>-</td><td>-</td><td>-</td><td>6</td><td>4S</td><td>B</td><td>A</td>

<td></td><td>C5</td><td>PET</td><td>200</td><td>Ti oxide</td><td>35</td><td>70</td><td>27</td><td>1</td><td>2</td><td>-</td><td>-</td><td>-</td><td>-</td><td>12</td><td>38</td><td>A</td><td>A</td>

<td></td><td>C6</td><td>PP</td><td>5n</td><td>Al oxide</td><td>20</td><td>90</td><td>-</td><td>-</td><td>10</td><td>-</td><td>-</td><td>-</td><td>-</td><td>29</td><td>9</td><td>Λ</td><td>A</td>

<td></td><td>C7</td><td>PP</td><td>50</td><td>Ga oxide</td><td>20</td><td>75</td><td>25</td><td></td><td></td><td></td><td>-</td><td></td><td></td><td>10</td><td>61</td><td>B</td><td>A</td>

<td rowspan="3">this hair</td><td>C8</td><td>PP</td><td>100</td><td>w oxides</td><td>75</td><td>99.8</td><td></td><td></td><td>-</td><td></td><td></td><td></td><td>0.2</td><td>18</td><td>28</td><td>A</td><td>A</td>

<td>C9</td><td>PP</td><td>100</td><td>Mo oxide</td><td>15</td><td>54</td><td>35</td><td>-</td><td>11</td><td>-</td><td>-</td><td>-</td><td>-</td><td>18</td><td>44</td><td>A</td><td>A</td>

<td>C10</td><td>PP</td><td>200</td><td>Si oxide</td><td>40</td><td>95</td><td></td><td></td><td>-</td><td></td><td></td><td></td><td>5</td><td>5</td><td>65</td><td>C</td><td>A</td>

<td rowspan="2">clear example</td><td>Cl I</td><td>PO</td><td>50</td><td>7r oxide</td><td>4</td><td>65</td><td>35</td><td></td><td></td><td></td><td>-</td><td></td><td></td><td>13</td><td>57</td><td>A</td><td>A</td>

<td>CI2</td><td>PO</td><td>5n</td><td>Ta oxide</td><td>30</td><td>steep)</td><td>-</td><td>-</td><td></td><td>-</td><td>-</td><td>-</td><td>-</td><td>4</td><td>SO</td><td>B</td><td>Λ</td>

<td></td><td>C13</td><td>PO</td><td>wo</td><td>y oxide</td><td>60</td><td>90</td><td>-</td><td>10</td><td>-</td><td>-</td><td>-</td><td>-</td><td>-</td><td>14</td><td>35</td><td>B</td><td>Λ</td>

<td></td><td>C14</td><td>PO</td><td>100</td><td>Gu oxide</td><td>20</td><td>62</td><td>31</td><td>-</td><td>-</td><td>1</td><td>3</td><td>3</td><td>-</td><td>8</td><td>68</td><td>B</td><td>A</td>

<td></td><td>C15</td><td>PO</td><td>200</td><td>Cu oxide</td><td>45</td><td>55</td><td>34</td><td>-</td><td>1 1</td><td>-</td><td>-</td><td>-</td><td>-</td><td>20</td><td>26</td><td>A</td><td>A</td>

<td></td><td>C16</td><td>PVC</td><td>50</td><td>Ag oxide</td><td>5n</td><td>S0</td><td>-</td><td>-</td><td>20</td><td>-</td><td>-</td><td>-</td><td>-</td><td>12</td><td>9</td><td>B</td><td>A</td>

<td></td><td>C17</td><td>PVC</td><td>50</td><td>1n oxide</td><td>25</td><td>S5</td><td>-</td><td>-</td><td>15</td><td>-</td><td>-</td><td>-</td><td>-</td><td>20</td><td>IS</td><td>A</td><td>A</td>

<td></td><td>CIS</td><td>PVC</td><td>100</td><td>Zn oxide</td><td>20</td><td>100</td><td></td><td></td><td></td><td>-</td><td></td><td></td><td></td><td>34</td><td>6</td><td>A</td><td>A</td>

<td></td><td>C19</td><td>PVC</td><td>100</td><td>A1 oxide</td><td>40</td><td>49</td><td>36</td><td>-</td><td>9</td><td>-</td><td>-</td><td>6</td><td>-</td><td>15</td><td>43</td><td>A</td><td>A</td>

<td></td><td>C20</td><td>PVC</td><td>200</td><td>Ga oxide</td><td>50</td><td>99.7</td><td></td><td></td><td>-</td><td></td><td></td><td></td><td>0.3</td><td>14</td><td>53</td><td>B</td><td>Λ</td>

[0301] [Table 8]

<td colspan="2" rowspan="3"></td><td colspan="2">transparent substrate</td><td colspan="2">basal layer</td><td colspan="9">copper layer</td><td colspan="3">Evaluation</td>

<td rowspan="2">material</td><td rowspan="2">Thickness (μm)</td><td rowspan="2">material</td><td rowspan="2">Thickness (nm)</td><td colspan="8">Composition (mass %)</td><td rowspan="2">Thickness (nm)</td><td rowspan="2">Transmittance (%)</td><td rowspan="2">Durability</td><td rowspan="2">Antibacterial</td>

<td>Cu</td><td>Zn</td><td>Sn</td><td>Ni</td><td>Si</td><td>Al</td><td>Mn</td><td>other</td>

<td rowspan="10">Example of the present invention</td><td>C21</td><td>acrylic acid</td><td>50</td><td>Cu oxide</td><td>25</td><td>85</td><td>15</td><td></td><td></td><td></td><td>-</td><td></td><td></td><td>9</td><td>4S</td><td>B</td><td>A</td>

<td>C22</td><td>acrylic acid</td><td>50</td><td>Nb oxide</td><td>15</td><td>99</td><td>-</td><td>-</td><td>-</td><td>-</td><td>1</td><td>-</td><td>-</td><td>IL</td><td>45</td><td>B</td><td>A</td>

<td>C23</td><td>acrylic acid</td><td>100</td><td>Ti oxide</td><td>5</td><td>95</td><td>-</td><td>5</td><td></td><td></td><td>-</td><td></td><td></td><td>11</td><td>40</td><td>A</td><td>A</td>

<td>C24</td><td>propionic acid</td><td>100</td><td>In oxide</td><td>50</td><td>85</td><td>-</td><td>-</td><td>15</td><td>-</td><td>-</td><td>-</td><td>-</td><td>7</td><td>47</td><td>B</td><td>A</td>

<td>C25</td><td>acrylic acid</td><td>200</td><td>Cu oxide</td><td>25</td><td>90</td><td>5</td><td>5</td><td></td><td></td><td>-</td><td></td><td></td><td>17</td><td>32</td><td>A</td><td>A</td>

<td>C26</td><td>Glass</td><td>50</td><td>Sn oxide</td><td>50</td><td>6n</td><td>-</td><td>-</td><td>40</td><td>-</td><td>-</td><td>-</td><td>-</td><td>S</td><td>60</td><td>B</td><td>A</td>

<td>C27</td><td>Glass</td><td>5n</td><td>In oxide</td><td>20</td><td>95</td><td>5</td><td></td><td></td><td></td><td>-</td><td></td><td></td><td>15</td><td>3H</td><td>Λ</td><td>Λ</td>

<td>C28</td><td>broken glass</td><td>100</td><td>Zn oxide</td><td>25</td><td>100</td><td></td><td></td><td></td><td>-</td><td></td><td></td><td></td><td>16</td><td>46</td><td>B</td><td>A</td>

<td>C29</td><td>Glass</td><td>100</td><td>W oxide</td><td>15</td><td>54</td><td>34</td><td>-</td><td>12</td><td>-</td><td>-</td><td>-</td><td>-</td><td>18</td><td>33</td><td>Λ</td><td>Λ</td>

<td>C3O</td><td>Glass</td><td>200</td><td>Si oxide</td><td>30</td><td>90</td><td>-</td><td>-</td><td>10</td><td>-</td><td>-</td><td>-</td><td>-</td><td>9</td><td>57</td><td>B</td><td>A</td>

<td rowspan="2">Comparative example</td><td>C1</td><td>Quilt</td><td>50</td><td>-</td><td>-</td><td>100</td><td></td><td></td><td></td><td>-</td><td></td><td></td><td></td><td>10</td><td>63</td><td>D</td><td>A</td>

<td>C2</td><td>PET</td><td>200</td><td>In oxide</td><td>20</td><td>100</td><td></td><td></td><td></td><td>-</td><td></td><td></td><td></td><td>LOO</td><td>0</td><td>A</td><td>A</td>

[0303] In Comparative Example C1 in which a copper layer with a thickness of 10 nm was directly formed on a transparent substrate (glass substrate) without forming a base layer, the durability was "D". It is presumed that the occurrence of aggregation of the copper layer could not be suppressed.

[0304] In Comparative Example C2 in which a base layer formed of a metal oxide was formed between the transparent substrate (PET substrate) and the copper layer, and the copper layer was formed with a thickness of 100 nm, the transmittance was 0%. Presumably because: the thickness of the copper layer is too thick.

On the other hand, between the transparent substrate and the copper layer, a base layer formed of a metal oxide that transmits visible light is formed, and in Examples C1-C30 of the present invention in which the thickness of the copper layer is set to 20 nm or less, the transparent The over-rate is sufficiently high. In addition, durability is also excellent.

And, in the copper layer of the composition shown in the table, the reduction rate of bacteria all exceeded 2, and was evaluated as "A".

[0307] Confirmed from the above content, according to the present invention, a kind of excellent antibacterial property and visible light transmittance can be provided, and the generation of poor appearance can be suppressed, and the transparent antibacterial component that can be used stably.

Industrial Applicability

[0309] The present invention can provide an antibacterial member that is excellent in antibacterial properties and flexibility and can be used stably.

Symbol Description

110 antibacterial parts

[03 (2) 111 Substrate

112 base layer

H3 copper layer

115 Adhesive Layer

<td>[0316]</td><td>120</td><td>Jig for bending test</td>

<td>[0317]</td><td>120a</td><td>Clamping body</td>

<td>[0318]</td><td>120b</td><td>seat</td>

<td>[0319]</td><td>210</td><td>Antibacterial parts</td>

<td>[0320]</td><td>211</td><td>substrate</td>

<td>[0321]</td><td>212</td><td>basal layer</td>

<td>[0322]</td><td>213</td><td>copper layer</td>

<td>[0323]</td><td>215</td><td>adhesive layer</td>

<td>[0324]</td><td>310</td><td>Transparent Antimicrobial Parts</td>

<td>[0325]</td><td>311</td><td>transparent substrate</td>

<td>[0326]</td><td>312</td><td>basal layer</td>

313 copper layer

315 Adhesive Layer