Bioactive Coated Substrates

Abstract

A bioactive coated substrate comprises a base substrate, an indicator layer arranged on the base substrate, and a bioactive layer arranged on the indicator layer, wherein the indicator layer has a color different enough from that of the bioactive layer so that the bioactive layer can be visually perceived by a user when the bioactive layer is worn away.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims the benefit of U.S. Provisional Application Serial No. 63 / 122,240, filed on December 7, 2020, the disclosure of which is hereby incorporated by reference in its entirety. Technical Field

[0003] In at least one aspect, the present invention is directed to a coating system having bioactive properties formed by physical vapor deposition and / or related methods, particularly a copper-based antimicrobial PVD coating having a wear indicator. Background Art

[0004] Physical vapor deposition (PVD) is a technique for thin film formation or coating substrates. PVD involves the evaporation of a material, which then condenses on a surface to form a coating. PVD may result in the deposition of large particles, which are often considered defects. These large particles may be loosely bound to the coated layer. Mechanical methods can be used to remove these large particles, but removal leaves small holes, which are also often considered defects. For example, cathodic arc evaporation (CAE), a form of PVD involving a high current, low voltage arc on the surface of a cathode target, produces large particles. Because large particles and small holes are considered defects, great efforts are made to eliminate or reduce the size and number of large particles.

[0005] Coatings with bioactive properties can be used for various purposes. Bioactive materials refer to materials that have biological or physiological effects on organisms. For example, bioactive materials include materials that cause changes in the normal biological functions or physiological mechanisms of organisms. As used herein, bioactivity includes beneficial and harmful effects on microorganisms or changes in the normal functions of microorganisms. A common bioactive material is an antimicrobial substance. Antimicrobial coatings have many uses. Antimicrobial coatings usually inhibit the growth of microorganisms (like viruses, bacteria or fungal organisms) or kill them. A particularly relevant example includes preventing the spread of communicable diseases by using antimicrobial materials. Antimicrobial materials can also be used for sanitary purposes. The desire to prevent the spread of disease and enhance hygiene has led to significant efforts in the development of antimicrobial materials. The use of antimicrobial materials in healthcare facilities and health treatments can provide significant benefits. Healthcare facilities (such as hospitals) present a unique environment that combines high concentrations of germs and individuals with fragile immunity. Therefore, facilities (such as hospitals) benefit greatly from antimicrobial surfaces. Antimicrobial materials used in medical equipment can reduce the burden of disinfection and prevent the spread of disease. In addition, affordable antimicrobial surfaces can present benefits on any surface that comes into contact with organisms. For example, surfaces involved in cooking or commonly touched surfaces like door handles can greatly benefit from antimicrobial properties. Even surfaces that are primarily decorative, if affordable, can benefit from antimicrobial properties and help inhibit the spread and growth of harmful or undesirable antimicrobial organisms.

[0006] But producing antimicrobial materials can be difficult and expensive. In addition, antimicrobial materials can have other undesirable properties. For example, some antimicrobial materials can be too soft. Other antimicrobial materials can have poor wear resistance. is an antimicrobial coating comprising silver particles dispersed in an organic matrix. Antimicrobial coatings involving organic matrices may have a painted aesthetic appearance. In some applications, the painted appearance may be undesirable. Some antimicrobial coatings may use nanoparticle vapor deposition to deposit nanoparticles having antimicrobial properties on the surface of the coating. For example, Protec Antimicrobial coatings are those that use nanoparticles. However, using nanoparticles can be complex and expensive. In addition, such coatings can have a brittle surface or poor wear resistance. Another example of an antimicrobial material includes various metals. For example, silver is known to have antimicrobial properties. However, as mentioned above, silver can be expensive, and its properties may not be suitable for many applications. For example, the appearance or wear resistance of silver may not be suitable for certain applications.

[0007] Therefore, there is a need for an antimicrobial coating that addresses one or more of these problems or provides an alternative to existing antimicrobial materials. Summary of the invention

[0008] In at least one aspect, a bioactive coated substrate is provided. The bioactive coated substrate comprises a base substrate, an indicator layer disposed on the base substrate, and a bioactive layer disposed on the indicator layer. Characteristically, the indicator layer has a color different enough from the bioactive layer to be visually perceived by a user when the bioactive layer is worn away.

[0009] In another aspect, a bioactive coated substrate is provided. The bioactive coated substrate comprises a base substrate, a bottom layer arranged on the base substrate; and a plurality of alternating bioactive layers and intermediate layers arranged on the bottom layer. Characteristically, at least one of the bottom layer and / or the intermediate layer is an indicator layer having a color different enough from the bioactive layer to be visually perceived by a user when one or more of the bioactive layers are worn away.

[0010] In yet another aspect, a bioactive coated substrate is provided, comprising a base substrate, an outermost bioactive layer disposed on the base substrate, and an indicator layer disposed under the outermost bioactive layer. BRIEF DESCRIPTION OF THE DRAWINGS

[0011] Figure 1A is a schematic cross-section of a bioactive coated substrate having a bioactive layer and an indicator layer.

[0012] Figure 1B is a schematic cross-section of a bioactive coated substrate having a plurality of alternating bioactive layers, an intermediate layer, and at least one layer is an indicator layer. DETAILED DESCRIPTION

[0013] Reference will now be made in detail to the presently preferred compositions, embodiments and methods of the present invention, which constitute the best modes of carrying out the present invention known to the inventors at present. The accompanying drawings are not necessarily drawn to scale. However, it should be understood that the disclosed embodiments are merely examples of the present invention, and the present invention may be implemented in different alternative forms. Therefore, the specific details disclosed herein should not be construed as limiting, but only as representative bases for any aspect of the present invention and / or for teaching those skilled in the art to adopt the present invention in various ways.

[0014] Except in the examples or otherwise explicitly stated, all numerical quantities in this specification indicating the amount of material or reaction and / or use conditions should be understood as being modified by the word "about" when describing the broadest scope of the invention. Practice within the specified numerical limits is generally preferred. In addition, unless expressly specified to the contrary, percentages, "parts" and ratios are by weight; in conjunction with the present invention, describing a group or class of materials as suitable or preferred for a given purpose means that a mixture of any two or more members of the group or class is also suitable or preferred; describing the components in chemical terms refers to the components when added to any combination specified in the description, and once mixed, chemical interactions between the components of the mixture are not necessarily excluded; the first definition of an acronym or other abbreviation applies to all subsequent uses of the same abbreviation herein, and applies to normal grammatical variations of the initially defined abbreviation with necessary changes; and, unless expressly specified to the contrary, the measurement of a property is determined by the same technique as previously or later cited for the same property.

[0015] It must also be noted that, as used in this specification and the appended claims, the singular forms "a," "an," and "the" include plural referents unless the context clearly dictates otherwise. For example, a reference to a component in the singular is intended to include a plurality of components.

[0016] The phrase “composed of” means “including” or “comprising.” Typically, the phrase is used to indicate that an object is formed from a material.

[0017] The term "comprising" is synonymous with "including," "having," "containing," or "characterized by." These terms are inclusive and open-ended and do not exclude additional, unrecited elements or method steps.

[0018] The phrase "consisting of" excludes any element, step, or ingredient not specified in the claim. When this phrase appears in a clause in the body of a claim, rather than immediately following the preamble, it limits only the elements listed in that clause; other elements are not excluded from the claim as a whole.

[0019] The phrase "consisting essentially of" limits the scope of a claim to the specified materials or steps and those that do not materially affect one or more basic and novel characteristics of the claimed subject matter.

[0020] With respect to the terms "comprising," "consisting of," and "consisting essentially of," where one of these three terms is used herein, the presently disclosed and claimed subject matter may include the use of either of the other two terms.

[0021] The terms "substantially," "generally," or "about" may be used herein to describe disclosed or claimed embodiments. The term "substantially" may modify a value or relative characteristic disclosed or claimed in the present disclosure. In such cases, "substantially" may mean that the value or relative characteristic it modifies is within ±0%, 0.1%, 0.5%, 1%, 2%, 3%, 4%, 5%, or 10% of that value or relative characteristic.

[0022] It should also be understood that the integer range explicitly includes all intermediate integers. For example, the integer range 1 to 10 explicitly includes 1, 2, 3, 4, 5, 6, 7, 8, 9 and 10. Similarly, the range 1 to 100 includes 1, 2, 3, 4 .... 97, 98, 99, 100. Similarly, when any range is needed, the intermediate digit (which is the difference between the upper limit and the lower limit divided by 10 increments) can be considered as an alternative upper limit or lower limit. For example, if the range is 1.1 to 2.1, the following digits 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9 and 2.0 can be selected as the lower limit or upper limit. In the specific examples described herein, concentration, temperature and reaction conditions (for example, pressure, flow rate, etc.) can be implemented with the addition or subtraction of 50% of the value shown rounded to three significant figures. In a refinement, the concentration, temperature and reaction conditions (e.g., pressure, flow rate, etc.) can be implemented with plus or minus 30% of the values ​​provided in the examples rounded to three significant figures. In another refinement, the concentration, temperature and reaction conditions (e.g., flow rate, etc.) can be implemented with plus or minus 10% of the values ​​provided in the examples rounded to three significant figures.

[0023] In the examples described herein, the concentrations, temperatures, and reaction conditions (e.g., pressures, flow rates, etc.) may be implemented with the values ​​provided in the examples rounded or truncated (rounded) to two significant figures of the values ​​shown plus or minus 50%. In a refinement, the concentrations, temperatures, and reaction conditions (e.g., pressures, flow rates, etc.) may be implemented with the values ​​provided in the examples rounded or truncated (rounded) to two significant figures of the values ​​shown plus or minus 30%. In another refinement, the concentrations, temperatures, and reaction conditions (e.g., pressures, flow rates, etc.) may be implemented with the values ​​provided in the examples rounded or truncated (rounded) to two significant figures of the values ​​shown plus or minus 10%.

[0024] For all compounds represented as empirical chemical formulas with multiple letter and number subscripts (e.g., CHO), the value of the subscript may be rounded or truncated (truncated) to two significant figures plus or minus 50% of the indicated value. For example, if CHO is indicated, the formula C (0.8-1.2) H (1.6-2.4) O (0.8-1.2)In a refinement, the value of the subscript may be plus or minus 30% of the value shown rounded or truncated to two significant figures. In yet another refinement, the value of the subscript may be plus or minus 20% of the value shown rounded or truncated to two significant figures.

[0025] Throughout this application, where publications are referenced, the disclosures of these publications are hereby incorporated by reference into this application in their entireties to more fully describe the state of the art to which this invention pertains.

[0026] abbreviation:

[0027] "DLC" means diamond-like carbon.

[0028] "CAE" means cathodic arc evaporation.

[0029] "PVD" means physical vapor deposition.

[0030] Figure 1A and Figure 1B A cross section of a substrate coated with a bioactive layer and having an indicator layer is provided. Figure 1A , the bioactive coated substrate 10 includes a base substrate 12 and an indicator layer 14 arranged on the base substrate and optionally in contact with it. The term "base substrate" refers to a substrate before being coated to form a bioactive substrate described below. The bioactive layer 16 is arranged on the indicator layer 14 and optionally in contact with it. Characteristically, the indicator layer 14 can serve as a visual indication that the outermost bioactive layer 16 is damaged. In particular, the indicator layer has a color different enough from the bioactive layer to be visually perceived by the user when the bioactive layer is worn away, thereby providing the user with a visual warning that the bioactive layer 16 is damaged. Regarding setting the color of each layer so that the color difference can be determined, it should be understood that the color of each of the above-mentioned layers can be independently changed by adjusting the thickness and / or stoichiometry of the layer. In an improved scheme, the indicator layer 14 typically has a thickness from about 20 to 300nm. In another improved scheme, the bioactive layer 16 has a thickness from about 50 to 1500nm. Each of the layers of the bioactive coating substrate 10 may be fabricated by CVD, PVD (which may be sputtering), or CAE.

[0031] Figure 1BA schematic cross section of a bioactive coated substrate having a plurality of alternating bioactive layers and an intermediate layer 22 is provided. In this variant, the bioactive coated substrate 10' comprises a bottom substrate 12 and an optional bottom layer 18 arranged on the bottom substrate and optionally in contact with it. A plurality of alternating bioactive layers 16' and an intermediate layer 22 are arranged on the substrate 12 and the bottom layer 18 (if present). Typically, there may be 1 to 10 bioactive layers 16' and 1 to 10 intermediate layers 22. Characteristically, at least one of the bottom layer 18 and / or the intermediate layer 22 is an indicator layer. Typically, the outermost layer of the coated substrate 10' is a bioactive layer. In a refinement, the bottom layer 18 and / or the intermediate layer 22 may be composed of zirconium carbonitride, zirconium nitride, zirconium carbon oxide, zirconium oxynitride or zirconium carbon nitride oxide. In another refinement, the intermediate layer 22 may also be a bioactive layer, but has a different thickness and / or stoichiometry from the bioactive layer it contacts on the opposite side. In this regard, the intermediate layer 22 can be composed of various copper alloys as described below. In another improvement, the intermediate layer 22 can be composed of metal nitrides. For example, the intermediate layer 22 can be composed of zirconium nitride (ZrN), titanium nitride (TiN), zirconium oxycarbide (ZrOC), zirconium oxide (ZrO2), diamond-like carbon (DLC) or a combination thereof. In another variant, one or more of the intermediate layers 22 can be an indicator layer. Each of the layers of the bioactive coating substrate 10 can be manufactured by CVD, PVD (which can be sputtering) or CAE.

[0032] In a refinement, the bottom layer 18 and / or the middle layer 22 each independently have a thickness from about 20 to 300 nm. In another refinement, the bioactive layer 16 has a thickness from about 50 to 1500 nm.

[0033] exist Figure 1A and Figure 1B In some variations of the coated substrate depicted in , the indicator layer can be composed of zirconium carbonitride, zirconium nitride, zirconium oxycarbide, zirconium oxynitride or zirconium oxycarbonitride, titanium nitride, zirconium oxide, titanium oxide, or diamond-like. The indicator layer 14 typically has a thickness of from about 20 to 300 nm. It should be understood that embodiments of the present invention are not limited by the specific deposition method used to deposit the indicator layer 14 and the bioactive layer 16. For example, these layers can be manufactured by CVD, PVD (which can be sputtering) or CAE.

[0034] Figure 1A and Figure 1BThe bioactive layers 16 and 16' can be any material with bioactive properties. In particular, the bioactive layers 16 and 16' are antimicrobial layers. Therefore, the bioactive layers 16 and 16' can include materials with antimicrobial properties. In an improved embodiment, the bioactive layers 16 and 16' can be composed of components (having antimicrobial properties) selected from the group consisting of: bioactive metals, bioactive metal alloys, bioactive metal-containing compounds (such as metal oxides), and combinations thereof. For example, the bioactive layers 16 and 16' can be composed of: copper metal, silver metal, copper-containing metal compounds, silver-containing metal compounds, and combinations thereof.

[0035] In another improvement, the bioactive layers 16 and 16' can be composed of components selected from the group consisting of: copper alloys, copper-containing compounds, and combinations thereof. Such copper-containing compounds include copper atoms or combinations of copper atoms in +1 or +2 oxidation states. Examples of copper-containing compounds include, but are not limited to, copper, copper oxides, copper nitrides, copper oxides containing carbon atoms, and combinations thereof. In one variant, the copper alloy includes copper and nickel. Typically, each copper alloy includes nickel in an amount of from about 8 to 28 weight % of the total weight of the bioactive layer, wherein copper is present in an amount of from about 72 to 92 weight % of the total weight of the bioactive layer. In an improvement, the copper alloy includes nickel in an amount of from about 10 to 25 weight % of the total weight of the bioactive layer and copper in an amount of from about 75 to 90 weight % of the total weight of the bioactive layer. In some variants, the copper alloy can independently include additional elements such as iron, zirconium, tungsten, chromium, and combinations thereof. In a refinement, each of these additional elements is independently present in an amount from about 0.01 to about 5 weight percent of the total weight of the biologically active layer. In a refinement, each of these additional elements is independently present in an amount from about 0.01 to about 5 weight percent of the total weight of the biologically active layer. Examples of copper alloys are commercially available from Olin Brass, located in Louisville, Kentucky. White Bronze and Rose.

[0036] In other variations, the bioactive layers 16 and 16' include silver, silver alloys, silver-containing compounds (e.g., silver oxides), or any combination thereof. Other metals that may exhibit antimicrobial properties include, but are not limited to, gallium (Ga), gold (Au), magnesium (Mg), titanium (Ti), and zinc (Zn). The bioactive layers 16 and 16' may include a combination of metals, metal oxides, or metal alloys. This includes, for example, a bioactive layer 16 that includes copper (Cu) and silver (Ag).

[0037] In a refinement, each of the one or more bioactive layers 16 and 16' is independently made of CuOx In another refinement, each of the one or more bioactive layers 16 and 16' is independently composed of CuO a N b wherein a is from 0.0 to 1.2 and b is from 0.01 to 0.4. In yet another refinement, each of the one or more bioactive layers 16 and 16' is independently made of CuO c C d wherein c is from 0.0 to 1.2 and d is from 0.01 to 0.4. In a variant, each of the one or more bioactive layers 14 and 14' is independently composed of copper metal, CuO x , CuO a N b and CuO c C d any combination of; therefore, one or more biologically active layers 16 and 16 'each independently composed of: copper metal, CuO x , CuO a N b and CuO c C d A combination of Cu metal and CuO x A combination of Cu metal and CuO a N b Combination of; copper metal and CuO c C d mixture, or copper metal, CuO x and CuO a N b Combination of copper metal, CuO x and CuO c C d Combination of copper metal, CuO a N b and CuO c C d Combination of CuO x , CuO a N b and CuO c C d Combination of CuO x and CuO a N b Combination of CuO a N b and CuO c C d Combination of CuO x , CuO a N b and CuOc C d Some suitable bioactive layers can be made of Cu x O y , Cu x N y , Cu x O y N z and Cu x O y C z wherein x can be 1, 2, or 3; y can be 1, 2, or 3; and z can be 1, 2, or 3.

[0038] In another variation, the one or more bioactive layers are comprised of a mixture of a copper metal alloy and a component selected from the group consisting of zirconium nitride, titanium nitride, zirconium oxycarbide, zirconium oxide, diamond-like carbon, and combinations thereof.

[0039] In another variant, the layers 16 and 16 ′ consist of a mixture of a copper alloy and at least one of the following: zirconium nitride, titanium nitride, zirconium oxycarbide, zirconium oxide, or diamond-like carbon.

[0040] The indicator layer 14, the bottom layer 18, the intermediate layer 22, and the bioactive layers 16 and 16' can be applied to any suitable substrate 12. The suitable substrate 12 can be made of any material that exhibits thermal stability at the operating (i.e., the temperature of the bioactive coated substrate) or deposition temperature of each of these layers. In particular, the substrate 12 should be thermally stable at a temperature of at least 80°C. In an improved solution, the substrate 12 should be thermally stable at a temperature of at least 250°C. In some improved solutions, the suitable substrate 12 can be made of any material that is conductive. For example, suitable materials that can constitute the bottom substrate include, but are not limited to, metals, metal alloys, and / or carbon materials. Additional examples of suitable materials that can constitute the bottom substrate include, but are not limited to, stainless steel, chrome-plated nickel brass, chrome-plated nickel copper zinc, chrome-plated nickel copper ABS plastic, and chrome-plated nickel copper aluminum.

[0041] In another variation, the bottom layer 18 and the intermediate layer 22 are independently composed of zirconium or titanium, carbon and nitrogen, wherein zirconium is present in an amount of at least 50 mol %, and each of carbon and nitrogen is present in an amount of at least 0.02 mol % and 0.1 mol %, respectively. In a refinement, the bottom layer 18 and the intermediate layer 22 are independently composed of a compound having the following formula:

[0042] M 1-x-y C x N y

[0043] wherein M is zirconium or titanium and x is 0.0 to 0.3 and Y is 0.1 to 0.5. In a refinement, x is 0.0 to 0.2 and y is 0.2 to 0.3. In another refinement, x is at least (in increasing order of preference) 0.0, 0.02, 0.03, 0.04, 0.05, 0.07 or 0.09 and at most (in increasing order of preference) 0.5, 0.4, 0.3, 0.25, 0.2, 0.15 or 0.11. Similarly, in this refinement, y is at least (in increasing order of preference) 0.1, 0.15, 0.2, 0.25, 0.27 or 0.29 and at most (in increasing order of preference) 0.6, 0.5, 0.40, 0.35, 0.33 or 0.31. In another refinement, the bottom layer is Zr 0.60 C 0.10 N 0.30 The zirconium carbonitride is composed.

[0044] In yet another variation, the bottom layer 18 and the intermediate layer 22 are independently composed of zirconium or titanium, carbon and oxygen, wherein zirconium is present in an amount of at least 50 mol %, and each of carbon and oxygen is present in an amount of at least 0.02 mol % and 0.1 mol %, respectively. In a refinement, the bottom layer 18 and the intermediate layer 22 are independently composed of a compound having the formula:

[0045] M 1-x-y O x C y .

[0046] wherein M is zirconium or titanium and x is 0.1 to 0.4 and y is 0.5 to 0.2. In another refinement, the bottom layer is composed of Zr 0.50 O 0.35 C 0.15 The zirconium carbide is composed of the above-mentioned zirconium carbide.

[0047] In capturing the color difference between the indicator layer and the bioactive layers 16 and 16', it should be understood that the bioactive layers 16 and 16' and the indicator layer 14 (as well as the substrate and other layers) can be characterized by the Lab color space coordinates L*, a*, and b* relative to the CIE standard illuminant D50. In a refinement, at least one of the Lab color space coordinates L*, a*, and b* of the bioactive layer (e.g., typically the outermost bioactive layer) relative to the CIE standard illuminant D50 differs from that of the indicator layer by at least (in increasing order of preference) 5%, 10%, 15%, 20%, 25%, or 50%. In another refinement, each of the Lab color space coordinates L*, a*, and b* of the bioactive layer (e.g., typically the outermost bioactive layer) relative to the CIE standard illuminant D50 differs from those of the indicator layer by at least (in increasing order of preference) 5%, 10%, 15%, 20%, 25%, or 50%. In a variant, ΔE (2000), which quantifies the distance between two points in a color space, can be used to quantify the difference between two colors. The visual or obvious difference between two colors may be affected by various factors, including the observer, texture, and gloss. In a refinement, a ΔE greater than or equal to 1.0 is a sufficient color difference for an indicator. In another refinement, a ΔE greater than or equal to 2.0 is a sufficient color difference. In yet another refinement, a ΔE greater than or equal to 5.0 is a sufficient color difference. In some variants, a ΔE greater than or equal to the following is a sufficient color difference: in increasing order of preference, 2.0, 5.0, 8.0, 10.0, 15.0, and 20.0.

[0048] In another embodiment, Figure 1A and Figure 1BThe bioactive coated substrate is included in the article. In a refinement, the useful article further comprises an indicator layer, as described above. Many healthcare or hospital surfaces can greatly benefit from the bioactive coated substrate. For example, useful articles can include, but are not limited to, bed rails, risers, nightstands, knobs, handles, safety rails, carts, push boards, kickboards, mop boards, stretcher boards, faucets, drains, sinks, faucets, drain rods, drinking fountain components, sanitizer / soap dispensers, hand dryers, common buttons, headrests, shower heads, countertops, hinges, locks, latches, trim, toilet or urinal hardware, light switches, handrails, thermostats, telephones, floor tiles, ceiling tiles, wall tiles, instrument handles (e.g., drug delivery systems, monitoring systems, hospital beds, office equipment, operating room equipment, stands and fixtures), IV poles, trays, pans, walkers, wheelchairs, keyboards, computer mouse surfaces, exercise equipment, rehabilitation equipment, physical therapy equipment, lamps, lighting systems, covers, hangers, remote controls, cup holders, toothbrush holders, dress snaps, and window sills. Likewise, public or public areas in general can benefit from articles having bioactive coated substrates. For example, some articles or surfaces may include, but are not limited to, shopping carts, shopping cart handles, child seats, handrails, cash register keyboards, cash register housings, ATMs, lockers, elevator controllers, paper towel dispensers, toilet paper dispensers, vending machines, and restroom surfaces. Similar articles and surfaces may be beneficial for residential areas, public transportation, laboratories, religious gathering facilities, or any frequently visited facility. Other uses may include, but are not limited to, writing utensils, eyeglass frames, combs, cell phone cases, tablet computer cases, headphones, and bottle openers (to name a few).

[0049] Although exemplary embodiments are described above, it is not intended that these embodiments describe all possible forms of the present invention. On the contrary, the words used in this specification are descriptive rather than restrictive, and it should be understood that various changes may be made without departing from the spirit and scope of the present invention. In addition, the features of various implementation embodiments may be combined to form further embodiments of the present invention.

Claims

1. A bioactive coated substrate comprising: base substrate; an indicator layer disposed on the base substrate; as well as a bioactive layer disposed on the indicator layer, wherein the indicator layer has a color sufficiently distinguishable from the bioactive layer so as to be visually perceptible to a user when the bioactive layer is worn away, Wherein, the bioactive layer is composed of CuO a N b and / or CuO c C d wherein a is from 0.0 to 1.2 and b is from 0.01 to 0.4, wherein c is from 0.0 to 1.2 and d is from 0.01 to 0.4, Therein, the bioactive layer has a thickness of from 50 to 1500 nm and the indicator layer has a thickness of from 20 to 300 nm.

2. The bioactive coated substrate of claim 1, wherein: The indicator layer is made of zirconium carbonitride, zirconium nitride, zirconium oxycarbide, zirconium oxynitride, zirconium oxycarbonitride, titanium nitride, zirconium oxide, titanium oxide, or diamond-like carbon.

3. The bioactive coated substrate of claim 1, wherein: The bioactive layer is composed of CuO c C d In the case of the bioactive layer further comprising CuO a N b Composition, wherein a is from 0.0 to 1.2 and b is from 0.01 to 0.

4.

4. The bioactive coated substrate of claim 1, wherein: The bioactive layer is composed of CuO a N b In the case of the bioactive layer further comprising CuO c C d Composition, wherein c is from 0.0 to 1.2 and d is from 0.01 to 0.

4.

5. The bioactive coated substrate of claim 1, wherein: At least one of the Lab color space coordinates L*, a* and b* of the biologically active layer relative to CIE standard illuminant D50 differs from that of the indicator layer by at least 5%.

6. The bioactive coated substrate of claim 1, wherein: Each of the Laboratory color space coordinates L*, a* and b* of the biologically active layer relative to CIE standard illuminant D50 differs from those of the indicator layer by at least 5%.

7. The bioactive coated substrate of claim 1, wherein: The ΔE of the bioactive layer and the indicator layer is greater than or equal to 2.

0.

8. The bioactive coated substrate of claim 1, wherein: The ΔE of the bioactive layer and the indicator layer is greater than or equal to 5.

0.

9. A bioactive coated substrate comprising: base substrate; a bottom layer disposed on the bottom substrate; as well as a plurality of alternating bioactive layers and intermediate layers disposed on the base layer, wherein at least one of the base layer and / or the intermediate layers is an indicator layer having a color sufficiently distinguishable from the bioactive layers so as to be visually perceived by a user when one or more of the bioactive layers are worn away, Wherein, the bioactive layer is composed of CuO a N b and / or CuO c C d Composition, wherein a is from 0.0 to 1.2 and b is from 0.01 to 0.4, wherein c is from 0.0 to 1.2 and d is from 0.01 to 0.4, wherein each bioactive layer has a thickness from 50 to 1500 nm, each intermediate layer has a thickness from 20 to 300 nm, and the bottom layer has a thickness from 20 to 300 nm.

10. The bioactive coated substrate of claim 9, wherein: The base layer and each intermediate layer are composed of zirconium carbonitride, zirconium nitride, zirconium oxycarbide, zirconium oxynitride, zirconium oxycarbonitride, titanium nitride, zirconium oxide, titanium oxide, or diamond-like carbon.

11. The bioactive coated substrate of claim 9, wherein: At least one of the Lab color space coordinates L*, a* and b* of the outermost biologically active layer relative to CIE standard illuminant D50 differs from that of the indicator layer by at least 5%.

12. The bioactive coated substrate of claim 9, wherein: The Lab color space coordinates L*, a* and b* of the outermost biologically active layer relative to CIE standard illuminant D50 each differ by at least 5% from those of the indicator layer.

13. The bioactive coated substrate of claim 9, wherein: The ΔE of the outermost bioactive layer and the indicator layer is greater than or equal to 2.

0.

14. The bioactive coated substrate of claim 9, wherein: The ΔE of the outermost bioactive layer and the indicator layer is greater than or equal to 5.

0.

15. The bioactive coated substrate of claim 9, wherein: The bioactive layer is composed of CuO c C d In the case of the bioactive layer further comprising CuO a N b Composition, wherein a is from 0.0 to 1.2 and b is from 0.01 to 0.

4.

16. The bioactive coated substrate of claim 9, wherein: The bioactive layer is composed of CuO a N b In the case of the bioactive layer further comprising CuO c C d Composition, wherein c is from 0.0 to 1.2 and d is from 0.01 to 0.4.

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