ANTIMICROBIAL COATING SOLUTION DEVELOPED FOR GLASS SURFACES, ANTIMICROBIAL COATED GLASS AND THE APPLICATION PROCESS THEREOF

Abstract

An antimicrobial coating solution developed to be used on glass surfaces is provided. In an alcohol and/or water environment, the antimicrobial coating solution includes at least one copper salt in a hydrate form and at least one tin source. A process of applying the antimicrobial coating solution to a complex shaped glass surface is further provided. The antimicrobial coating solution is configured to be applied to the complex shaped glass surface when a temperature of the complex shaped glass surface is 400° C. and higher. The complex shaped glass surface is a flat glass or a glassware.

Claims

1. An antimicrobial coating solution developed to be used on glass surfaces, wherein in an alcohol and/or water environment, the antimicrobial coating solution comprises at least one copper salt in a hydrate form, and at least one tin source.

2. The antimicrobial coating solution according to claim 1, wherein the at least one copper salt comprises at least one of copper(II) sulfate, copper(II) chloride, and copper(II) nitrate in a predetermined proportion.

3. The antimicrobial coating solution according to claim 1, wherein the at least one tin source comprises at least one of monobutyltin trichloride, tin tetrachloride, and dibutyl tin diacetate (DBTDA) in a predetermined proportion.

4. The antimicrobial coating solution according to claim 1, wherein the antimicrobial coating solution is suitable for an application by pyrolytic spray or atmospheric chemical vapor settling methods.

5. A process of applying the antimicrobial coating solution according to claim 1 to a complex shaped glass surface, wherein the antimicrobial coating solution is configured to be applied to the complex shaped glass surface when a temperature of the complex shaped glass surface is 400° C. and higher, and the complex shaped glass surface is a flat glass or a glassware.

6. The process according to claim 5, wherein the antimicrobial coating solution is configured to be applied to the complex shaped glass surface from a single feeding port or multiple feeding ports.

7. The process according to claim 6, wherein the at least one tin source and the at least one copper salt are delivered to the complex shaped glass surface by separate channels in the multiple feeding ports.

8. An antimicrobial coating developed to be applied to glass surfaces, wherein the antimicrobial coating comprises at least one copper salt in a hydrate form and at least one tin source.

9. The antimicrobial coating according to claim 8, wherein the at least one copper salt comprises at least one of copper(II) sulfate, copper(II) chloride, and copper(II) nitrate in a predetermined proportion.

10. The antimicrobial coating according to claim 8, wherein the at least one tin source comprises at least one of monobutyltin trichloride and tin tetrachloride in a predetermined proportion.

11. The antimicrobial coating according to claim 8, wherein the at least one tin source comprises dibutyl tin diacetate.

12. The antimicrobial coating according to claim 8, wherein a thickness of the antimicrobial coating in flat glass applications is at most 200 nm.

13. The antimicrobial coating according to claim 8, wherein a thickness of the antimicrobial coating in glassware applications is at most 20 nm.

14. The antimicrobial coating according to claim 8, wherein the antimicrobial coating is in a form of an oxide.

15. The antimicrobial coating according to claim 8, wherein the antimicrobial coating is a coating without a chemical release from a coating surface to an environment.

16. The antimicrobial coating according to claim 8, wherein the antimicrobial coating is configured to be tempered.

17. The antimicrobial coating according to claim 8, wherein an antibacterial effect of the antimicrobial coating against E. coli and S. aureus bacteria is at least 90% according to an ISO 22196 standard.

18. The antimicrobial coating according to claim 8, wherein an antiviral effect of the antimicrobial coating against Poliovirus Type-1, Adenovirus Type-5, Murine Norovirus Type 1 S99, and B. Coronavirus viruses is at least 90% according to an ISO 21702 standard.

19. The antimicrobial coating solution according to claim 2, wherein the antimicrobial coating solution is suitable for an application by pyrolytic spray or atmospheric chemical vapor settling methods.

20. The antimicrobial coating solution according to claim 3, wherein the antimicrobial coating solution is suitable for an application by pyrolytic spray or atmospheric chemical vapor settling methods.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0038] FIG. 1 shows the XRD analysis of the flat glass sample coated with a solution containing tin and copper.

[0039] FIGS. 2A-2C show the cross-section STEM analysis of the coating and STEM-EDX map of tin and copper across the coated flat glass example (magnification: 50 k×).

[0040] FIGS. 3A-3D show the surface FEG-SEM images of the copper doped tin oxide coated flat glass sample taken at different magnifications (40 k×, 70 k×, 100 k× ve 120 k×).

DETAILED DESCRIPTION OF THE EMBODIMENTS

[0041] In this detailed description, the antimicrobial coating solution of the invention and the method of application to glass and coated glass are explained only with examples that do not have any limiting effect for a better understanding of the subject matter.

[0042] Agents that prevent bacterial growth on surfaces are called “antibacterial” and agents that prevent virus growth are called “antiviral”, and agents that prevent fungal growth are called “antifungal”. Antimicrobial materials are defined as surfaces that show activity on different microorganisms such as bacteria, viruses, and mold/fungus. Viruses, bacteria and fungi differ from each other in terms of physical size, structural complexity, genetic material, metabolic activity, and reproduction traits. The antimicrobial property described in the present invention is defined as the simultaneous occurrence of antiviral and antibacterial effects.

[0043] ISO 21702 (Measurement of antiviral activity on plastics and other non-porous surfaces) standards were used to measure antiviral activity numerically, and ISO 22196 (Measurement of antibacterial activity on plastics and other non-porous surfaces) standards were used to measure antibacterial activity.

[0044] The present invention relates to tin oxide-based thin-film coatings with high optical transmittance and permanent antimicrobial effect and their chemical formulations and the application of this coating on a glass substrate. In the coating obtained with the solution of the invention, in addition to its antimicrobial property, it is ensured that there is no or minimum level of chemical release. In the alternative embodiment, the chemical and mechanical strength of the coating with the same property has been increased.

[0045] In the environment of water and/or alcohol, the solution of the invention comprises; [0046] At least one copper salt selected from copper(II) sulphate, copper(II) chloride, copper(II) nitrate in hydrate form at a ratio of 5-15% by weight, or its mixtures in a certain ratio; [0047] At least one tin source selected from monobutyltin trichloride (MBTC), tin tetrachloride, dibutyltin diacetate (DBTDA) at a ratio of 20-40% by weight, or its mixtures in a certain ratio.

[0048] Ethanol is preferably used as the carrier alcohol.

[0049] The obtained solution is obtained by first dissolving the salt components in water or water and alcohol mixed medium and then adding the tin source into the solution. If water and alcohol are used together, alcohol and tin sources are added to the solution after the salt components have been dissolved in water. Thus, the solution is ensured to be optically clear, with no phase separation or precipitation occurring.

[0050] The obtained solution can be applied to glass samples that are formed at high temperatures or flat directly under atmospheric conditions. The pyrolytic spray is used in one embodiment of the invention. In another embodiment of the invention, the atmospheric chemical vapor settling method is used.

[0051] During the production of coated glass, in cases that the ambient temperature is 400° C. and higher, the solution can be applied directly to the glass surface by using pyrolytic spray or chemical vapor settling techniques, and thus on-line coatings are obtained. Chemical vapor settling reactors can have laminar or turbulent flows. The solution is preferably applied to the glass surface when the glass surface is between 400° C.-650° C. When the solution is applied to the on-line glass surface at the ambient temperature between 400° C.-650° C., the solution content is decomposed and a thin film layer in the oxide structure is formed by combining with the oxygen in the environment. Even if the solution components are fed from separate ports, a homogeneous reactant atmosphere can be created and a homogeneous layer can be formed on the glass surface.

[0052] Depending on the selected composition, the starting components can be applied to the glass surface in single or multiple ports. Multiple port application is preferred, especially when using a direct water-immiscible tin source (for example, Dibutyltin diacetate) or when a higher concentration of copper on the surface is desired. In multiple applications, the tin-containing mixture can be applied from one port and the copper-containing mixture dissolved in water and/or alcohol can be applied on another port simultaneously to the glass surface. For monobutyltin trichloride and tin tetrachloride, the presence of water in the reactant atmosphere is known to increase the growth rate of the oxide layer (A. B. M. van Mol, Y. Chae, A. H. McDaniel and M. D. Allendorf, “Chemical vapor deposition of tin oxide: Fundamentals and applications,” Thin Solid Films, vol. 502, pp. 72-78, 2006). Thereby, coating homogeneity problems caused by the presence of water and variable glass surface temperatures can also be minimized.

[0053] According to the thin film XRD results in FIG. 1, the chemical framework of the final layer is mostly a tin oxide layer in the cassiterite phase and its optical properties are practically the same as the tin oxide layer without copper addition. The tin and copper percentage ratios of the coating films were measured by surface SEM-EDX and cross-section STEM-EDX analyses. In FIGS. 3A-3D, it has been determined that the coating thickness of the Cu doped tin oxide coated flat glass example is at most 190 nm.

[0054] For samples of glassware with Cu and Sn coating, the coating thickness is 20 nm and less. It is known that undesirable iridescent coloration behavior, which is noticeable to the naked eye, is observed at layer thicknesses of 100 nm and more in applications on glass (U.S. Pat. No. 4,187,336 patent publication). If thick layers are selected in practice, it is possible to remove the iridescence permanently by using one or more dielectric layers that suppresses color (U.S. Pat. No. 4,187,336 patent publication).

TABLE-US-00001 TABLE 1 SEM-EDX analysis results taken from the surface of the Cu and Sn coated flat glass sample (@8 kV) Anal- ysis O % Na % Mg % Al % Si % S % Ca % Cu % Sn % 1 23.93 0.19 0.02 0.17 0.37 1.29 N/A 1.38 72.65 2 24.48 0.2 N/A 0.06 0.43 1.24 0.15 1.56 71.88 3 24.46 0.15 N/A 0.13 0.25 1.06 N/A 1.4 72.55 4 24.58 0.12 0.04 0.18 0.4 1.17 0.01 1.4 72.09 Aver- 24.36 0.16 0.02 0.14 0.36 1.19 0.04 1.44 72.29 age

[0055] Tin sources are also used as a hot end coating material in the solution. Thus, inorganic coatings with high scratch/mechanical strength, heat resistance, and detergent resistance are obtained. Another advantage of tin (IV) oxide-based coatings is that their refraction index of about 2 in the visible region is lower than that of titanium dioxide whose refraction index is 2.5-2.6 and display similar levels of antimicrobial activity. Due to the relatively low refraction index in the visible region, undesired coloring/reflection effects due to thickness inhomogeneity are less pronounced. Thus, it can tolerate higher thickness variations that may occur during application.

[0056] There is no need for active chemical agent release to obtain the antimicrobial effect in the said coating. The release properties of the basic metal elements in the coating content from the surface were measured by the ICP-OES method.

TABLE-US-00002 TABLE 3 Release values obtained in 24 ± 0.5 hours at 22 ± 2° C. by using 4% acetic acid solution. Surface Area (dm.sup.2) Cu release (mg/dm.sup.2) Sn release (mg/dm.sup.2) 0.603 0.0200 0.0006

[0057] The high temperature process in an open atmosphere contributes to the formation of an oxide coating. The release can be minimized by using an oxide layer that does not contain high mobility free ions and has strong thermal, mechanical, and chemical stability. Our thin-film coating according to the invention contains a high proportion of tin oxide (tin (IV) oxide) and copper additive homogeneously distributed throughout the coating cross section.

TABLE-US-00003 TABLE 4 Antiviral and antibacterial activity results according to relevant standards Virus (ISO 21702) Bacteria (ISO 22196) Poliovirus Adenovirus Murine Norovirus B. Name E. coli S. Aureus Type-1 Type-5 Type 1 S99 Coronavirus Strain ATCC ATCC ATCC Adenoid 75, ATCC-PTA ATCC 8739 6538 VR-192 ATCC VR-5 5935 VR-874 Reduction >90% >90% >90% >90% >90% >90% (%)

[0058] The coating solution of the invention can be applied directly to glasses at high temperatures. The layer structure formed with the coating solution can be thermally tempered. At the same time, it offers streamlined production and cost advantage since there is no need for a secondary heat treatment for firing after cold end application on glass.

[0059] The scope of protection of the invention is specified in the attached claims and it cannot be limited to what is explained in this detailed description for the sake of example. It is clear that a person skilled in the art can provide similar embodiments in the light of the above, without departing from the main theme of the invention.