Composite antibacterial antiviral agent and method of preparation, protective glaze, ceramic tile and method of preparation

Abstract

The application discloses a kind of composite antibacterial antiviral agent and preparation method, protective glaze, ceramic tile and preparation method, it is related to ceramic tile technical field.The preparation method of the composite antibacterial antiviral agent of the present application includes the following steps: after mixing silicon dioxide, aluminum oxide, copper carbonate, strontium carbonate, boron oxide, soda ash and nickel hydroxide, melt under reducing atmosphere, obtain melt, after melt is quenched by water, dried and broken, obtain green antibacterial antiviral frit;Mix copper carbonate, calcined zinc oxide, silver-loaded zirconium phosphate and calcined alumina to obtain red antibacterial antiviral agent;Green antibacterial antiviral frit and red antibacterial antiviral agent are mixed to obtain composite antibacterial antiviral agent.The composite antibacterial antiviral agent with good antibacterial antiviral effect and without affecting the original color of ceramic tile can be prepared, which is suitable for ceramic tile field, and solves the problem that materials with good antiviral effect easily affect the original decorative color of ceramic tile.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of ceramic tiles, and particularly relates to a composite antibacterial and antiviral agent, a preparation method thereof, a protective glaze, a ceramic tile and a preparation method thereof. BACKGROUND

[0002] A ceramic tile is a kind of practical decorative building material prepared by using refractory metal oxides and semi-metal oxides through grinding, mixing, pressing, glazing and sintering. People pay more and more attention to the health indicators of indoor decoration materials, and especially common ceramic tiles are very easy to adsorb viruses and breed bacteria, which seriously threatens human health. At present, there are many ceramic tiles with antibacterial effect on the market, but there are very few ceramic tiles with antiviral effect. Therefore, developing ceramic tiles with good antibacterial and antiviral effects has become a research focus in the field of ceramic tiles.

[0003] At present, common antibacterial and antiviral materials are zinc ion materials, silver ion materials and copper ion materials. The zinc ion materials, silver ion materials and copper ion materials have certain effects in antibacterial and antiviral aspects. Among them, the zinc ion materials and silver ion materials have good antibacterial effect, but the antiviral effect is relatively poor, while the copper ion has excellent antiviral effect. At present, zinc ion materials and silver ion materials are widely used in the field of ceramic tiles because they do not affect the original decorative color of ceramic tiles. The ceramic tiles prepared by using zinc ion materials and silver ion materials usually have excellent antibacterial effect, but the antiviral effect is poor. Since the compounds containing copper all have color, they easily affect the original decorative color of ceramic tiles. Therefore, although the copper ion material has excellent antiviral effect, it is still rarely used in the field of ceramic tiles. Therefore, it is urgent to develop an antibacterial and antiviral material suitable for the field of ceramic tiles, which is the basis for researching antibacterial and antiviral ceramic tiles. SUMMARY

[0004] In view of the above shortcomings of the prior art, one of the purposes of the present application is to provide a preparation method of a composite antibacterial and antiviral agent, which can prepare a composite antibacterial and antiviral agent with good antibacterial and antiviral effects and without affecting the original color of ceramic tiles, is suitable for the field of ceramic tiles and can be used to prepare ceramic tiles with antibacterial and antiviral effects, thereby solving the problem that the existing materials with good antiviral effect easily affect the original decorative color of ceramic tiles.

[0005] The second purpose of the present application is to provide a composite antibacterial and antiviral agent prepared by the above preparation method, which has excellent antibacterial and antiviral effects, and when the composite antibacterial and antiviral agent is applied to prepare ceramic tiles, the color of the composite antibacterial and antiviral agent after firing is suitable for the original color of the ceramic tiles.

[0006] The third object of the present application is to provide an antibacterial and antiviral protective glaze using the above-mentioned composite antibacterial and antiviral agent, having excellent antibacterial and antiviral effects, and applicable to the preparation of ceramic tiles.

[0007] The fourth object of the present application is to provide an antibacterial and antiviral ceramic tile, sequentially comprising a tile body, a pattern layer, and an antibacterial and antiviral protective layer from bottom to top, the antibacterial and antiviral protective layer being fired from the above-mentioned antibacterial and antiviral protective glaze, having excellent antibacterial and antiviral effects, and the antibacterial and antiviral protective layer not affecting the original decorative color of the pattern layer.

[0008] The fifth object of the present application is to provide a preparation method of an antibacterial and antiviral ceramic tile, capable of preparing an antibacterial and antiviral ceramic tile with strong antibacterial and antiviral effects.

[0009] To achieve the above-mentioned objects, the present application adopts the following technical solutions.

[0010] A preparation method of a composite antibacterial and antiviral agent, comprising the following steps:

[0011] (1) mixing silica, alumina, copper carbonate, strontium carbonate, boron oxide, soda ash, and nickel hydroxide, and then melting under a reducing atmosphere to obtain a melt, and then obtaining a green antibacterial and antiviral frit by water quenching, drying, and crushing the melt;

[0012] (2) mixing copper carbonate, calcined zinc oxide, silver-loaded zirconium phosphate, and calcined alumina to obtain a red antibacterial and antiviral agent;

[0013] (3) mixing the green antibacterial and antiviral frit and the red antibacterial and antiviral agent to obtain a composite antibacterial and antiviral agent.

[0014] Preferably, in step (3), the green antibacterial and antiviral frit and the red antibacterial and antiviral agent are mixed in a mass ratio of (0.5-2.5):1 to obtain the composite antibacterial and antiviral agent.

[0015] Preferably, the operation method of step (1) comprises: mixing silica 20-50 parts, alumina 5-10 parts, copper carbonate 20-40 parts, strontium carbonate 1-5 parts, boron oxide 10-20 parts, soda ash 10-30 parts, and nickel hydroxide 0.02-2 parts by mass fraction, and then melting under a reducing atmosphere to obtain a melt.

[0016] Preferably, in step (1), the temperature for melting under a reducing atmosphere is 1500-1600°C.

[0017] Preferably, the operation method of step (2) comprises: mixing, in terms of mass fraction, 20-40 parts of copper carbonate, 20-40 parts of calcined zinc oxide, 1-10 parts of silver-loaded zirconium phosphate, and 10-40 parts of calcined aluminum oxide to obtain the red antibacterial and antiviral agent.

[0018] A composite antibacterial and antiviral agent is prepared by the preparation method of the composite antibacterial and antiviral agent, and comprises green antibacterial and antiviral frit and red antibacterial and antiviral agent, and the mass ratio of the green antibacterial and antiviral frit to the red antibacterial and antiviral agent is (0.5-2.5):1.

[0019] In terms of mass fraction, the raw materials of the green antibacterial and antiviral frit comprise 20-50 parts of silicon dioxide, 5-10 parts of aluminum oxide, 20-40 parts of copper carbonate, 1-5 parts of strontium carbonate, 10-20 parts of boron oxide, 10-30 parts of soda ash, and 0.02-2 parts of nickel hydroxide.

[0020] The raw materials of the red antibacterial and antiviral agent comprise 20-40 parts of copper carbonate, 20-40 parts of calcined zinc oxide, 1-10 parts of silver-loaded zirconium phosphate, and 10-40 parts of calcined aluminum oxide.

[0021] An antibacterial and antiviral protective glaze comprises a protective glaze base and the composite antibacterial and antiviral agent.

[0022] Preferably, in terms of mass fraction, the antibacterial and antiviral protective glaze comprises 100 parts of the protective glaze base and 1-5 parts of the composite antibacterial and antiviral agent.

[0023] An antibacterial and antiviral ceramic tile comprises, from bottom to top, a tile body, a pattern layer, and an antibacterial and antiviral protective layer, and the antibacterial and antiviral protective layer is fired from the antibacterial and antiviral protective glaze.

[0024] A preparation method of an antibacterial and antiviral ceramic tile is used to prepare the antibacterial and antiviral ceramic tile, and comprises the following steps.

[0025] (1) Inkjet printing is performed on the surface of the tile body to obtain the pattern layer.

[0026] (2) A formula amount of the composite antibacterial and antiviral agent is added to a formula amount of the protective glaze base, and is subjected to a colloidal ball mill to obtain the antibacterial and antiviral protective glaze.

[0027] (3) The antibacterial and antiviral protective glaze is coated on the surface of the pattern layer to form the antibacterial and antiviral protective layer, and is fired to obtain the antibacterial and antiviral ceramic tile.

[0028] The technical scheme provided by the embodiments of the present application can have the following beneficial effects.

[0029] 1. In order to prevent the original decorative color of the ceramic tile from being affected and to obtain better antibacterial and antiviral effects, the technical scheme develops a composite antibacterial and antiviral agent suitable for the field of ceramic tiles, which is prepared by compounding nickel hydroxide, part of copper carbonate and other raw materials, melting in a reducing atmosphere to form a green antibacterial and antiviral frit, and compounding part of copper carbonate, calcined zinc oxide, silver-loaded zirconium phosphate and calcined aluminum oxide to form a red antibacterial and antiviral agent. By using the principle of complementary colors of red and green, the influence of the composite antibacterial and antiviral agent on the original color of the ceramic tile can be reduced.

[0030] 2. By compounding silicon dioxide, aluminum oxide, copper carbonate, strontium carbonate, boron oxide, soda ash and nickel hydroxide, melting in a reducing atmosphere, the various antibacterial and antiviral components can be solid-solution formed into a melt in advance, achieving the effect of enhancing antibacterial and antiviral effects. The raw materials of the red antibacterial and antiviral agent include copper carbonate, calcined zinc oxide, silver-loaded zirconium phosphate and calcined aluminum oxide, which are compounded for use, further enhancing the antibacterial and antiviral effects and achieving the effect of synergism, which is better than the effect of using silver-loaded zirconium phosphate and copper carbonate alone. The composite antibacterial and antiviral agent of the technical scheme is prepared into green antibacterial and antiviral frit and red antibacterial and antiviral agent respectively, which not only reduces the influence on the original color of the ceramic tile, making the composite antibacterial and antiviral agent suitable for the field of ceramic tiles, but also achieves excellent antibacterial and antiviral effects. DETAILED DESCRIPTION

[0031] In order to facilitate the understanding of the present application, the present application will be described more fully below. The present application can be implemented in many different forms and is not limited to the embodiments described herein. On the contrary, the purpose of providing these embodiments is to make the disclosure of the present application more thorough and comprehensive.

[0032] In the embodiments, the specific techniques or conditions not specified are carried out according to the techniques or conditions described in the literature in the art or according to the product instructions. The raw materials not specified by the manufacturer are all conventional products that can be obtained by purchase.

[0033] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the present application belongs. The terms used in the specification of the present application herein are only for the purpose of describing the specific embodiments and are not intended to limit the present application. The term "and / or" used herein includes any and all combinations of one or more related listed items.

[0034] The technical scheme of the present application will be further described below in conjunction with the specific embodiments.

[0035] A preparation method of a composite antibacterial and antiviral agent, comprising the following steps:

[0036] (1) mixing silica, alumina, copper carbonate, strontium carbonate, boron oxide, soda ash and nickel hydroxide, melting under a reducing atmosphere to obtain a melt, and then obtaining a green antibacterial and antiviral frit by water quenching, drying and crushing the melt;

[0037] (2) mixing copper carbonate, calcined zinc oxide, silver-loaded zirconium phosphate and calcined alumina to obtain a red antibacterial and antiviral agent;

[0038] (3) mixing the green antibacterial and antiviral frit and the red antibacterial and antiviral agent to obtain a composite antibacterial and antiviral agent.

[0039] It is worth noting that nickel hydroxide and copper carbonate can provide Ni 2+ and Cu 2+ , Ni 2+ and Cu 2+ have strong antibacterial and antiviral effects. Since copper-containing compounds and nickel-containing compounds are colored, if nickel hydroxide and copper carbonate are directly added to the glaze and used to prepare ceramic tiles, the original decorative color of the ceramic tiles will be affected. In order to prevent the original decorative color of the ceramic tiles from being affected and to obtain better antibacterial and antiviral effects, the present technical solution develops a composite antibacterial and antiviral agent suitable for the field of ceramic tiles, which is prepared by compounding nickel hydroxide, part of copper carbonate and other raw materials, melting under a reducing atmosphere to obtain a green antibacterial and antiviral frit, and compounding the remaining copper carbonate, calcined zinc oxide, silver-loaded zirconium phosphate and calcined alumina to obtain a red antibacterial and antiviral agent. By using the principle of complementary colors of red and green, the influence of the composite antibacterial and antiviral agent on the original color of the ceramic tiles can be reduced.

[0040] Specifically, the principle of complementary colors of red and green that can reduce the influence on the original color of the ceramic tiles is as follows: red and green mixed in a certain proportion can present yellow or gray, and the current mainstream decorative color of ceramic tiles is yellow, beige and gray. Therefore, the color of the composite antibacterial and antiviral agent prepared by the present technical solution is coordinated with the current mainstream decorative color of ceramic tiles. Therefore, the use of the composite antibacterial and antiviral agent of the present technical solution in ceramic tiles can effectively reduce the influence on the original decorative color of the ceramic tiles.

[0041] Further explanation, the present technical solution melts nickel hydroxide, copper carbonate and other raw materials of green antibacterial and antiviral frit under a reducing atmosphere to obtain a green frit. The color of the green frit is partly derived from the fact that copper carbonate will generate light yellow cuprous hydroxide and blue copper hydroxide under the conditions of alkalinity and reducing atmosphere at high temperature. Yellow cuprous hydroxide and blue copper hydroxide mixed together will turn green, and the other part is derived from Gu 2+The solid solution in the hexagonal columnar lattice generated by silica and alumina generates a structure similar to that of emerald and the same green color as emerald; and nickel hydroxide is a green powder, Ni 2+ can absorb red light, and Ni 2+ is also green, so the green antibacterial and antiviral frit is green. The red antibacterial and antiviral agent is prepared by mixing copper carbonate with other raw materials of the red antibacterial and antiviral agent. Since the firing process of the ceramic tile is carried out in an oxygen atmosphere, copper carbonate decomposes into red copper oxide and cuprous oxide at high temperature, so that the red antibacterial and antiviral agent appears red. The red antibacterial and antiviral agent is decolorized with the green antibacterial and antiviral frit, achieving the effect of affecting the original color of the ceramic tile.

[0042] Specifically, the raw materials of the green antibacterial and antiviral frit include silica, alumina, copper carbonate, strontium carbonate, boron oxide, soda ash, and nickel hydroxide. After the nickel hydroxide, copper carbonate, and strontium carbonate are made into a frit, Ni 2+ , Cu 2+ , and Sr 2+ ions are provided, so that the green antibacterial and antiviral frit has strong antibacterial and antiviral effects. At the same time, by compounding silica, alumina, copper carbonate, strontium carbonate, boron oxide, soda ash, and nickel hydroxide and melting under a reducing atmosphere, the various antibacterial and antiviral components can be solid-solved in advance to form a melt, achieving the effect of enhancing antibacterial and antiviral effects. The raw materials of the red antibacterial and antiviral agent include copper carbonate, calcined zinc oxide, silver-loaded zirconium phosphate, and calcined alumina, and the use of each raw material can further enhance the antibacterial and antiviral effects, achieving the effect of synergism, which is better than the effect of using silver-loaded zirconium phosphate and copper carbonate alone. The composite antibacterial and antiviral agent of the technical solution is prepared into a green antibacterial and antiviral frit and a red antibacterial and antiviral agent, respectively, which not only achieves the effect of reducing the influence on the original color of the ceramic tile, but also makes the composite antibacterial and antiviral agent applicable to the field of ceramic tiles, and achieves excellent antibacterial and antiviral effects.

[0043] It should be noted that the toxicity of nickel hydroxide is relatively large, so it is necessary to prepare a frit in advance to reduce its toxicity, and then incorporate it into the glaze (i.e. the protective glaze base below) for further offsetting its toxicity after firing, which can avoid pollution to the environment and harm to the operators. Although copper carbonate also has a certain toxicity, the toxicity of copper carbonate is not high. After compounding part of the copper carbonate and nickel hydroxide, a frit is prepared in advance, which can avoid harm and pollution to the environment and harm to the operators. At the same time, due to the low toxicity of copper carbonate, although the red antibacterial and antiviral agent also contains copper carbonate, the copper carbonate in the red antibacterial and antiviral agent can be solidified in the glaze layer to eliminate the toxicity after the composite antibacterial and antiviral agent is mixed with the glaze and fired, so the red antibacterial and antiviral agent does not need to be prepared into a frit to eliminate the toxicity of copper carbonate. At the same time, by preparing a frit from strontium carbonate and part of the copper carbonate in advance, when the composite antibacterial and antiviral agent is used in the glaze later, it can avoid introducing too much carbonate into the glaze to produce too many bubbles, thereby affecting the glaze effect.

[0044] Specifically, in step (1), the obtained melt is water quenched, dried and crushed to obtain a green antibacterial and antiviral frit. The melt in a molten state is solidified into a solid state by water quenching, and the solid-state melt is dried to remove water and then crushed to make the melt into granular or powdery form, thereby facilitating and protecting the uniform mixing of the glaze base. Preferably, after crushing, the crushed material is sieved through a 200-mesh screen to obtain a green antibacterial and antiviral frit. The water quenching, drying and crushing methods in the present technical solution are all known, and can be performed according to conventional frit preparation methods in the art.

[0045] Further, in step (3), the green antibacterial and antiviral frit and the red antibacterial and antiviral agent are mixed in a mass ratio of (0.5-2.5):1 to obtain a composite antibacterial and antiviral agent.

[0046] It should be noted that by mixing the green antibacterial and antiviral frit and the red antibacterial and antiviral agent in a mass ratio of (0.5-2.5):1, the color effect of the green antibacterial and antiviral frit and the red antibacterial and antiviral agent can be decolorized during the firing process of the ceramic tile after the composite antibacterial and antiviral agent is mixed with the protective glaze base, so that the composite antibacterial and antiviral agent presents yellow or gray, which is coordinated with the original decorative color of the ceramic tile, avoiding that the composite antibacterial and antiviral agent presents too bright red or green, which affects the original decorative color of the ceramic tile.

[0047] Preferably, the mass ratio of the green antibacterial and antiviral frit and the red antibacterial and antiviral agent is (1-2):1. More preferably, the mass ratio of the green antibacterial and antiviral frit and the red antibacterial and antiviral agent is 1:1 or 2:1, which can achieve better decolorization effect and better antibacterial and antiviral effect of the prepared composite antibacterial and antiviral agent.

[0048] Further, the operation method of step (1) comprises: mixing 20-50 parts of silica, 5-10 parts of alumina, 20-40 parts of copper carbonate, 1-5 parts of strontium carbonate, 10-20 parts of boron oxide, 10-30 parts of soda ash and 0.02-2 parts of nickel hydroxide according to mass fraction, and then melting under a reducing atmosphere to obtain a melt.

[0049] The raw materials of the green antibacterial and antiviral frit in the present application include 20-50 parts of silica, 5-10 parts of alumina, 20-40 parts of copper carbonate, 1-5 parts of strontium carbonate, 10-20 parts of boron oxide, 10-30 parts of soda ash and 0.02-2 parts of nickel hydroxide. By matching these components, the various antibacterial and antiviral components can be solid-solved in advance under a reducing atmosphere, thereby enhancing the antibacterial and antiviral effect.

[0050] Preferably, the copper carbonate (CuCO3) is nano copper carbonate, which has smaller particle size and larger specific surface area, and is beneficial to improving the antibacterial and antiviral effect.

[0051] Further, the melting temperature under the reducing atmosphere in step (1) is 1500-1600℃.

[0052] It is worth noting that the raw materials of the green antibacterial and antiviral frit are mixed, and then the frit raw materials are placed in a glass tank kiln and melted under a reducing atmosphere at 1500-1600℃, so that a uniform glass frit is formed, the various antibacterial and antiviral components are solid-solved in advance, thereby enhancing the antibacterial and antiviral effect, and the toxicity of copper carbonate and nickel hydroxide is weakened. In addition, the copper carbonate is melted under a reducing atmosphere to generate green products, so that the prepared frit is green, thereby obtaining the green antibacterial and antiviral frit.

[0053] Specifically, the melting temperature under the reducing atmosphere in the present application is 1500-1600℃, which can melt the frit raw materials to form a uniform glass frit. If the temperature is too high, excessive bubbling and boiling will occur in the melting process of the mixture, which will cause the frit to overflow from the melting cavity of the glass tank kiln, resulting in loss. In addition, excessive bubbles during melting will affect the transparency of the prepared frit, thereby reducing the transparency of the prepared frit.

[0054] Further, the operation method of step (2) comprises: mixing, according to mass fraction, 20-40 parts of copper carbonate, 20-40 parts of calcined zinc oxide, 1-10 parts of silver-loaded zirconium phosphate and 10-40 parts of calcined aluminum oxide to obtain the red antibacterial and antiviral agent.

[0055] Specifically, the raw materials of the red antibacterial and antiviral agent of the technical solution comprise 20-40 parts of copper carbonate, 20-40 parts of calcined zinc oxide, 1-10 parts of silver-loaded zirconium phosphate and 10-40 parts of calcined aluminum oxide. Since copper carbonate will present red color in an oxidizing atmosphere, and the firing of the ceramic tile is carried out in an oxidizing atmosphere, the red antibacterial and antiviral agent of the technical solution will present red color after firing. The red antibacterial and antiviral agent and the green antibacterial and antiviral frit of two colors can be complementary, so that the composite antibacterial and antiviral agent after firing presents yellow or gray color, which is compatible with the original color of the ceramic tile, thereby playing a role of color elimination, avoiding that the composite antibacterial and antiviral agent presents red or green color, and affecting the original decorative color of the ceramic tile. Moreover, the red antibacterial and antiviral agent obtained by using the formula of the technical solution has better antibacterial and antiviral effect, and after compounding with the green antibacterial and antiviral frit, the antibacterial and antiviral effect can be further enhanced.

[0056] Preferably, the fineness of the calcined aluminum oxide in the technical solution is below 200 mesh.

[0057] A composite antibacterial and antiviral agent is prepared by the preparation method of the composite antibacterial and antiviral agent, and comprises the green antibacterial and antiviral frit and the red antibacterial and antiviral agent, and the mass ratio of the green antibacterial and antiviral frit to the red antibacterial and antiviral agent is (0.5-2.5):1.

[0058] According to mass fraction, the raw materials of the green antibacterial and antiviral frit comprise 20-50 parts of silicon dioxide, 5-10 parts of aluminum oxide, 20-40 parts of copper carbonate, 1-5 parts of strontium carbonate, 10-20 parts of boron oxide, 10-30 parts of soda ash and 0.02-2 parts of nickel hydroxide.

[0059] The raw materials of the red antibacterial and antiviral agent comprise 20-40 parts of copper carbonate, 20-40 parts of calcined zinc oxide, 1-10 parts of silver-loaded zirconium phosphate and 10-40 parts of calcined aluminum oxide.

[0060] The composite antibacterial and antiviral agent of the technical solution has excellent antibacterial and antiviral effect. Meanwhile, the composite antibacterial and antiviral agent of the technical solution is applied to the protective glaze of the ceramic tile, and after firing, the composite antibacterial and antiviral agent presents yellow or gray color, which is compatible with the mainstream decorative color (yellow, beige and gray) of the ceramic tile, and thus is suitable for the ceramic tile.

[0061] A protective antibacterial and antiviral glaze comprises a protective glaze base and the composite antibacterial and antiviral agent.

[0062] Specifically, the protective glaze base in the technical solution is a protective glaze commonly used in the field of ceramic tiles.

[0063] Further, the antibacterial and antiviral protective glaze includes 100 parts of the protective glaze base and 1-5 parts of the composite antibacterial and antiviral agent, in terms of mass fraction.

[0064] Specifically, by adding 1-5 parts of the composite antibacterial and antiviral agent to the antibacterial and antiviral protective glaze (calculated based on the dry weight of the protective glaze base), a better antibacterial and antiviral effect can be achieved, and the cost is not too high.

[0065] An antibacterial and antiviral ceramic tile includes, from bottom to top, a tile body, a pattern layer, and an antibacterial and antiviral protective layer, wherein the antibacterial and antiviral protective layer is fired from the antibacterial and antiviral protective glaze described above.

[0066] It is worth noting that the antibacterial and antiviral protective layer is set on the surface of the antibacterial and antiviral ceramic tile, and the antibacterial and antiviral protective layer is fired from the antibacterial and antiviral protective glaze of the technical solution, which can significantly improve the antibacterial and antiviral effects of the ceramic tile, and the ceramic tile has strong antiviral activity against EV71, H3N2, and other viruses, and also has strong antibacterial activity against Escherichia coli and Staphylococcus aureus. The pattern layer is set between the tile body and the antibacterial and antiviral protective layer, which can make the ceramic tile present various beautiful patterns and textures, thereby increasing the decorative effect and the texture of the ceramic tile. In addition, the antiviral ceramic tile of the technical solution can also include a base glaze layer, which is arranged between the tile body and the pattern layer. By setting the base glaze layer on the surface of the tile body, the color and defects of the tile body can be covered, and the base glaze can also protect the body from physical and chemical damage from the outside, improve the mechanical strength, stain resistance, wear resistance, and durability of the body, etc.

[0067] A method for preparing an antibacterial and antiviral ceramic tile, which is used to prepare the antibacterial and antiviral ceramic tile described above, includes the following steps:

[0068] (1) Inkjet printing is performed on the surface of the tile body to obtain a pattern layer;

[0069] (2) A formula amount of the composite antibacterial and antiviral agent is added to a formula amount of the protective glaze base, and gel ball milling is performed to obtain an antibacterial and antiviral protective glaze;

[0070] (3) The antibacterial and antiviral protective glaze is coated on the surface of the pattern layer to form an antibacterial and antiviral protective layer, and firing is performed to obtain the antibacterial and antiviral ceramic tile.

[0071] Specifically, the preparation step (1) of the antibacterial and antiviral protective glaze comprises: adding 1-5 parts of the composite antibacterial and antiviral agent to 100 parts of the protective glaze base material according to the dry weight of the protective glaze base material, adding sodium hexametaphosphate and sodium tripolyphosphate according to the conventional amount of debonding agent for debonding and ball milling, and controlling the fineness and specific gravity of the antibacterial and antiviral protective glaze according to the conventional fineness and specific gravity of the protective glaze, so as to obtain the antibacterial and antiviral protective glaze.

[0072] As preferred, in one embodiment of the present application, the preparation method of the antibacterial and antiviral protective glaze in step (1) is as follows: according to the mass fraction, 1-5 parts of the composite antibacterial and antiviral agent is added to 100 parts of the protective glaze base material, and then 0.5-2 parts of sodium hexametaphosphate, 0.5-2 parts of sodium tripolyphosphate and an appropriate amount of water are added for debonding and ball milling, the material is ball milled until the particle size is less than 45 microns, and the specific gravity is adjusted to 1.3-1.45 g / cm 3 , to obtain the antibacterial and antiviral protective glaze. The amount of water is controlled in the range of 28%-33% (wt%) of the water content of the glaze material after the whole ball milling. The specific gravity of the antibacterial and antiviral protective glaze is adjusted to 1.3-1.45 g / cm 3 , which is beneficial to keep the glaze surface smooth after glazing and does not appear obvious glaze dripping effect, so that a thin and continuous antibacterial and antiviral protective layer can be formed on the surface of the ceramic tile, and the ceramic tile surface can exhibit good antibacterial and antiviral effect.

[0073] Specifically, the drying step is further included before the sintering in step (2), which mainly removes the water in the green tile and the antibacterial and antiviral protective glaze, and is beneficial to the later sintering. The drying process in the present application adopts the conventional process in the art. Meanwhile, the sintering process of the antibacterial and antiviral ceramic tile in the present application is known, and the sintering can be carried out by using the conventional process in the art, such as sintering the green tile coated with the antibacterial and antiviral protective glaze at 1080-1280°C, and obtaining the antibacterial and antiviral ceramic tile after sintering.

[0074] It is worth mentioning that the preparation method of the antibacterial and antiviral ceramic tile of the technical solution further comprises an inkjet printing step, and the inkjet printing step comprises: performing inkjet printing on the surface of the green tile to obtain a pattern layer, so that the ceramic tile has a decorative pattern and color. When performing inkjet printing, blue ink, black ink, red ink and yellow ink are usually required. In order to further enable the ceramic tile to maintain the original pattern color unchanged after being coated with the antibacterial and antiviral protective glaze, as a preferred, when performing inkjet printing, the inkjet amount of the blue ink channel is increased by 10-50% compared with usual (i.e. when the protective glaze is only the protective glaze base described in the present solution); the inkjet amount of the black ink, red ink and yellow ink channels is reduced by 20-90% compared with usual, and the inkjet amount of each channel is adjusted according to the color change of the tile surface, so that the original pattern color of the ceramic tile can be maintained unchanged. For example, when preparing a ceramic tile of a specified decorative color in a conventional manner, the inkjet amount of blue ink accounts for 5%, the inkjet amount of black ink accounts for 21%, the inkjet amount of red ink accounts for 5%, and the inkjet amount of yellow ink accounts for 33%. In an embodiment of the present application, the same ceramic tile of the specified decorative color is prepared, and the antibacterial and antiviral protective glaze of the present solution is coated on the surface of the ceramic tile. In order to make the final decorative color of the prepared ceramic tile closer to the original color, therefore, when performing inkjet printing, the inkjet amount of blue ink accounts for 7%, the inkjet amount of black ink accounts for 16%, the inkjet amount of red ink accounts for 3%, and the inkjet amount of yellow ink accounts for 5%.

[0075] Examples 1-5

[0076] The composite antibacterial and antiviral agent of Examples 1-5 all comprises a green antibacterial and antiviral frit and a red antibacterial and antiviral agent, and the mass ratio of the green antibacterial and antiviral frit and the red antibacterial and antiviral agent is (0.5-2.5):1;

[0077] According to the mass fraction, the raw materials of the green antibacterial and antiviral frit include 20-50 parts of silicon dioxide, 5-10 parts of aluminum oxide, 20-40 parts of copper carbonate, 1-5 parts of strontium carbonate, 10-20 parts of boron oxide, 10-30 parts of soda ash and 0.02-2 parts of nickel hydroxide; the raw materials of the red antibacterial and antiviral agent include 20-40 parts of copper carbonate, 20-40 parts of calcined zinc oxide, 1-10 parts of silver-loaded zirconium phosphate and 10-40 parts of calcined aluminum oxide; wherein, the formula of the composite antibacterial and antiviral agent in Examples 1-5 is shown in Table 1 as follows:

[0078] The preparation method of the composite antibacterial and antiviral agent of the present embodiment comprises the following steps:

[0079] (1) According to the proportion, the silica, alumina, copper carbonate, strontium carbonate, boron oxide, soda ash and nickel hydroxide are mixed, then placed in a reducing atmosphere for melting, the melting temperature is 1500-1600℃, to obtain a melt, the melt is quenched by water, dried and crushed to obtain a green antibacterial and antiviral frit;

[0080] (2) The copper carbonate, calcined zinc oxide, silver-loaded zirconium phosphate and calcined alumina are mixed to obtain a red antibacterial and antiviral agent;

[0081] (3) The green antibacterial and antiviral frit and the red antibacterial and antiviral agent are mixed in a mass ratio of (1-2) : 1 to obtain a composite antibacterial and antiviral agent.

[0082] Table 1 Composition of the composite antibacterial and antiviral agent in Examples 1-5

[0083]

[0084]

[0085] Specifically, the composite antibacterial and antiviral agents prepared in Examples 1-5 are respectively used to prepare antibacterial and antiviral ceramic tiles, and antibacterial and antiviral ceramic tiles are obtained, wherein the preparation method of the antibacterial and antiviral ceramic tiles comprises the following steps:

[0086] (1) Inkjet printing is performed on the surface of the green tile to obtain a pattern layer;

[0087] (2) 3 parts of the composite antibacterial and antiviral agent are added to 100 parts of the protective glaze base material, and ball milling is performed to obtain an antibacterial and antiviral protective glaze;

[0088] (3) The antibacterial and antiviral protective glaze is coated on the surface of the pattern layer to form an antibacterial and antiviral protective layer, and then fired to obtain the antibacterial and antiviral ceramic tile.

[0089] Specifically, the antiviral activity and antibacterial performance of the antibacterial and antiviral ceramic tiles prepared by using the composite antibacterial and antiviral agents of Examples 1-5 are detected respectively. Since there is no relevant national and industry standard for antiviral in the ceramic tile industry, the antiviral activity detection in this technical solution is detected according to the standard “ISO 201702:2019 Plastics and other non-porous surfaces Antiviral activity test”, the antibacterial performance is detected according to the standard “JC / T897-2014 Antibacterial ceramic products Antibacterial performance”, and the antibacterial and antiviral activity detection results are shown in Table 2. At the same time, the tile surface effect is observed, whether the antibacterial and antiviral protective glaze affects the original pattern color of the ceramic tile, and the detection results are shown in Table 2.

[0090] Table 2 Antibacterial and antiviral performance detection results

[0091]

[0092]

[0093] From the detection results of Table 2, it can be seen that the ceramic tiles prepared by using the composite antibacterial and antiviral agent prepared in Examples 1-5 all have excellent antibacterial and antiviral effects, the antiviral activity rate against EV71 virus reaches 95.2% to 97.8%, the antiviral activity rate against H3N2 virus reaches 90.3% to 96.2%, the antibacterial rate against Escherichia coli reaches 98.1% to 99.3%, and the antibacterial rate against Staphylococcus aureus reaches 95.8% to 99.5%. At the same time, it can be seen from the tile surface effect of the prepared ceramic tiles that the composite antibacterial and antiviral agent prepared in Examples 1-5 does not affect the original pattern color of the ceramic tiles.

[0094] The technical principles of the present application are described above in combination with specific examples. These descriptions are only for explaining the principles of the present application, and cannot be interpreted as limiting the protection scope of the present application in any way. Based on the explanations herein, other specific embodiments of the present application can be conceived by those skilled in the art without creative efforts, and these embodiments will all fall within the protection scope of the present application.

Claims

1. A method of preparing a composite antimicrobial antiviral agent, characterized by, The method comprises the following steps: (1) mixing silica, alumina, copper carbonate, strontium carbonate, boron oxide, soda ash and nickel hydroxide, melting under a reducing atmosphere to obtain a melt, and obtaining green antibacterial and antiviral frit after water quenching, drying and crushing; (2) mixing copper carbonate, calcined zinc oxide, silver-loaded zirconium phosphate and calcined alumina to obtain a red antibacterial and antiviral agent; (3) mixing the green antibacterial and antiviral frit and the red antibacterial and antiviral agent to obtain a composite antibacterial and antiviral agent.

2. The method for preparing the composite antibacterial and antiviral agent according to claim 1, characterized in that, In step (3), the green antibacterial and antiviral frit and the red antibacterial and antiviral agent are mixed at a mass ratio of (0.5-2.5):1 to obtain the composite antibacterial and antiviral agent.

3. The method for preparing the composite antibacterial and antiviral agent according to claim 1, characterized in that, The operation method of step (1) comprises: mixing silica 20-50 parts, alumina 5-10 parts, copper carbonate 20-40 parts, strontium carbonate 1-5 parts, boron oxide 10-20 parts, soda ash 10-30 parts and nickel hydroxide 0.02-2 parts according to the mass fraction, and then melting under a reducing atmosphere to obtain a melt.

4. The method of claim 3, wherein the composite antiviral agent is prepared by the steps of: a) mixing the antiviral agent and the antimicrobial agent; b) adding the mixture to the carrier; and c) drying the mixture to form the composite antiviral agent. In step (1), the melting temperature under a reducing atmosphere is 1500-1600°C.

5. The method of claim 1, wherein the composite antiviral agent is prepared by the steps of: a) mixing the antiviral agent and the antimicrobial agent; b) adding the mixture to the carrier; and c) drying the mixture to form the composite antiviral agent. The operation method of step (2) comprises: mixing copper carbonate 20-40 parts, calcined zinc oxide 20-40 parts, silver-loaded zirconium phosphate 1-10 parts and calcined alumina 10-40 parts according to the mass fraction to obtain a red antibacterial and antiviral agent.

6. A composite antimicrobial antiviral agent, characterized in that, The composite antibacterial and antiviral agent prepared by the method of any one of claims 1-5 comprises a green antibacterial and antiviral frit and a red antibacterial and antiviral agent, and the mass ratio of the green antibacterial and antiviral frit to the red antibacterial and antiviral agent is (0.5-2.5):1; According to the mass fraction, the raw materials of the green antibacterial and antiviral frit comprise silica 20-50 parts, alumina 5-10 parts, copper carbonate 20-40 parts, strontium carbonate 1-5 parts, boron oxide 10-20 parts, soda ash 10-30 parts and nickel hydroxide 0.02-2 parts; The raw materials of the red antibacterial and antiviral agent comprise copper carbonate 20-40 parts, calcined zinc oxide 20-40 parts, silver-loaded zirconium phosphate 1-10 parts and calcined alumina 10-40 parts.

7. An antibacterial antiviral protective enamel characterized in that, The composite antibacterial and antiviral agent of claim 6 is used as a protective glaze base.

8. The anti-bacterial anti-viral protective enamel according to claim 7, wherein, According to the mass fraction, the composite antibacterial and antiviral agent comprises protective glaze base 100 parts and composite antibacterial and antiviral agent 1-5 parts.

9. An antibacterial antiviral tile, characterized in that, From bottom to top, the green brick comprises a green brick, a pattern layer and an antibacterial and antiviral protective layer, and the antibacterial and antiviral protective layer is prepared by firing the antibacterial and antiviral protective glaze of claim 7 or 8.

10. A method for preparing an antibacterial and antiviral ceramic tile, characterized in that, The method for preparing the antibacterial and antiviral ceramic tile of claim 9 comprises the following steps: (1) inkjet printing on the surface of the green brick to obtain a pattern layer; (2) adding a formula amount of the composite antibacterial and antiviral agent to a formula amount of the protective glaze base, and performing a colloidal ball mill to obtain an antibacterial and antiviral protective glaze; (3) coating the antibacterial and antiviral protective glaze on the surface of the pattern layer to form an antibacterial and antiviral protective layer, and firing to obtain an antibacterial and antiviral ceramic tile.

Images