Antibacterial and stain-resistant ceramic glaze and method of making same

Abstract

The application relates to the technical field of glazes, and discloses an antibacterial and stain-resistant ceramic glaze and a preparation method thereof. The ceramic glaze is prepared by taking bentonite, potash feldspar, kaolin, talcum powder, dolomite, calcite, zircon, limestone, albite, a modified carrier type antibacterial agent and a thickening agent as raw materials, ball-milling and mixing, and then adding water to adjust the specific gravity. The modified carrier type antibacterial agent is prepared by loading silver on the surface of tourmaline and coating a continuous organic silicon layer. After the coating of the organic silicon layer, the tourmaline particles can be dispersed from each other, silver can be uniformly distributed in the glaze layer formed by ablation, and the antibacterial performance of the glaze is improved. The continuous organic silicon layer forms a silica sol in the sintering process of the glaze, protects the silver, prevents the silver from being ablated, ensures that the glaze still has good antibacterial activity after sintering, and the silica sol has excellent hydrophobic effect, so that the glaze layer has a super-hydrophobic surface and excellent stain-resistant and stain-proof performance.

Description

Technical Field

[0001] This invention relates to the field of glaze technology, specifically to an antibacterial and stain-resistant ceramic glaze and its preparation method. Background Technology

[0002] With the improvement of people's living standards and the increasing demand for healthy living environments, functional modification has become an important development direction for the industry. In daily use scenarios, the surface of ceramic products is extremely prone to the growth of bacteria, mold, and other microorganisms, especially in humid environments such as kitchens and bathrooms. The attachment and reproduction of microorganisms not only affect hygiene but may also cause cross-infection, posing a potential threat to human health. Therefore, endowing ceramic surfaces with long-lasting and broad-spectrum antibacterial functions has become an important technical indicator for high-end ceramic products.

[0003] Meanwhile, the stain resistance of ceramic surfaces directly affects the product's aesthetics and cleaning and maintenance costs. Traditional ceramic glazes, due to micropores or insufficient glaze hardness, easily attract dust, oil, ink, tea, and other contaminants during use, which are difficult to remove completely. Long-term accumulation leads to yellowing, staining, and decreased gloss, severely impacting the decorative effect and lifespan. Currently, the industry primarily achieves antibacterial properties in ceramics by adding metal ions such as silver, copper, and zinc, or their oxides, as antibacterial agents to the glaze. However, existing silver-based antibacterial agents generally suffer from poor dispersibility and agglomeration, resulting in uneven distribution of antibacterial components in the glaze layer and affecting the stability of antibacterial efficiency. Furthermore, silver ions are easily eroded during high-temperature firing, causing a decline in antibacterial performance. In addition, while copper and zinc-based antibacterial agents are lower in cost, their antibacterial activity is relatively weak and they easily cause glaze discoloration, affecting the product's appearance. Regarding stain resistance, existing technologies primarily focus on adding hydrophobic / oleophobic additives. However, hydrophobic additives are prone to decomposition and failure during high-temperature firing, and their poor compatibility with the glaze matrix makes it difficult to form a uniform and stable low surface energy layer. More importantly, existing technologies often treat antibacterial and stain resistance as independent modification targets, lacking a systematic design of their synergistic mechanism. Therefore, how to achieve stable loading, uniform distribution, and long-lasting release of antibacterial components while ensuring excellent stain resistance of the glaze, and simultaneously avoiding mutual constraints between the two functions, has become a pressing technical challenge in this field.

[0004] To address the aforementioned problems, this invention provides a ceramic glaze that can solve the problems existing in the prior art. Summary of the Invention

[0005] In order to solve the problems mentioned in the background art, the purpose of this invention is to provide an antibacterial and stain-resistant ceramic glaze and its preparation method.

[0006] The objective of this invention can be achieved through the following technical solutions: An antibacterial and stain-resistant ceramic glaze is made from the following raw materials measured in parts by weight: 26-34 parts bentonite, 5-8 parts potassium feldspar, 4-10 parts kaolin, 2-4 parts talc, 1-2 parts dolomite, 2-5 parts calcite, 3-6 parts zircon, 1-2 parts limestone, 3-4 parts sansine, 2-6 parts modified carrier-type antibacterial agent, 2-6 parts thickener; The modified carrier-type antibacterial agent is silver-loaded tourmaline with a continuous silicon layer on its surface.

[0007] As a further aspect of the present invention, the preparation method of the modified carrier-type antibacterial agent includes the following steps: Step 1: Disperse tourmaline in toluene to form a uniform dispersion. Then add an acid anhydride modifier and catalyst to the dispersion. After the addition is complete, heat to 70-80℃, keep warm and stir for 4-8 hours, then stop heating, cool down and discharge the material. Collect the product, wash and dry it to obtain organic tourmaline. Step 2: Add organic tourmaline to deionized water and disperse it evenly. Then, add silver ammonia solution to the resulting dispersion to adjust the pH. Heat the mixture to 60-65℃ and keep it under heat for 4-6 hours. Then, stop heating and allow it to cool naturally. Centrifuge the solid material and wash and dry it to obtain the loaded tourmaline modified material. Step 3: Disperse the supported tourmaline modifier evenly in anhydrous ethanol, purge with nitrogen, then add a bridging agent. After the addition is complete, heat to 70-80℃, then add a platinum catalyst. Keep warm and stir for 2-4 hours, then add 1,3-bis(4-acryloyloxybutyl)tetramethyldisiloxane. Keep warm and stir for 12-16 hours, then cool down and discharge the material. The product is purified to obtain the modified carrier-type antibacterial agent.

[0008] As a further aspect of the present invention, in step one, the anhydride modifier is maleic anhydride.

[0009] As a further aspect of the present invention, in step one, the catalyst is p-toluenesulfonic acid.

[0010] As a further embodiment of the present invention, in step two, the pH is 10-12.

[0011] As a further embodiment of the present invention, in step three, the bridging agent is any one of 1,1,3,3,5,5-hexamethyltrisiloxane, decamethyldihydropentasiloxane, or 1,1,3,3,5,5,7,7-octamethyltetrasiloxane.

[0012] As a further embodiment of the present invention, in step three, the mass ratio of the supported tourmaline modifier, the bridging agent and 1,3-bis(4-acryloyloxybutyl)tetramethyldisiloxane is 1:0.2-0.3:0.1-0.2.

[0013] It should be noted that in the above technical solution, firstly, under the action of a catalyst, an anhydride modifier is used to modify the surface of tourmaline, and active carboxyl substituents are modified on the surface of the tourmaline to obtain organic tourmaline. Then, under an alkaline environment, the carboxyl substituents of the organic tourmaline can complex silver ammonia ions, thereby complexing the silver ammonia ions on the tourmaline surface. Through the carbonyl group of the organic tourmaline, the silver ammonia complex ions are reduced, so that silver particles grow in situ on the tourmaline surface to obtain a supported tourmaline modified material. Finally, using the unsaturated alkenyl substituents of the organic tourmaline as active initiation sites, the Si-H of the bridging agent and the unsaturated alkenyl substituents of 1,3-bis(4-acryloyloxybutyl)tetramethyldisiloxane undergo a continuous hydrosilylation reaction, thereby forming an organosilicon continuous layer on the tourmaline surface to obtain a modified carrier-type antibacterial agent.

[0014] As a further embodiment of the present invention, the thickener is sodium carboxymethyl cellulose or carboxymethyl starch.

[0015] A method for preparing a stain-resistant ceramic glaze includes the following steps: Step S1: Weigh each raw material according to the weight proportions; Step S2: First, add bentonite, potassium feldspar, kaolin, talc, dolomite, calcite, zircon, limestone, sanspar and modified carrier-type antibacterial agent into a ball mill and ball mill and mix until the residue on a 10,000-mesh sieve is less than 0.1% to obtain the precursor material. Step S3: Mix the precursor material and thickener thoroughly, then add water to adjust the specific gravity to 1.55-1.6 g / cm³. 3 To obtain ceramic glaze.

[0016] The beneficial effects of this invention are: This invention prepares a modified carrier-type antibacterial agent by loading silver onto the surface of tourmaline and coating it with a continuous organosilicon layer. On one hand, after being coated with the organosilicon layer, the tourmaline particles can disperse to form a well-dispersed system, which is distributed in the glaze, ensuring uniform silver distribution in the glaze layer formed by ablation, thus giving the glaze excellent antibacterial properties. On the other hand, during the sintering process of the glaze, the continuous organosilicon layer forms silica sol, which protects the silver and prevents it from being ablated, thus ensuring that the glaze still exhibits good antibacterial activity after sintering. Furthermore, the silica sol itself has excellent hydrophobic properties, enabling the glaze layer to exhibit a superhydrophobic surface, thereby endowing the glaze layer with excellent anti-fouling and stain-resistant properties.

[0017] Of course, any product implementing this invention does not necessarily need to achieve all of the advantages described above at the same time. Detailed Implementation

[0018] The technical solution of the present invention will be clearly and completely described below with reference to the embodiments. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0019] Example 1 An antibacterial and stain-resistant ceramic glaze is made from the following raw materials measured in parts by weight: 26 parts bentonite, 5 parts potassium feldspar, 4 parts kaolin, 2 parts talc, 1 part dolomite, 2 parts calcite, 3 parts zircon, 1 part limestone, 3 parts sanspar, 2 parts modified carrier-type antibacterial agent, and 2 parts sodium carboxymethyl cellulose. The method for preparing the ceramic glaze includes the following steps: Step S1: Weigh each raw material according to the weight proportions; Step S2: First, add bentonite, potassium feldspar, kaolin, talc, dolomite, calcite, zircon, limestone, sanspar and modified carrier-type antibacterial agent into a ball mill and ball mill and mix until the residue on a 10,000-mesh sieve is less than 0.1% to obtain the precursor material. Step S3: Mix the precursor material with sodium carboxymethyl cellulose until homogeneous, then add water to adjust the specific gravity to 1.6 g / cm³. 3 To obtain ceramic glaze.

[0020] The preparation method of the modified carrier-type antibacterial agent includes the following steps: Step 1: Disperse 2.4g of tourmaline in toluene to form a uniform dispersion. Then add 0.5g of maleic anhydride and 0.1g of p-toluenesulfonic acid to the dispersion. After the addition is complete, heat to 75℃, keep warm and stir for 6 hours, then stop heating, cool down and discharge the material. Collect the product, wash and dry it to obtain organic tourmaline. Step 2: Add 2g of organic tourmaline to deionized water and disperse it evenly. Then add 0.5mL of silver ammonia solution to the resulting dispersion to adjust the pH to 11. Heat the mixture to 60℃ and keep it under heat for 4 hours. Then stop heating and allow it to cool naturally. Centrifuge the solid material and wash and dry it to obtain the loaded tourmaline modified material. Step 3: Disperse 1.5g of supported tourmaline modifier evenly in anhydrous ethanol, purge with nitrogen, then add 0.4g of 1,1,3,3,5,5-hexamethyltrisiloxane. After the addition is complete, heat to 75℃, then add 0.01g of platinum catalyst, keep warm and stir for 3h, then add 0.2g of 1,3-bis(4-acryloyloxybutyl)tetramethyldisiloxane, keep warm and stir for 16h, then cool and discharge. The product is purified to obtain the modified carrier-type antibacterial agent.

[0021] The silver ammonia solution is prepared by the following method: Add 2% ammonia solution dropwise to a 2% silver nitrate solution until the solution is just clear and transparent.

[0022] Example 2 An antibacterial and stain-resistant ceramic glaze is made from the following raw materials measured in parts by weight: 28 parts bentonite, 6 parts potassium feldspar, 8 parts kaolin, 3 parts talc, 1.5 parts dolomite, 3 parts calcite, 4 parts zircon, 1.5 parts limestone, 3.5 parts sansine, 5 parts modified carrier-type antibacterial agent, and 3 parts sodium carboxymethyl cellulose. The method for preparing the ceramic glaze includes the following steps: Step S1: Weigh each raw material according to the weight proportions; Step S2: First, add bentonite, potassium feldspar, kaolin, talc, dolomite, calcite, zircon, limestone, sanspar and modified carrier-type antibacterial agent into a ball mill and ball mill and mix until the residue on a 10,000-mesh sieve is less than 0.1% to obtain the precursor material. Step S3: Mix the precursor material with sodium carboxymethyl cellulose until homogeneous, then add water to adjust the specific gravity to 1.6 g / cm³. 3 To obtain ceramic glaze.

[0023] The preparation method of the modified carrier-type antibacterial agent is the same as that in Example 1.

[0024] Example 3 An antibacterial and stain-resistant ceramic glaze is made from the following raw materials measured in parts by weight: 34 parts bentonite, 8 parts potassium feldspar, 10 parts kaolin, 4 parts talc, 2 parts dolomite, 5 parts calcite, 6 parts zircon, 2 parts limestone, 4 parts sansobionic acid, 6 parts modified carrier-type antibacterial agent, and 6 parts carboxymethyl cellulose. The method for preparing the ceramic glaze includes the following steps: Step S1: Weigh each raw material according to the weight proportions; Step S2: First, add bentonite, potassium feldspar, kaolin, talc, dolomite, calcite, zircon, limestone, sanspar and modified carrier-type antibacterial agent into a ball mill and ball mill and mix until the residue on a 10,000-mesh sieve is less than 0.1% to obtain the precursor material. Step S3: Mix the precursor material with sodium carboxymethyl cellulose until homogeneous, then add water to adjust the specific gravity to 1.6 g / cm³. 3 To obtain ceramic glaze.

[0025] The preparation method of the modified carrier-type antibacterial agent is the same as that in Example 1.

[0026] Comparative Example 1 A ceramic glaze is made from the following raw materials, measured in parts by weight: 28 parts bentonite, 6 parts potassium feldspar, 8 parts kaolin, 3 parts talc, 1.5 parts dolomite, 3 parts calcite, 4 parts zircon, 1.5 parts limestone, 3.5 parts sanspar, 5 parts loaded tourmaline modifier, and 3 parts sodium carboxymethyl cellulose. The method for preparing the ceramic glaze includes the following steps: Step S1: Weigh each raw material according to the weight proportions; Step S2: First, add bentonite, potassium feldspar, kaolin, talc, dolomite, calcite, zircon, limestone, sanspar, and loaded tourmaline modifier into a ball mill and ball mill until the residue on the 10,000-mesh sieve is less than 0.1% to obtain the precursor material. Step S3: Mix the precursor material with sodium carboxymethyl cellulose until homogeneous, then add water to adjust the specific gravity to 1.6 g / cm³. 3 To obtain ceramic glaze.

[0027] The preparation method of the load-bearing tourmaline modified material is described in Example 1.

[0028] Comparative Example 2 A ceramic glaze is made from the following raw materials, measured in parts by weight: 28 parts bentonite, 6 parts potassium feldspar, 8 parts kaolin, 3 parts talc, 1.5 parts dolomite, 3 parts calcite, 4 parts zircon, 1.5 parts limestone, 3.5 parts sansine, 5 parts modified tourmaline, and 3 parts sodium carboxymethyl cellulose. The method for preparing the ceramic glaze includes the following steps: Step S1: Weigh each raw material according to the weight proportions; Step S2: First, add bentonite, potassium feldspar, kaolin, talc, dolomite, calcite, zircon, limestone, sanspar and modified tourmaline into a ball mill and mix until the residue on a 10,000-mesh sieve is less than 0.1% to obtain the precursor material. Step S3: Mix the precursor material with sodium carboxymethyl cellulose until homogeneous, then add water to adjust the specific gravity to 1.6 g / cm³. 3 To obtain ceramic glaze.

[0029] The preparation method of modified tourmaline includes the following steps: Step 1: Disperse 2.4g of tourmaline in toluene to form a uniform dispersion. Then add 0.5g of maleic anhydride and 0.1g of p-toluenesulfonic acid to the dispersion. After the addition is complete, heat to 75℃, keep warm and stir for 6 hours, then stop heating, cool down and discharge the material. Collect the product, wash and dry it to obtain organic tourmaline. Step 2: Disperse 1.5g of organic tourmaline evenly in anhydrous ethanol, purge with nitrogen, then add 0.4g of 1,1,3,3,5,5-hexamethyltrisiloxane. After the addition is complete, heat to 75℃, then add 0.01g of platinum catalyst, keep warm and stir for 3h, then add 0.2g of 1,3-bis(4-acryloyloxybutyl)tetramethyldisiloxane, keep warm and stir for 16h, then cool and discharge. The product is purified to obtain modified tourmaline.

[0030] Test case A ceramic blank measuring 10cm×10cm×5mm was sintered in a sintering furnace at 650℃ for 4 hours. After sintering, the blank was removed and impregnated with the ceramic glaze from the examples and comparative examples. Five blanks were impregnated with the glaze, and the glaze thickness on the surface of the blank was controlled to be 0.1mm. The blanks were then placed in a sintering furnace and sintered at 1280℃ for 8 hours. After sintering, the blanks were removed and allowed to cool naturally to form samples. According to standard JC / T 897-2014, Staphylococcus aureus was selected as the test strain to test the antibacterial properties of the samples. Use a water contact angle meter to test the water contact angle of the sample; The test results are recorded in the table below:

[0031] Analysis of the test results shows that the ceramic glaze prepared in this embodiment of the invention, after sintering, forms a glaze layer with good antibacterial properties and exhibits superhydrophobic characteristics, providing excellent antifouling and stain-resistant performance. When the modified carrier-type antibacterial agent is replaced with a supported tourmaline modifier, the silver cannot be protected by the silica sol layer during sintering, resulting in ablation and a decrease in the glaze layer's antibacterial performance. Furthermore, the water contact angle is significantly reduced, and the antifouling and stain-resistant performance is also noticeably diminished. Replacing the modified carrier-type antibacterial agent with modified tourmaline, without silver loading, leads to a significant decrease in the glaze layer's antibacterial performance.

[0032] This document uses specific examples to illustrate the principles and implementation methods of the present invention. The descriptions of these embodiments are merely to aid in understanding the method and core ideas of the present invention, including the best mode, and to enable any person skilled in the art to practice the present invention, including manufacturing and using any device or system, and implementing any combined method. It should be noted that those skilled in the art can make various improvements and modifications to the present invention without departing from its principles, and these improvements and modifications also fall within the scope of protection of the claims. The scope of protection of this patent is defined by the claims and may include other embodiments that can be conceived by those skilled in the art. If these other embodiments have structural elements similar to those expressed in the claims, or if they include equivalent structural elements that are not substantially different from those expressed in the claims, then these other embodiments should also be included within the scope of the claims.

[0033] The above embodiments are only used to illustrate the technical solutions of the present invention, and are not intended to limit it. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some of the technical features. Such modifications or substitutions will not cause the essence of the corresponding technical solutions to deviate from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims

1. An antibacterial and stain-resistant ceramic glaze, characterized in that, It is made from the following raw materials, measured in parts by weight: 26-34 parts bentonite, 5-8 parts potassium feldspar, 4-10 parts kaolin, 2-4 parts talc, 1-2 parts dolomite, 2-5 parts calcite, 3-6 parts zircon, 1-2 parts limestone, 3-4 parts sansine, 2-6 parts modified carrier-type antibacterial agent, 2-6 parts thickener; The modified carrier-type antibacterial agent is silver-loaded tourmaline with a continuous silicon layer on its surface.

2. The antibacterial and stain-resistant ceramic glaze according to claim 1, characterized in that, The preparation method of the modified carrier-type antibacterial agent includes the following steps: Step 1: Disperse tourmaline in toluene to form a uniform dispersion. Then add an acid anhydride modifier and catalyst to the dispersion. After the addition is complete, heat to 70-80℃, keep warm and stir for 4-8 hours, then stop heating, cool down and discharge the material. Collect the product, wash and dry it to obtain organic tourmaline. Step 2: Add organic tourmaline to deionized water and disperse it evenly. Then, add silver ammonia solution to the resulting dispersion to adjust the pH. Heat the mixture to 60-65℃ and keep it under heat for 4-6 hours. Then, stop heating and allow it to cool naturally. Centrifuge the solid material and wash and dry it to obtain the loaded tourmaline modified material. Step 3: Disperse the supported tourmaline modifier evenly in anhydrous ethanol, purge with nitrogen, then add a bridging agent. After the addition is complete, heat to 70-80℃, then add a platinum catalyst. Keep warm and stir for 2-4 hours, then add 1,3-bis(4-acryloyloxybutyl)tetramethyldisiloxane. Keep warm and stir for 12-16 hours, then cool down and discharge the material. The product is purified to obtain the modified carrier-type antibacterial agent.

3. The antibacterial and stain-resistant ceramic glaze according to claim 2, characterized in that, In step one, the anhydride modifier is maleic anhydride.

4. The antibacterial and stain-resistant ceramic glaze according to claim 2, characterized in that, In step one, the catalyst is p-toluenesulfonic acid.

5. The antibacterial and stain-resistant ceramic glaze according to claim 2, characterized in that, In step two, the pH is 10-12.

6. The antibacterial and stain-resistant ceramic glaze according to claim 2, characterized in that, In step three, the bridging agent is any one of 1,1,3,3,5,5-hexamethyltrisiloxane, decamethyldihydropentasiloxane, or 1,1,3,3,5,5,7,7-octamethyltetrasiloxane.

7. The antibacterial and stain-resistant ceramic glaze according to claim 2, characterized in that, In step three, the mass ratio of the supported tourmaline modifier, the bridging agent, and 1,3-bis(4-acryloyloxybutyl)tetramethyldisiloxane is 1:0.2-0.3:0.1-0.

2.

8. The antibacterial and stain-resistant ceramic glaze according to claim 1, characterized in that, The thickener is sodium carboxymethyl cellulose or carboxymethyl starch.

9. A method for preparing an antibacterial and stain-resistant ceramic glaze as described in claim 1, characterized in that, Includes the following steps: Step S1: Weigh each raw material according to the weight proportions; Step S2: First, add bentonite, potassium feldspar, kaolin, talc, dolomite, calcite, zircon, limestone, sanspar and modified carrier-type antibacterial agent into a ball mill and ball mill and mix until the residue on a 10,000-mesh sieve is less than 0.1% to obtain the precursor material. Step S3: Mix the precursor material and thickener thoroughly, then add water to adjust the specific gravity to 1.55-1.6 g / cm³. 3 To obtain ceramic glaze.

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