A rare earth antibacterial glaze composition and its preparation method

Abstract

This application relates to the field of antibacterial glaze technology, specifically providing a rare earth-based antibacterial glaze composition and its preparation method. The rare earth-based antibacterial glaze composition of this application, by weight, comprises the following raw material components: 3-10 parts potassium feldspar, 5-13 parts quartz powder, 0.5-2 parts alumina powder, 1-2.2 parts calcite, 1.5-4 parts dolomite, 50-80 parts frit, and 2-10 parts composite rare earth antibacterial agent dispersion; the composite rare earth antibacterial agent dispersion is obtained by reacting an amino-modified rare earth antibacterial agent with an epoxy-modified nano-inorganic oxide. The rare earth-based antibacterial glaze composition of this application features good antibacterial properties and high antibacterial uniformity.

Description

Technical Field

[0001] This application relates to the field of antibacterial glaze technology, specifically to a rare earth type antibacterial glaze composition and its preparation method. Background Technology

[0002] As people's living standards improve, they place higher demands on hygiene and health, leading to greater requirements for the antibacterial properties of sanitary ware such as toilets. The glaze is the surface layer of sanitary ware. Existing technologies report that using various antibacterial agents in the glaze of toilets and other sanitary ware can significantly improve the antibacterial properties of the glaze. This typically involves adding metal or metal compound antibacterial agents, such as nano-silver particles, silver oxide, rare earth antibacterial agents, and zinc oxide. The antibacterial agents are added to the glaze slurry and processed uniformly before being applied to the surface of the sanitary ware body and sintered together, resulting in sanitary ware with good antibacterial properties. Summary of the Invention

[0003] The antibacterial effect of an antibacterial agent depends on the uniformity of its mixing in the glaze slurry. The more uniform the mixing, the better the antibacterial properties of the glaze surface, especially the uniformity of antibacterial properties across different areas. However, in existing technologies, the antibacterial agent is usually directly mixed with the various raw material components of the glaze slurry and then ground, making it difficult to achieve a very high degree of uniformity. If a water-soluble inorganic salt antibacterial agent is used, metal ions may be adsorbed by other components in the glaze slurry, leading to poor antibacterial properties and uniformity. If a poorly soluble inorganic salt antibacterial agent is used, the dispersion uniformity needs to be improved. To solve the above technical problems, the inventors conducted extensive analysis and experimental research. Therefore, a rare earth-based antibacterial glaze composition and its preparation method are proposed.

[0004] The technical solution adopted in this application is as follows:

[0005] A rare earth antibacterial glaze composition, by weight, comprises the following raw material components: 3-10 parts potassium feldspar, 5-13 parts quartz powder, 0.5-2 parts alumina powder, 1-2.2 parts calcite, 1.5-4 parts dolomite, 50-80 parts frit, and 2-10 parts composite rare earth antibacterial agent dispersion.

[0006] The composite rare earth antibacterial agent dispersion was prepared according to the following method:

[0007] Rare earth antibacterial agents are surface-treated to obtain amino-modified rare earth antibacterial agents;

[0008] Surface treatment of nano-inorganic oxides yields epoxy-modified nano-inorganic oxides;

[0009] The amino-modified rare earth antibacterial agent and the epoxy-modified nano-inorganic oxide are co-dispersed in water and reacted to obtain the composite rare earth antibacterial agent dispersion.

[0010] Preferably, the surface treatment agent for the rare earth antibacterial agent is an aminosilane coupling agent, and the general formula of the aminosilane coupling agent is (NH2R). 1 Me x Si(OR 2 ) 3-x , where R 1 Selected from C3-C18 alkylene, C4-C18 substituted alkylene, C8-C18 cycloalkylene, or C8-C18 substituted cycloalkylene, where Me represents methyl and R represents methyl. 2 Selected from C1-C4 alkyl groups, x = 0-1.

[0011] Preferably, the surface treatment agent for the nano-inorganic oxide is an epoxy-based silane coupling agent, and the general formula of the epoxy-based silane coupling agent is [(CH2OCH)CH2OR]. 3 Me y Si(OR 4 ) 3-y , where R 3 Selected from C2-C18 alkylene, C3-C18 substituted alkylene, C8-C18 cycloalkylene, or C8-C18 substituted cycloalkylene, where Me represents methyl and R represents methyl. 4 Selected from C1-C4 alkyl groups, y = 0-1.

[0012] Preferably, the nano-inorganic oxide is selected from one or more combinations of nano-silica, nano-titanium dioxide, nano-alumina, nano-cerium oxide, nano-lanthanum oxide, nano-zinc oxide, and nano-yttrium oxide, and the average particle size of the nano-inorganic oxide is 5-100 nm.

[0013] Preferably, the reaction further includes the following step: adjusting the pH to 1-5.

[0014] Preferably, the weight ratio of the amino-modified rare earth antibacterial agent to the epoxy-modified nano-inorganic oxide is 1:0.3-5.

[0015] Preferably, the preparation method of the composite rare earth antibacterial agent dispersion further includes amino-modified silver nanoparticles; the amino-modified rare earth antibacterial agent, the amino-modified silver nanoparticles, and the epoxy-modified nano-inorganic oxide are dispersed together in water and reacted to obtain the composite rare earth antibacterial agent.

[0016] More preferably, the weight ratio of the amino-modified rare earth antibacterial agent, the amino-modified silver nanoparticles, and the epoxy-modified inorganic nano-oxide is 1:0.1-5:0.5-5.

[0017] More preferably, the reaction is followed by the step of adjusting the pH to 1-5.

[0018] A method for preparing a rare earth antibacterial glaze composition according to any of the above embodiments includes: mixing each of the raw material components, adding water and ball milling until the fineness of the slurry is such that the residue rate on a 325-mesh sieve is not more than 0.1%, and the weight content of the raw material components with a particle size of less than 10 μm is 75-90%, thus obtaining the slurry.

[0019] In summary, this application has the following beneficial effects:

[0020] 1. This application uses nano-inorganic oxides with good hydrophilicity as dispersants for rare earth antibacterial agents. Through the reaction of amino and epoxy groups, the rare earth antibacterial agents are combined with nano-inorganic oxides, which achieves good dispersion of rare earth antibacterial agents in water and has spatial distribution structural characteristics. This improves the dispersion uniformity of rare earth antibacterial agents in glaze slurry and gives the glaze layer a better antibacterial effect, especially with excellent antibacterial uniformity.

[0021] 2. In this application, the nano-inorganic oxide and rare earth antibacterial agent are reacted with epoxy groups and amino groups, wherein the secondary amino group forms a cation under acidic conditions, which can improve hydrophilicity and antistatic properties, and further improve the uniformity and stability of dispersion.

[0022] 3. The nano-inorganic oxides of this application can be further used with antibacterial nano-inorganic oxides and / or other antibacterial components, which can synergistically enhance the antibacterial effect of composite rare earth antibacterial agents with different antibacterial mechanisms. Detailed Implementation

[0023] To make the objectives, technical solutions, and advantages of this invention clearer, the technical solutions of this invention will be described in detail below.

[0024] Throughout this specification, unless otherwise specified, the terminology used herein should be understood as having the meaning commonly used in the art. Therefore, 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 this invention pertains. In the event of any conflict, this specification shall prevail.

[0025] This application provides a rare earth antibacterial glaze composition, which, by weight, comprises 3-10 parts potassium feldspar, 5-13 parts quartz powder, 0.5-2 parts alumina powder, 1-2.2 parts calcite, 1.5-4 parts dolomite, 50-80 parts frit, and 2-10 parts composite rare earth antibacterial agent dispersion.

[0026] The above-mentioned composite rare earth antibacterial agent dispersion was prepared according to the following method:

[0027] Rare earth antibacterial agents are surface-treated to obtain amino-modified rare earth antibacterial agents. In this application, the rare earth antibacterial agent is not particularly limited and can be a rare earth oxide, for example, one or a combination of cerium oxide, lanthanum oxide, yttrium oxide, europium oxide, and samarium oxide; it can also be a rare earth carbonate, for example, one or a combination of cerium carbonate, yttrium carbonate, europium carbonate, and samarium carbonate. To better disperse the rare earth antibacterial agent in water, the average particle size can be 5-100 μm, or further, 5-50 μm.

[0028] Surface treatment of nano-inorganic oxides yields epoxy-modified nano-inorganic oxides. In this application, there are no particular limitations on the nano-inorganic oxides. For example, they may be one or a combination of nano-silica, nano-titanium dioxide, nano-alumina, nano-cerium oxide, nano-lanthanum oxide, nano-zinc oxide, and nano-yttrium oxide. The average particle size of the nano-inorganic oxides is 5-100 nm, or further, the average particle size is 5-50 nm.

[0029] The above-mentioned amino-modified rare earth antibacterial agent and the above-mentioned epoxy-modified nano-inorganic oxide were co-dispersed in water and reacted to obtain a composite rare earth antibacterial agent dispersion.

[0030] In this application, the hydrophilic nano-inorganic oxide can be stably dispersed in water. Through chemical bonding with the rare earth antibacterial agent, the hydrophilic nano-inorganic oxide can assist in the dispersion of the rare earth antibacterial agent in water. In this application, the weight ratio of the aforementioned amino-modified rare earth antibacterial agent and epoxy-modified nano-inorganic oxide can be 1:0.3-5, or further, 1:0.5-3. For example, the weight ratio can be 1:0.5, 1:0.8, 1:1, 1:1.3, 1:1.6, 1:2, 1:2.2, 1:2.5, 1:3, etc. In this application, the weight percentage concentration of the composite rare earth antibacterial agent dispersion can be 20-50%, such as 20%, 25%, 30%, 35%, 40%, 45%, 50%, etc.

[0031] In a preferred embodiment of this application, the surface treatment agent for the rare earth antibacterial agent is an aminosilane coupling agent, the general formula of which is (NH2R). 1 Me x Si(OR 2 ) 3-x , where R 1 Selected from C3-C18 alkylene, C4-C18 substituted alkylene, C8-C18 cycloalkylene, or C8-C18 substituted cycloalkylene, where Me represents methyl and R represents methyl. 2The components are selected from C1-C4 alkyl groups, where x = 0-1. In this application, an aminosilane coupling agent is used to treat the rare earth antibacterial agent, which can graft amino groups onto the surface of the rare earth antibacterial agent. For example, the aminosilane coupling agent can be 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-β-aminoethyl-γ-aminopropyltrimethoxysilane, N-β-aminoethyl-γ-aminopropylmethyldimethoxysilane, N-β-aminoethyl-γ-aminopropyltriethoxysilane, 6-aminohexyl-3-aminopropyltrimethoxysilane, 6-aminohexyl-1-aminomethyltrimethoxysilane, etc.

[0032] In a preferred embodiment of this application, the surface treatment agent for the nano-inorganic oxide is an epoxy silane coupling agent, the general formula of which is [(CH2OCH)CH2OR]. 3 Me y Si(OR 4 ) 3-y , where R 3 Selected from C2-C18 alkylene, C3-C18 substituted alkylene, C8-C18 cycloalkylene, or C8-C18 substituted cycloalkylene, where Me represents methyl and R represents methyl. 4 Selected from C1-C4 alkyl groups, y = 0-1. In this application, an epoxy silane coupling agent is used to treat nano-inorganic oxides, which can graft epoxy groups onto the surface of the nano-inorganic oxides. For example, the epoxy silane coupling agent can be 3-(2,3-epoxypropoxy)propyltriethoxysilane, 3-(2,3-epoxypropoxy)propyltrimethoxysilane, 3-(2,3-epoxypropoxy)propylmethyldiethoxysilane, 3-(2,3-epoxypropoxy)propylmethyldimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltriethoxysilane, β-(3,4-epoxycyclohexyl)ethylmethyldimethoxysilane, epoxybutyltrimethoxysilane, 5,6-epoxyhexyltriethoxysilane, 5,6-epoxyhexyltrimethoxysilane, etc.

[0033] The reaction between amino and epoxy groups is highly reactive. The reaction can be carried out at room temperature for 1-24 hours, or it can be accelerated by heating, such as at 40-60°C, for 1-6 hours. Using amino and epoxy groups in the reaction serves two purposes: firstly, to chemically bond the nano-inorganic oxide and rare earth antibacterial agent; secondly, the secondary amino and hydroxyl groups produced by the reaction of primary amino and epoxy groups possess hydrophilicity, which can improve the stability of the composite rare earth antibacterial agent dispersion; and thirdly, the secondary amino groups can form cations in an acidic environment, exhibiting stronger hydrophilicity, while the strong electrostatic repulsion between cations further enhances the stability of the composite rare earth antibacterial agent dispersion. Preferably, after the reaction, the process further includes the following step: adding acid to adjust the pH of the dispersion to 1-5. The acid is not particularly limited and can be an inorganic acid, such as sulfuric acid, hydrochloric acid, or nitric acid, or an organic acid, such as acetic acid, formic acid, acetic acid, or malic acid.

[0034] To synergistically leverage the antibacterial mechanisms of several antibacterial agents and enhance their antibacterial efficacy, the preparation method of the composite rare earth antibacterial agent dispersion of this application may further include amino-modified silver nanoparticles. Specifically, the amino-modified rare earth antibacterial agent, amino-modified silver nanoparticles, and epoxy-modified inorganic nano-oxides are co-dispersed in water and reacted to obtain the composite rare earth antibacterial agent dispersion. The weight ratio of the amino-modified rare earth antibacterial agent, amino-modified silver nanoparticles, and epoxy-modified inorganic nano-oxides is 1:0.1-5:0.5-5.

[0035] To further improve the stability of the composite rare earth antibacterial agent dispersion containing nano-silver particles, the following step is included after the reaction: adding acid to adjust the pH of the dispersion to 1-5. There are no particular restrictions on the acid; it can be an inorganic acid, such as sulfuric acid, hydrochloric acid, or nitric acid, or an organic acid, such as acetic acid, formic acid, acetic acid, or malic acid.

[0036] In this application, the above-mentioned amino-modified rare earth antibacterial agent, amino-modified nano-silver particles, and epoxy-modified nano-inorganic oxides can be processed by the following method: 1-10 parts by weight of solid particles (such as nano-inorganic oxides) are dispersed in 100-500 parts by weight of organic solvent (such as anhydrous ethanol), and 0.1-1 parts by weight of the corresponding silane coupling agent (such as epoxy-silane coupling agent) are added. The mixture is stirred at room temperature for 1-12 hours, or the reaction is accelerated by heating, for example, reacting at 50-60°C for 1-5 hours. After the reaction is complete, the mixture is filtered or centrifuged to collect the solid. The solid can be washed with anhydrous ethanol and then dried to obtain the final product.

[0037] In this application, there are no particular restrictions on the frit; every 100 parts by weight can consist of 40-60 parts by weight of SiO2, 20-30 parts by weight of Al2O3, 5-15 parts by weight of CaO, 1-5 parts by weight of MgO, 1-5 parts by weight of Na2O, 0-1 parts by weight of K2O, 0-1 parts by weight of Fe2O3, and 0-3 parts by weight of ZnO. For example, a specific frit composition could be: 52.7 parts by weight of SiO2, 26.1 parts by weight of Al2O3, 12.4 parts by weight of CaO, 2.2 parts by weight of MgO, 3.1 parts by weight of Na2O, 0.7 parts by weight of K2O, 0.5 parts by weight of Fe2O3, and 2.3 parts by weight of ZnO.

[0038] Another aspect of this application provides a method for preparing the rare earth antibacterial glaze composition described in any of the above embodiments, comprising: mixing the raw material components, adding water and ball milling until the fineness of the slurry is such that the residue rate on a 325-mesh sieve does not exceed 0.1%, and the weight content of the raw material components with a particle size of less than 10 μm is 75-90%, thus obtaining the slurry.

[0039] Alternatively, the rare earth antibacterial glaze composition of this application can be prepared by the following method: mix the raw material components other than the composite rare earth antibacterial agent dispersion, add water and ball mill until the fineness of the slurry is such that the residue rate on a 325-mesh sieve does not exceed 0.1%, then add the composite rare earth antibacterial agent dispersion and ball mill until the weight content of the raw material components with a particle size of less than 10 μm is 75-90%, and the product is obtained.

[0040] The technical solution of this application will be described in detail below with reference to preparation examples, embodiments, and comparative examples. Unless otherwise specified, all parts in the following preparation examples, embodiments, and comparative examples are parts by weight.

[0041] Preparation Example 1

[0042] Five parts of nano-silica with an average particle size of 20 nm were dispersed in 200 parts of anhydrous ethanol. 0.2 parts of 6-aminohexyl-3-aminopropyltrimethoxysilane were added. The mixture was stirred at room temperature for 1 hour, then heated to 50-55 °C and reacted for 1 hour. After the reaction was complete, the mixture was centrifuged, the solid was collected, washed twice with anhydrous ethanol, and dried at 60 °C overnight to obtain amino-modified nano-silica.

[0043] Three parts of cerium carbonate with an average particle size of 45 μm were dispersed in 100 parts of anhydrous ethanol. 0.15 parts of 3-(2,3-epoxypropoxy)propyltriethoxysilane were added. The mixture was stirred at room temperature for 2 hours, then heated to 50-55 °C and reacted for 1 hour. After the reaction was complete, the mixture was centrifuged, the solid was collected, washed twice with anhydrous ethanol, and dried overnight at 60 °C to obtain epoxy-modified cerium carbonate.

[0044] The above-mentioned amino-modified nano-silica and epoxy-modified cerium carbonate were added to water at a weight ratio of 1:1 to prepare a concentration of 30wt%. The mixture was ultrasonically dispersed evenly, stirred and reacted for 2 hours, and then heated to 50-55℃ and reacted for 2 hours to obtain a composite rare earth antibacterial agent dispersion.

[0045] Preparation Example 2

[0046] In Preparation Example 1, dilute sulfuric acid was added to the composite rare earth antibacterial agent dispersion to make the pH of the dispersion 2.5, while the other steps remained unchanged.

[0047] Preparation Example 3

[0048] Three parts of nano-titanium dioxide with an average particle size of 15 nm were dispersed in 100 parts of anhydrous ethanol. 0.2 parts of N-β-aminoethyl-γ-aminopropyltrimethoxysilane were added. The mixture was stirred at room temperature for 2 hours, then heated to 50-55 °C and reacted for 1 hour. After the reaction was complete, the mixture was centrifuged, the solid was collected, washed twice with anhydrous ethanol, and dried overnight at 60 °C to obtain amino-modified nano-titanium dioxide.

[0049] One part of silver nanoparticles with an average particle size of 10 nm was dispersed in 100 parts of anhydrous ethanol, and 0.1 part of 3-aminopropyltrimethoxysilane was added. The mixture was stirred at room temperature for 2 hours, and then heated to 50-55 °C for 1 hour. After the reaction was completed, the mixture was centrifuged, the solid was collected, and the solid was washed twice with anhydrous ethanol and dried at 60 °C overnight to obtain amino-modified silver nanoparticles.

[0050] Seven parts of yttrium oxide with an average particle size of 60 μm were dispersed in 200 parts of anhydrous ethanol. 0.3 parts of 5,6-epoxyhexyltriethoxysilane were added, and the mixture was stirred at room temperature for 2 hours. The temperature was then raised to 50-55 °C and reacted for 2 hours. After the reaction was completed, the mixture was centrifuged, and the solid was collected. The solid was washed twice with anhydrous ethanol and dried at 60 °C overnight to obtain epoxy-modified yttrium oxide.

[0051] The above-mentioned amino-modified nano-titanium dioxide, amino-modified nano-silver particles and epoxy-modified yttrium oxide were added to water at a weight ratio of 1:0.1:0.8 to prepare a concentration of 25wt%. The mixture was ultrasonically dispersed evenly, stirred and reacted for 2 hours, and then heated to 50-55℃ and reacted for another 2 hours to obtain a composite rare earth antibacterial agent dispersion.

[0052] Preparation Example 4

[0053] In Preparation Example 2, dilute sulfuric acid was added to the composite rare earth antibacterial agent dispersion to make the pH of the dispersion 2, while the other steps remained unchanged.

[0054] Comparative Preparation Example 1

[0055] In Preparation Example 1, nano-silica and cerium carbonate were added to water at a weight ratio of 1:1 to prepare a concentration of 30 wt%. The mixture was then ultrasonically dispersed to obtain a composite antibacterial agent dispersion.

[0056] Comparative Preparation Example 2

[0057] In Preparation Example 3, nano-titanium dioxide, nano-silver particles, and epoxy-modified cerium carbonate were added to water at a weight ratio of 1:0.1:0.8 to prepare a concentration of 25 wt%. The mixture was then ultrasonically dispersed to obtain a composite antibacterial agent dispersion.

[0058] Test: Take 80 ml of each of the freshly prepared composite antibacterial agent dispersions from Preparation Examples 1-4 and Comparative Preparation Examples 1 and 2, place them in 100 ml transparent plastic bottles, seal them, and observe the time it takes for precipitation to occur in the dispersions. Three samples were tested in parallel. The results are shown in Table 1 below.

[0059] Table 1

[0060]

[0061] As shown in Table 1, the composite rare earth antibacterial agent dispersion of this application has good stability. Therefore, when the composite rare earth antibacterial agent dispersion of this application is used in glaze slurry, even if the glaze slurry is left to stand for a short period of time due to processes such as 0.5 days, the rare earth antibacterial agent will not settle or become uneven.

[0062] Example 1

[0063] The following raw material components were prepared: 6.3 parts potassium feldspar, 8.1 parts quartz powder, 1.1 parts alumina powder, 1.5 parts calcite, 2.3 parts dolomite, 72 parts frit, and 4 parts of the composite rare earth antibacterial agent dispersion of Preparation Example 1. The raw material components were mixed, water was added, and the mixture was ball-milled until the fineness of the slurry was such that the residue on a 325-mesh sieve was no more than 0.1%, and the weight content of the raw material components with a particle size of less than 10 μm was 82%, thus obtaining the rare earth antibacterial glaze composition.

[0064] The frit consists of 52.7 parts SiO2, 26.1 parts Al2O3, 12.4 parts CaO, 2.2 parts MgO, 3.1 parts Na2O, 0.7 parts K2O, 0.5 parts Fe2O3 and 2.3 parts ZnO.

[0065] Example 2

[0066] In Example 1, the composite rare earth antibacterial agent dispersion of Preparation Example 1 was replaced with an equal weight portion of the composite rare earth antibacterial agent dispersion of Preparation Example 2, while the remaining steps remained unchanged.

[0067] Comparative Example 1

[0068] In Example 1, the composite rare earth antibacterial agent dispersion of Preparation Example 1 was replaced with an equal weight portion of freshly prepared composite rare earth antibacterial agent dispersion of Comparative Preparation Example 1, while the remaining steps remained unchanged.

[0069] Example 3

[0070] The following raw material components were used: 7.5 parts potassium feldspar, 6.2 parts quartz powder, 1.4 parts alumina powder, 1.8 parts calcite, 3.1 parts dolomite, 75.2 parts frit from Example 1, and 8 parts of the composite rare earth antibacterial agent dispersion from Preparation Example 3. The other raw material components except the composite rare earth antibacterial agent dispersion were mixed, water was added, and the mixture was ball-milled until the fineness of the slurry was such that the residue on a 325-mesh sieve did not exceed 0.1%. Then, the composite rare earth antibacterial agent dispersion was added and ball-milled until the weight content of the raw material component with a particle size of less than 10 μm was 77%, thus obtaining the rare earth antibacterial glaze composition.

[0071] Example 4

[0072] In Example 3, the composite rare earth antibacterial agent dispersion of Preparation Example 3 was replaced with an equal weight portion of the composite rare earth antibacterial agent dispersion of Preparation Example 4, while the remaining steps remained unchanged.

[0073] Example 5

[0074] According to the same weight proportions of the composite rare earth antibacterial agent in the composite rare earth antibacterial agent dispersion, in Example 3, the composite rare earth antibacterial agent dispersion of Preparation Example 3 was replaced with the composite rare earth antibacterial agent dispersion of Preparation Example 1, and the remaining steps remained unchanged.

[0075] Example 6

[0076] In Example 3, the amount of the composite rare earth antibacterial agent dispersion prepared in Example 3 was reduced from 8 parts to 3 parts, while the remaining steps remained unchanged.

[0077] Example 7

[0078] In Example 3, the preparation of the composite rare earth antibacterial agent dispersion of Example 3 was adjusted from 8 parts to 10 parts, while the remaining steps remained unchanged.

[0079] Comparative Example 2

[0080] In Example 3, the composite rare earth antibacterial agent dispersion of Preparation Example 1 was replaced with an equal weight portion of freshly prepared composite rare earth antibacterial agent dispersion of Comparative Preparation Example 2, while the remaining steps remained unchanged.

[0081] Comparative Example 3

[0082] The following raw material components were used: 7.5 parts potassium feldspar, 6.2 parts quartz powder, 1.4 parts alumina powder, 1.8 parts calcite, 3.1 parts dolomite, 75.2 parts frit from Example 1, and 0.95 parts yttrium nitrate. The raw material components were mixed, water was added, and the mixture was ball-milled until the fineness of the slurry was such that the residue on a 325-mesh sieve did not exceed 0.1%, and the weight content of the raw material components with a particle size of less than 10 μm was 77%, thus obtaining the rare earth antibacterial glaze composition.

[0083] Comparative Example 4

[0084] The following raw material components were used: 7.5 parts potassium feldspar, 6.2 parts quartz powder, 1.4 parts alumina powder, 1.8 parts calcite, 3.1 parts dolomite, 75.2 parts frit from Example 1, 0.84 parts yttrium nitrate, and 0.11 parts nano-silver particles with an average particle size of 10 nm. The raw material components were mixed, water was added, and the mixture was ball-milled until the fineness of the slurry was such that the residue on a 325-mesh sieve did not exceed 0.1%, and the weight content of the raw material components with a particle size less than 10 μm was 77%, thus obtaining the rare earth antibacterial glaze composition.

[0085] The rare earth antibacterial glaze compositions of Examples 1-7 and Comparative Examples 1-4 were sieved to remove iron, and then adjusted to a specific gravity of 1.650-1.680. The mixtures were applied to a dry white glaze layer at a flow rate of 80-100 seconds, with a thickness controlled at 0.1-0.15 mm. The sintering procedure was as follows: 2 hours from room temperature to 500°C, 2 hours from 500°C to 900°C, 1.5 hours from 900°C to 1220°C, and sintered at a constant temperature of 1220-1240°C for 2 hours, followed by cooling.

[0086] Antibacterial uniformity: The antibacterial properties of the same glaze surface were tested at nine locations along the same direction (left, center, right, front, center, and back) according to JC / T897-2014 "Antibacterial Properties of Antibacterial Ceramic Products". The average value was taken and the standard deviation was calculated. Tested bacteria: Staphylococcus aureus and Escherichia coli.

[0087] The results are shown in Table 2 below.

[0088] Table 2 Antibacterial rate / %

[0089]

[0090]

[0091] Therefore, as can be seen from the data in Table 2, the glaze layer formed after sintering of the rare earth antibacterial glaze composition of this application has high antibacterial properties and good antibacterial uniformity.

[0092] This specific embodiment is merely an explanation of this application and is not intended to limit it. After reading this specification, those skilled in the art can make modifications to this embodiment without contributing any inventive step, but such modifications are protected by patent law as long as they fall within the scope of the claims of this application.

Claims

1. A rare earth-based antibacterial glaze composition, characterized in that, By weight, the raw material components include 3-10 parts potassium feldspar, 5-13 parts quartz powder, 0.5-2 parts alumina powder, 1-2.2 parts calcite, 1.5-4 parts dolomite, 50-80 parts frit, and 2-10 parts composite rare earth antibacterial agent dispersion. The composite rare earth antibacterial agent dispersion was prepared according to the following method: Rare earth antibacterial agents are surface-treated to obtain amino-modified rare earth antibacterial agents; the surface-treatment agent for the rare earth antibacterial agent is an aminosilane coupling agent, and the general formula of the aminosilane coupling agent is (NH2R). 1 Me x Si(OR 2 ) 3-x , where R 1 Selected from C3-C18 alkylene, C4-C18 substituted alkylene, C8-C18 cycloalkylene, or C8-C18 substituted cycloalkylene, where Me represents methyl and R represents methyl. 2 Selected from C1-C4 alkyl groups, x=0-1; the rare earth antibacterial agent is a rare earth oxide or a rare earth carbonate; Surface treatment of nano-inorganic oxides yields epoxy-modified nano-inorganic oxides; Nano-silver particles are surface-treated to obtain amino-modified nano-silver particles; The amino-modified rare earth antibacterial agent, the amino-modified silver nanoparticles, and the epoxy-modified inorganic nano-oxides are dispersed together in water, reacted, and the pH is adjusted to 1-5 to obtain the composite rare earth antibacterial agent dispersion. The weight ratio of the amino-modified rare earth antibacterial agent, the amino-modified silver nanoparticles, and the epoxy-modified inorganic nano-oxide is 1:0.1-5:0.5-5.

2. The rare earth antibacterial glaze composition according to claim 1, characterized in that, The surface treatment agent for the nano-inorganic oxide is an epoxy-based silane coupling agent, and the general formula of the epoxy-based silane coupling agent is [(CH2OCH)CH2OR]. 3 Me y Si(OR 4 ) 3-y , where R 3 Selected from C2-C18 alkylene, C3-C18 substituted alkylene, C8-C18 cycloalkylene, or C8-C18 substituted cycloalkylene, where Me represents methyl and R represents methyl. 4 Selected from C1-C4 alkyl groups, y=0-1.

3. The rare earth antibacterial glaze composition according to claim 1, characterized in that, The nano-inorganic oxide is selected from one or more combinations of nano-silica, nano-titanium dioxide, nano-alumina, nano-cerium oxide, nano-lanthanum oxide, nano-zinc oxide, and nano-yttrium oxide, and the average particle size of the nano-inorganic oxide is 5-100 nm.

4. A method for preparing a rare earth-type antibacterial glaze composition according to any one of claims 1-3, characterized in that, include: Mix all the raw material components, add water, and ball mill until the fineness of the slurry is such that the residue rate on a 325-mesh sieve is no more than 0.1%, and the weight content of the raw material components with a particle size of less than 10 μm is 75-90%.

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