An antibacterial glaze and its preparation method

Abstract

This application relates to the field of ceramic technology, and particularly to an antibacterial glaze and a preparation method thereof. The raw materials include the following parts by mass: 25-35 parts of potassium feldspar, 25-35 parts of quartz powder, 4-10 parts of kaolin, 1-5 parts of alumina, 10-18 parts of calcite, 4-8 parts of wollastonite, 3-6 parts of zinc oxide, 8-12 parts of frit, 1-3 parts of talc powder, and 2-4 parts of antibacterial agent. By precisely controlling the particle size distribution of the raw materials, the surface density and fineness of the antibacterial glaze are improved, and the obtained ceramic glaze surface has the functions of easy cleaning and high-efficiency antibacterial.

Description

Technical Field

[0001] This application relates to the field of ceramic technology, and particularly to an antibacterial glaze and a preparation method thereof. Background Art

[0002] Antibacterial materials are an important part of a healthy life. Specifically in the sanitary ware industry, sanitary wares are widely used in daily life for their beauty and practicality. However, when people use toilets, a large number of bacteria will breed.

[0003] Sanitary wares are prone to adhering dirt, which not only affects their beauty but also becomes a breeding ground for bacteria. Developing sanitary ceramics with easy-cleaning and antibacterial functions meets the market demand without increasing the production process and without reducing the glaze quality. Summary of the Invention

[0004] The purpose of this application is to provide an easy-cleaning and antibacterial sanitary ceramic and its preparation process in view of the deficiencies of the current technology. By precisely controlling the particle size distribution of raw materials, the density and fineness of the antibacterial glaze surface are improved. At the same time, an inorganic antibacterial material is added, and the obtained ceramic glaze has the functions of easy cleaning and antibacterial.

[0005] To achieve the above purpose, this application provides the following technical solutions:

[0006] An antibacterial glaze, comprising the following raw materials in parts by mass: 25 - 35 parts of potassium feldspar, 25 - 35 parts of quartz powder, 4 - 10 parts of kaolin, 1 - 5 parts of alumina, 10 - 18 parts of calcite, 4 - 8 parts of wollastonite, 3 - 6 parts of zinc oxide, 8 - 12 parts of frit, 1 - 3 parts of talc powder, 2 - 4 parts of antibacterial agent. The particle size distribution of the potassium feldspar, the quartz powder, the kaolin, the alumina, the calcite, the wollastonite, the zinc oxide, the frit, and the talc powder is 7 - 10% for 325 - 625 mesh, 10 - 15% for 625 - 1250 mesh, and 75% - 83% for less than 1250 mesh.

[0007] Preferably, an antibacterial glaze, comprising the following raw materials in parts by mass: 29 - 31 parts of potassium feldspar, 27 - 30 parts of quartz powder, 4 - 6 parts of kaolin, 2 - 3 parts of alumina, 13 - 15 parts of calcite, 5 - 7 parts of wollastonite, 3 - 4 parts of zinc oxide, 8 - 10 parts of frit, 1 - 3 parts of talc powder, 2 - 3 parts of antibacterial agent. The particle size distribution of the potassium feldspar, the quartz powder, the kaolin, the alumina, the calcite, the wollastonite, the zinc oxide, the frit, and the talc powder is 7 - 8% for 325 - 625 mesh, 11 - 13% for 625 - 1250 mesh, and 78% - 81% for less than 1250 mesh.

[0008] By adopting the above technical solution, through precise control of the particle size distribution of the raw materials, the density and fineness of the glaze layer surface are improved, thereby enhancing the surface easy-to-clean performance.

[0009] The function of alumina is to increase the heat-resistant temperature of the formulation system and avoid the low antibacterial effect caused by excessive melting of the material during the firing process; the function of zinc oxide is, on the one hand, as a solvent to increase the melting performance of the material, and on the other hand, to increase the antibacterial function of the product against the contacted bacteria.

[0010] Preferably, the antibacterial agent is an inorganic antibacterial agent, and the inorganic antibacterial agent is composed of zinc phosphate, vanadium dioxide, nano-soluble glass silver-loaded antibacterial agent and thorium dioxide.

[0011] By adopting the above technical solution, the antibacterial mechanism of zinc phosphate is as follows: the surface glaze layer can release Zn 2+ , Zn 2+ is freed, because Zn 2+ has oxidation-reduction properties. When Zn 2+ contacts the cell membrane and reacts with organic substances, attacking the membrane protein structure to complete the sterilization process. Therefore, zinc ions need to directly contact the bacteria. After the bacteria are killed, Zn 2+ will be freed from the bacterial cells again and contact other bacteria to complete continuous sterilization. The function of thorium dioxide is to be antibacterial, and its mechanism of action is as follows: The atomic number of Th element is high and the atomic radius is large. It has an unfilled electron shell structure, diverse electron energy levels, and is very easy to lose outer electrons, with special variable valence characteristics and chemical activity. Therefore, its radiation energy is high and the half-life is long. Therefore, a high concentration of negative ions is generated near the glaze surface, which can complete the following functions: a. Acting on the cell wall and cell membrane system; b. Acting on reaction enzymes or other active substances; c. Acting on genetic materials or genetic particle structures; Therefore, it still has good antibacterial effects on bacteria that do not directly contact the glaze surface or are isolated due to dust and stains. The antibacterial mechanism of the nano-soluble glass silver-loaded antibacterial agent: Ag + can play the role of a catalytic active center, activate the surrounding oxygen, generate hydroxyl radicals (·OH) and reactive oxygen ions (O 2- ), which have strong oxidation-reduction effects and destroy the proliferation ability of microbial cells, inhibiting or killing bacteria.

[0012] Preferably, the inorganic antibacterial agent is a mixture of zinc phosphate, vanadium dioxide, nano-soluble glass silver-loaded antibacterial agent and thorium dioxide in a mass percentage of 1:2 - 4:3 - 5:4 - 6.

[0013] Preferably, the silver ion mass content in the nano-soluble glass silver-loaded antibacterial agent is 0.1%.

[0014] By adopting the above technical solutions, the selected composite inorganic antibacterial agent has excellent antibacterial effects on sanitary ceramics, and the antibacterial rates against Staphylococcus aureus and Escherichia coli are greater than 99.9%.

[0015] A preparation method of an antibacterial glaze, using the raw materials of the above antibacterial glaze, the preparation method includes the following steps:

[0016] S1 Mixing materials: Screen, weigh and mix potassium feldspar, quartz powder, kaolin, alumina, calcite, wollastonite, zinc oxide, frit, talc powder evenly according to the formula ratio to obtain the glaze.

[0017] S2 Preparing glaze slurry: Put the glaze into a stirring device, and add water and antibacterial agent to stir and mix to obtain the glaze slurry.

[0018] S3 Glazing: Spray the obtained glaze slurry onto the surface of the green body by pressure glazing method to obtain a glazed product with a glaze layer thickness of 0.1 - 0.2 mm.

[0019] S4 Firing: After drying the glazed product at 130 °C, load it into a kiln, fire it, and then cool it naturally to room temperature to obtain an antibacterial glaze ceramic product.

[0020] Preferably, in step S2 of preparing glaze slurry, the performance parameters of the glaze slurry are: specific gravity is 1.650 kg / L - 1.680 kg / L, and viscosity is 80 - 100 seconds / 100 mL.

[0021] Preferably, the green body is a ceramic product with a white glaze layer sprayed on and the surface dried well.

[0022] Preferably, the firing includes: after loading into the kiln, the heating rate is 120 °C / hour, the firing temperature is 1220 - 1240 °C, and the firing time is 2 - 3 hours to fire the antibacterial glaze ceramic product.

[0023] By adopting the above technical solutions, spraying the obtained glaze slurry onto the surface of the green body that has just been dried, the glaze layer and the matrix ceramic layer are integrated into one body, and the bonding force is very strong. At the same time, they are sintered together, saving a large amount of energy.

[0024] To sum up, the beneficial technical effects of this application are as follows:

[0025] 1) By precisely controlling the particle size distribution of the raw materials, the surface density and fineness of the antibacterial glaze are improved, and the obtained ceramic glaze surface has the function of being easy to clean.

[0026] 2) The inorganic antibacterial agent realizes the combined antibacterial effect through zinc phosphate, vanadium dioxide, nano-soluble glass silver-loaded antibacterial agent and thorium dioxide, and can achieve a non-contact antibacterial process, sterilize bacteria that do not directly contact the glaze surface, has good antibacterial effect, the antibacterial rates against Staphylococcus aureus and Escherichia coli are greater than 99.0%, and the antibacterial persistence is strong. Detailed implementation manners

[0027] The following will describe the implementation schemes of the present application in detail in combination with examples and preparation examples. However, those skilled in the art will understand that the following examples are only used to illustrate the present application and should not be regarded as limiting the scope of the present application. For those not specified in the examples, they are carried out according to conventional conditions or the conditions recommended by the manufacturer. For the reagents or instruments not specified for the manufacturer, they are all conventional products that can be obtained through commercial purchase.

[0028] Example 1

[0029] An antibacterial glaze includes the following raw materials in parts by mass: 25 kg of potassium feldspar, 25 kg of quartz powder, 4 kg of kaolin, 1 kg of alumina, 10 kg of calcite, 4 kg of wollastonite, 3 kg of zinc oxide, 8 kg of frit, 1 kg of talc powder, and 2 kg of antibacterial agent. The particle size distribution of the potassium feldspar, the quartz powder, the kaolin, the alumina, the calcite, the wollastonite, the zinc oxide, the frit, and the talc powder is 7% for 325 mesh - 625 mesh, 10% for 625 - 1250 mesh, and 83% for less than 1250 mesh. The inorganic antibacterial agent is a mixture of zinc phosphate, vanadium dioxide, nano-soluble glass silver-loaded antibacterial agent and thorium dioxide in a mass percentage of 1:2:3:4. The silver ion mass content in the nano-soluble glass silver-loaded antibacterial agent is 0.1%.

[0030] Example 2

[0031] An antibacterial glaze includes the following raw materials in parts by mass: 35 kg of potassium feldspar, 35 kg of quartz powder, 10 kg of kaolin, 5 kg of alumina, 18 kg of calcite, 8 kg of wollastonite, 6 kg of zinc oxide, 12 kg of frit, 3 kg of talc powder, and 4 kg of antibacterial agent. The particle size distribution of the potassium feldspar, the quartz powder, the kaolin, the alumina, the calcite, the wollastonite, the zinc oxide, the frit, and the talc powder is 10% for 325 mesh - 625 mesh, 15% for 625 - 1250 mesh, and 75% for less than 1250 mesh. The inorganic antibacterial agent is a mixture of zinc phosphate, vanadium dioxide, nano-soluble glass silver-loaded antibacterial agent and thorium dioxide in a mass percentage of 1:4:5:6. The silver ion mass content in the nano-soluble glass silver-loaded antibacterial agent is 0.1%.

[0032] Example 3

[0033] An antibacterial glaze, comprising raw materials in the following parts by mass: 30 kg of potassium feldspar, 28 kg of quartz powder, 5 kg of kaolin, 3 kg of alumina, 14 kg of calcite, 6 kg of wollastonite, 4 kg of zinc oxide, 10 kg of frit, 2 kg of talc powder, and 3 kg of antibacterial agent. The particle size distribution of the potassium feldspar, the quartz powder, the kaolin, the alumina, the calcite, the wollastonite, the zinc oxide, the frit, and the talc powder is 8% for 325 mesh - 625 mesh, 12% for 625 - 1250 mesh, and 80% for less than 1250 mesh. The inorganic antibacterial agent is a mixture of zinc phosphate, vanadium dioxide, nano-soluble glass silver-loaded antibacterial agent, and thorium dioxide in a mass percentage ratio of 1:3:4:5. The silver ion mass content in the nano-soluble glass silver-loaded antibacterial agent is 0.1%.

[0034] Comparative Example 1

[0035] Same as Example 3, except that: the particle size distribution of the potassium feldspar, the quartz powder, the kaolin, the alumina, the calcite, the wollastonite, the zinc oxide, the frit, and the talc powder is 89% for 325 mesh - 625 mesh and 11% for 625 - 1250 mesh.

[0036] Comparative Example 2

[0037] Same as Example 3, except that: the inorganic antibacterial agent is a mixture of zinc phosphate, nano-soluble glass silver-loaded antibacterial agent, and thorium dioxide in a mass percentage ratio of 1:4:5, without vanadium dioxide.

[0038] Preparation Example 1

[0039] A preparation method of an antibacterial glaze, using the raw materials in Example 1, and the preparation method comprises the following steps:

[0040] S1 Mixing: Screen, weigh, and mix the potassium feldspar, quartz powder, kaolin, alumina, calcite, wollastonite, zinc oxide, frit, and talc powder according to the formula ratio to obtain the glaze.

[0041] S2 Glaze slurry preparation: Put the glaze into a stirring device, and add water and antibacterial agent for stirring and mixing to obtain the glaze slurry. The specific gravity of the glaze slurry is 1.650 kg, and the viscosity is 100 seconds / 100 mL.

[0042] S3 Glazing: Spray the obtained glaze slurry onto the surface of the ceramic product with a good white glaze layer and a well-dried surface layer by the pressure glazing method to obtain a glazed product with a glaze layer thickness of 0.2 mm.

[0043] S4 Firing: After drying the glazed product at 130°C, it is loaded into a kiln. The firing process is as follows: the heating rate is 120°C per hour, the firing temperature is 1220°C, the firing time is 3 hours, and it is naturally cooled to room temperature to obtain an antibacterial glazed ceramic product.

[0044] Preparation Example 2

[0045] A method for preparing an antibacterial glaze, using the raw materials in Example 2, and its preparation method includes the following steps:

[0046] S1 Mixing: Feldspar, quartz powder, kaolin, alumina, calcite, wollastonite, zinc oxide, frit, and talc powder are screened, weighed, and mixed evenly according to the formula ratio to obtain a glaze.

[0047] S2 Glaze Slurry Preparation: The glaze is put into a stirring device, and water and an antibacterial agent are added and stirred and mixed to obtain a glaze slurry. The specific gravity of the glaze slurry is 1.680 kg / L, and the viscosity is 80 seconds / 100 mL.

[0048] S3 Glazing: The obtained glaze slurry is sprayed onto the surface of the ceramic product with a dried surface layer of the glaze layer that has been sprayed with white glaze by the pressure glazing method to obtain a glazed product with a glaze layer thickness of 0.1 mm.

[0049] S4 Firing: After drying the glazed product at 130°C, it is loaded into a kiln. The firing process is as follows: the heating rate is 120°C per hour, the firing temperature is 1240°C, the firing time is 2 hours, and it is naturally cooled to room temperature to obtain an antibacterial glazed ceramic product.

[0050] Preparation Example 3

[0051] A method for preparing an antibacterial glaze, using the raw materials in Example 4, and its preparation method includes the following steps:

[0052] S1 Mixing: Feldspar, quartz powder, kaolin, alumina, calcite, wollastonite, zinc oxide, frit, and talc powder are screened, weighed, and mixed evenly according to the formula ratio to obtain a glaze.

[0053] S2 Glaze Slurry Preparation: The glaze is put into a stirring device, and water and an antibacterial agent are added and stirred and mixed to obtain a glaze slurry. The specific gravity of the glaze slurry is 1.670 kg / L, and the viscosity is 90 seconds / 100 mL.

[0054] S3 Glazing: The obtained glaze slurry is sprayed onto the surface of the ceramic product with a dried surface layer of the glaze layer that has been sprayed with white glaze by the pressure glazing method to obtain a glazed product with a glaze layer thickness of 0.15 mm.

[0055] S4 Firing: After drying the glazed product at 130 °C, it is loaded into a kiln. The firing process is as follows: the heating rate is 120 °C / hour, the firing temperature is 1230 °C, and the firing time is 2.5 hours. It is then naturally cooled to room temperature to obtain the antibacterial glazed ceramic product.

[0056] Preparation Example 4

[0057] Same as Preparation Example 3, except that the materials in Comparative Example 1 are used.

[0058] Preparation Example 5

[0059] Same as Preparation Example 3, except that the materials in Comparative Example 2 are used.

[0060] Performance Test

[0061] Samples were taken from the antibacterial glazed ceramic products in Preparation Examples 1 - 5 and tested. The results of the easy - cleaning test are shown in Table 1.

[0062] Easy - cleaning property: Using the detection method of GB / T 31859 - 2015, A < 0.5 g / cm 2 , belonging to easy - cleaning ceramics.

[0063] Table 1

[0064] Preparation Example 1 Preparation Example 2 Preparation Example 3 Preparation Example 4 Preparation Example 5 <![CDATA[Ease of cleaning g / cm 3 > 0.08 0.3 0.12 0.5 0.12

[0065] From the analysis of Preparation Example 4, the particle size of the raw materials is larger than that of Preparation Example 3, and the easy - cleaning property of the surface of the obtained antibacterial glazed ceramic product is poor. This is mainly because the large particle size of the raw materials results in poor compactness of the glaze layer obtained after spraying, with pores, so it is not easy to clean.

[0066] Samples were taken from the antibacterial glazed ceramic products in Preparation Examples 1 - 5 and sent to the Guangdong Provincial Microbial Analysis and Inspection Center for antibacterial detection according to the antibacterial performance standard of JC / T 897 - 2014 for antibacterial ceramic products. The test results correspond to Tables 2, 3, 4, 5, and 6.

[0067] Table 2

[0068]

[0069] Table 3

[0070]

[0071] Table 4

[0072]

[0073]

[0074] Table 5

[0075]

[0076] Table 6

[0077]

[0078] From the analysis of Table 6, since there is no vanadium dioxide in the composite inorganic antibacterial agent, its antibacterial performance decreases, and the coordination effect of the composite inorganic antibacterial agent becomes poor.

[0079] The antibacterial glaze ceramic products obtained in Preparation Examples 1-5 were tested in accordance with GB 6566-2010 "Limit of Radionuclides in Building Materials". The results showed that the internal and external exposure indices met the requirements of Class A decorative building materials in the GB 6566-2010 standard.

[0080] The above embodiments and preparation examples are only used to explain the technical solutions of the present invention rather than limit them. Although the above embodiments have specifically described the present invention, those skilled in the art should understand that modifications or equivalent replacements can still be made to the specific embodiments of the present invention. Any modification and equivalent replacement without departing from the spirit and scope of the present invention should be covered by the scope of the claims of the present invention.

Claims

1. An antibacterial glaze, characterized in that, It comprises raw materials in the following parts by mass: 29 - 31 parts of potassium feldspar, 27 - 30 parts of quartz powder, 4 - 6 parts of kaolin, 2 - 3 parts of alumina, 13 - 15 parts of calcite, 5 - 7 parts of wollastonite, 3 - 4 parts of zinc oxide, 8 - 10 parts of frit, 1 - 3 parts of talc powder, and 2 - 3 parts of antibacterial agent. The particle size distribution of the potassium feldspar, the quartz powder, the kaolin, the alumina, the calcite, the wollastonite, the zinc oxide, the frit, and the talc powder is such that 7 - 8% is 325 - 625 mesh, 11 - 13% is 625 - 1250 mesh, and 78% - 81% is less than 1250 mesh; the antibacterial agent is an inorganic antibacterial agent, and the inorganic antibacterial agent is a mixture of zinc phosphate, vanadium dioxide, silver - loaded nano - soluble glass antibacterial agent, and thorium dioxide in a mass percentage ratio of 1:2 - 4:3 - 5:4 - 6. The silver ion mass content in the silver - loaded nano - soluble glass antibacterial agent is 0.1%.

2. A preparation method of an antibacterial glaze, characterized in that, Using the raw materials of the antibacterial glaze according to Claim 1, its preparation method comprises the following steps: S1 Mixing materials: Screen, weigh, and uniformly mix potassium feldspar, quartz powder, kaolin, alumina, calcite, wollastonite, zinc oxide, frit, and talc powder according to the formula ratio to obtain the glaze; S2 Preparing glaze slurry: Put the glaze into a stirring device, add water and the antibacterial agent, and stir and mix to obtain a glaze slurry with a specific gravity of 1.650 kg / L - 1.680 kg / L and a viscosity of 80 - 100 seconds / 100 mL; S3 Glazing: Spray the obtained glaze slurry onto the surface of the green body by the pressure glazing method to obtain a glazed product with a glaze layer thickness of 0.1 - 0.2 mm; the green body is a ceramic product with a white glaze layer sprayed on it and the surface dried well; S4 Firing: After drying the glazed product at 130°C, load it into a kiln for firing. The heating rate is 120°C / hour, the firing temperature is 1220 - 1240°C, the firing time is 2 - 3 hours, and then cool it naturally to room temperature to obtain the antibacterial glaze ceramic product.

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