Antibacterial master batch, antibacterial ceramic glaze and antibacterial ceramic

Abstract

The invention relates to the technical field of ceramic tiles, in particular to an antibacterial master batch, an antibacterial ceramic glaze and antibacterial ceramic, and the antibacterial master batch is prepared by the following steps: step 1, taking crushed sepiolite, uniformly mixing with a hydrochloric acid solution, filtering, washing and drying after reaction to obtain sepiolite powder; taking sepiolite powder, adding water to prepare suspension liquid, mixing the sepiolite powder suspension liquid with a sodium phosphate solution for reaction, filtering and drying to obtain sepiolite treated by phosphoric acid; uniformly mixing sepiolite treated by phosphoric acid with a silver nitrate solution, reacting, filtering, washing, drying, and grinding into powder, so as to obtain an antibacterial master batch; according to the antibacterial master batch prepared by the invention and the ceramic prepared by utilizing the antibacterial master batch, the antibacterial effect and the antibacterial durability are remarkably improved, and the antibacterial master batch has certain discoloration resistance.

Description

Technical Field

[0001] The present application relates to the field of ceramic technology, and in particular to an antibacterial masterbatch, an antibacterial ceramic glaze and an antibacterial ceramic. Background Art

[0002] Antibacterial ceramics are an environmentally friendly functional material, a combination of antibacterial materials and ceramic products. Antibacterial ceramics retain the physical and chemical properties of the original ceramic products and add antibacterial functions. They are widely used in health, medical, home, civil or industrial construction and other industries. Glaze is a very thin layer of material covering the surface of ceramics. It is a glassy layer formed by a series of physical and chemical reactions such as high-temperature melting and crystallization after being fully mixed with some natural minerals and certain chemical raw materials in an appropriate proportion.

[0003] At present, the antibacterial ceramics on the market are mainly: metal ion doped type and catalytic surface coating type; among them, metal ion doped antibacterial ceramics are made by directly adding antibacterial agents containing metal ions such as silver, zinc, and copper into ceramic glazes and firing them, and the most widely used metal ions are silver ions; although silver ions have good antibacterial effects, they are easily discolored and inactivated during use, making the antibacterial effect of existing ceramics poor. Summary of the invention

[0004] The present invention aims to overcome at least one defect of the above-mentioned prior art and provide an antibacterial masterbatch, an antibacterial ceramic glaze and an antibacterial ceramic to solve the problem of poor antibacterial effect of existing ceramics.

[0005] One of the purposes of the present invention is to provide an antibacterial masterbatch, wherein the steps for preparing the antibacterial masterbatch are as follows:

[0006] S1, taking the crushed sepiolite, mixing it evenly with a hydrochloric acid solution, filtering it after the reaction, washing and drying it to obtain a sepiolite powder;

[0007] S2, taking sepiolite powder, adding water to make a suspension, mixing the sepiolite powder suspension with a phosphate solution, filtering and drying to obtain phosphoric acid-treated sepiolite;

[0008] S3, mixing the sepiolite treated with phosphoric acid and the silver nitrate solution evenly, filtering after the reaction, washing and drying, grinding into powder, and obtaining an antibacterial masterbatch.

[0009] In this scheme, an antibacterial masterbatch is added to the raw material of ceramic glaze. The sepiolite in the antibacterial masterbatch has a pore structure inside, a large surface area, and a strong adsorption capacity. Silver ions have bactericidal and antibacterial effects. Sepiolite is added to the antibacterial masterbatch. The adsorption of sepiolite is used to adsorb silver ions with antibacterial effects, so that the antibacterial masterbatch made of sepiolite has antibacterial properties, thereby making the surface of the prepared ceramic have an antibacterial effect. Specifically, phosphate can utilize active sites such as oxides and hydroxyls on the surface of sepiolite, so that the adsorption effect of sepiolite and phosphate is better. After phosphate treatment, it is mixed with silver nitrate and heated, and then the silver ions are more stably chelated on the sepiolite, which has a good antibacterial effect. This chelate not only utilizes the bactericidal ability of silver ions to make ceramics have a bactericidal and mildew-proof effect, but also the sepiolite carrier with a pore structure solves the problem of easy discoloration and inactivation of silver ions.

[0010] Furthermore, in step S1, the concentration of the hydrochloric acid is 4-6%, and the hydrochloric acid and sepiolite are mixed and reacted in a liquid-solid ratio of 34-36:0.5-1.5.

[0011] Furthermore, in step S2, the phosphate is sodium phosphate, and the concentration of the sodium phosphate solution is 0.3-0.7 mol / L.

[0012] Furthermore, in step S2, the sodium phosphate solution and the sepiolite powder suspension are mixed and reacted in a weight ratio of 24-26:3-5.

[0013] Furthermore, the concentration of the silver nitrate solution in step S3 is 0.1-0.3 mol / L.

[0014] Furthermore, in step S3, the silver nitrate solution and the phosphoric acid-treated sepiolite are mixed and reacted in a weight ratio of 20-22:1-2.

[0015] The second object of the present invention is to provide an antibacterial ceramic glaze, which comprises the following components in parts by weight: 4-6 parts of antibacterial masterbatch, 24-26 parts of kaolin, 19-20 parts of silica sand, 16-18 parts of potassium feldspar, and 18-20 parts of sodium feldspar.

[0016] The third object of the present invention is to provide an antibacterial ceramic, wherein the preparation method of the antibacterial ceramic is as follows:

[0017] P1. Dry-mix and grind the antibacterial ceramic glaze, sieve to obtain a mixture, keep the mixture at 1270-1290° C. for 20-40 min, take it out and pour it into water, quench it to obtain a frit, and grind the frit to obtain a basic glaze;

[0018] P2. Prepare raw materials according to the following weight ratio: 55-65 parts of basic glaze, 40-50 parts of solvent, 0.1-0.5 parts of defoamer, 0.4-0.8 parts of leveling agent, 5-8 parts of dispersant. Mix the basic glaze, solvent, defoamer, leveling agent and dispersant according to the ratio, stir and mix to prepare glaze slurry;

[0019] P3. Apply glaze slurry to the surface of the body, dry it and then fire it in a kiln. The firing temperature is 1100-1140°C, the firing cycle is 40-50 minutes, and the holding time at the firing temperature is 6-8 minutes to obtain ceramics.

[0020] Furthermore, the solvent is a mixture of any one or more of ethanol, isopropanol, acetone, cyclohexanone, and butyl acetate.

[0021] The antibacterial ceramic glaze of the present invention can significantly increase the antibacterial effect and antibacterial durability by adding the prepared antibacterial masterbatch, and the prepared antibacterial ceramic also has a certain anti-discoloration property through the scientific and reasonable formula of the present invention.

[0022] Compared with the prior art, the present invention has the following beneficial effects:

[0023] 1. The present invention utilizes sepiolite in the antibacterial masterbatch to adsorb silver ions with bactericidal ability to form a stable chelate. The chelate not only utilizes the bactericidal ability of silver ions to make the ceramic have a bactericidal and mildew-proof effect, but also the sepiolite carrier with a porous structure solves the problem of easy discoloration and inactivation of silver ions.

[0024] 2. In the formula of the present invention, active sites such as oxides and hydroxyl groups on the surface of sepiolite are utilized to make the adsorption effect of silver phosphate on sepiolite better, thereby making the silver ions more stably adsorbed on the sepiolite, solving the discoloration problem of silver ions, and making the prepared antibacterial ceramic glaze have good anti-discoloration properties. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] Figure 1 Schematic diagram of the steps of the antibacterial ceramic preparation process proposed in the present invention.

[0026] Figure 2 Schematic diagram of the steps of the antibacterial masterbatch preparation process proposed in the present invention.

[0027] Figure 3 This is a color change comparison diagram of the test sample in the anti-color change test of the present invention. DETAILED DESCRIPTION

[0028] One of the purposes of the present invention is to provide an antibacterial masterbatch, wherein the steps for preparing the antibacterial masterbatch are as follows:

[0029] S1, taking the crushed sepiolite, mixing it evenly with a hydrochloric acid solution, filtering it after the reaction, washing and drying it to obtain a sepiolite powder;

[0030] S2, taking sepiolite powder, adding water to make a suspension, mixing the sepiolite powder suspension with a phosphate solution, filtering and drying to obtain phosphoric acid-treated sepiolite;

[0031] S3, mixing the sepiolite treated with phosphoric acid and the silver nitrate solution evenly, filtering after the reaction, washing and drying, grinding into powder, and obtaining an antibacterial masterbatch.

[0032] In this scheme, an antibacterial masterbatch is added to the raw material of ceramic glaze. The sepiolite in the antibacterial masterbatch has a pore structure inside, a large surface area, and a strong adsorption capacity. Silver ions have bactericidal and antibacterial effects. Sepiolite is added to the antibacterial masterbatch. The adsorption of sepiolite is used to adsorb silver ions with antibacterial effects, so that the antibacterial masterbatch made of sepiolite has antibacterial properties, thereby making the surface of the prepared ceramic have an antibacterial effect. Specifically, phosphate can utilize active sites such as oxides and hydroxyls on the surface of sepiolite, so that the adsorption effect of sepiolite and phosphate is better. After phosphate treatment, it is mixed with silver nitrate and heated, and then the silver ions are more stably chelated on the sepiolite, which has a good antibacterial effect. This chelate not only utilizes the bactericidal ability of silver ions to make ceramics have a bactericidal and mildew-proof effect, but also the sepiolite carrier with a pore structure solves the problem of easy discoloration and inactivation of silver ions.

[0033] Preferably, the concentration of the hydrochloric acid is 4-6%, and the hydrochloric acid and sepiolite are mixed and reacted in a liquid-solid ratio of 34-36:0.5-1.5.

[0034] Preferably, the phosphate in S2 is sodium phosphate, and the concentration of the sodium phosphate solution is 0.3-0.7 mol / L. When the sodium phosphate solution is lower than this concentration, the antibacterial rate of the ceramics prepared is low, and when the sodium phosphate solution is higher than this concentration, the antibacterial rate of the ceramics prepared becomes low, and the antibacterial effect is poor.

[0035] Preferably, the ratio of the sodium phosphate solution to the sepiolite powder suspension in S2 is 24-26:3-5.

[0036] Preferably, the concentration of the silver nitrate solution in S3 is 0.1-0.3 mol / L.

[0037] Preferably, the ratio of the silver nitrate solution to the phosphoric acid-treated sepiolite in S3 is 20-22:1-2.

[0038] In a preferred embodiment, Figure 2 As shown, the preparation method of the antibacterial masterbatch is as follows:

[0039] S1, taking the crushed sepiolite, mixing it with 4-6% hydrochloric acid at a liquid-solid ratio of 34-36:0.5-1.5, filtering after the reaction, washing and drying to obtain sepiolite powder;

[0040] S2, taking sepiolite powder, adding water to make a suspension, mixing the sepiolite powder suspension with 0.3-0.7 mol / L sodium phosphate in a ratio of 24-26:3-5, filtering and drying, and obtaining phosphoric acid-treated sepiolite;

[0041] S3. Evenly mix the phosphoric acid-treated sepiolite with 0.1-0.3 mol / L silver nitrate solution in a ratio of 20-22:1-2, filter after the reaction, wash and dry, grind into powder, and obtain an antibacterial masterbatch.

[0042] The second object of the present invention is to provide an antibacterial ceramic glaze, which comprises the following components in parts by weight: 4-6 parts of antibacterial masterbatch, 24-26 parts of kaolin, 19-20 parts of silica sand, 16-18 parts of potassium feldspar, and 18-20 parts of sodium feldspar.

[0043] The third object of the present invention is to provide an antibacterial ceramic, such as Figure 1 As shown, the preparation method of the antibacterial ceramic is as follows:

[0044] P1. Dry-mix and grind the antibacterial ceramic glaze, sieve to obtain a mixture, keep the mixture at 1270-1290° C. for 20-40 min, take it out and pour it into water, quench it to obtain a frit, and grind the frit to obtain a basic glaze;

[0045] P2. Prepare raw materials according to the following weight ratio: 55-65 parts of basic glaze, 40-50 parts of solvent, 0.1-0.5 parts of defoamer, 0.4-0.8 parts of leveling agent, 5-8 parts of dispersant. Mix the basic glaze, solvent, defoamer, leveling agent and dispersant according to the ratio, stir and mix to prepare glaze slurry;

[0046] P3. Apply glaze slurry to the surface of the body, dry it and then fire it in a kiln. The firing temperature is 1100-1140°C, the firing cycle is 40-50 minutes, and the holding time at the firing temperature is 6-8 minutes to obtain ceramics.

[0047] The antibacterial ceramic glaze of the present invention can significantly increase the antibacterial effect by adding the prepared antibacterial masterbatch, and the prepared antibacterial ceramic also has a certain anti-discoloration property through the scientific and reasonable formula of the present invention.

[0048] In a specific implementation, the solvent is any one or more mixtures of ethanol, isopropanol, acetone, cyclohexanone and butyl acetate.

[0049] During specific implementation, the defoaming agent uses BYK-052N polyurethane varnish defoaming agent produced by Guangdong Yuanfeng New Materials Co., Ltd. or other commercially available products with similar performance; the leveling agent uses Levaslip8629 flow leveling agent produced by Hunan Jiaxinzhi New Materials Technology Co., Ltd. or other commercially available products with similar performance; the dispersant uses BYK142 dispersant produced by Shanghai Puhao Chemical Co., Ltd., a German BYK brand.

[0050] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0051] The experimental methods used in the following examples are conventional methods unless otherwise specified. The materials, reagents, methods and instruments used are conventional materials, reagents, methods and instruments in the art unless otherwise specified, and can be obtained through commercial channels by those skilled in the art.

[0052] Example 1

[0053] This embodiment provides an antibacterial ceramic, and the specific preparation method is as follows:

[0054] (1) Preparation of antibacterial masterbatch:

[0055] ① Take the crushed sepiolite, first use hydrogen peroxide to remove the surface organic matter, then take 4% hydrochloric acid and sepiolite at a liquid-solid ratio of 34:0.5 and mix them evenly, react for 2 hours, filter, wash with water, and dry the filter cake to obtain sepiolite powder;

[0056] ② Take the dried sepiolite powder and make a suspension, mix the sepiolite powder suspension with 0.3 mol / L sodium phosphate in a weight ratio of 24:3, keep in a constant temperature water bath at 70°C, react for 8 hours, filter and dry to obtain phosphoric acid-treated sepiolite;

[0057] ③ Evenly mix the phosphoric acid-treated sepiolite with 0.1 mol / L silver nitrate solution in a weight ratio of 20:1, place in a constant temperature water bath at 70°C, react for 16 hours, filter, wash, dry, and grind into powder to obtain an antibacterial masterbatch.

[0058] (2) Preparation of antibacterial ceramics:

[0059] ① Dry-mix and grind the antibacterial masterbatch, kaolin, silica sand, potassium feldspar and sodium feldspar in a weight ratio of antibacterial masterbatch: kaolin: silica sand: potassium feldspar: sodium feldspar = 4:24:19:16:18, sieve to obtain a mixture, keep the mixture at 1270-1290° C. for 20-40 min, take out and pour into water to quench to obtain a frit, grind the frit to obtain a basic glaze;

[0060] ② Prepare the raw materials according to the following weight ratio: 55 parts of basic glaze, 40 parts of solvent, 0.1 parts of defoamer, 0.4 parts of leveling agent, 5 parts of dispersant, wherein the solvent is one or more of ethanol, isopropanol, acetone, cyclohexanone, and butyl acetate; the defoamer is BYK-052N polyurethane varnish defoamer produced by Guangdong Yuanfeng New Materials Co., Ltd.; the leveling agent is Levaslip8629 flow leveling agent produced by Hunan Jiaxinzhi New Materials Technology Co., Ltd.; the dispersant is BYK142 dispersant produced by Shanghai Puhao Chemical Co., Ltd.;

[0061] ③ The basic glaze, solvent, defoamer, leveling agent and dispersant are mixed according to the proportions in step S2, and stirred to form a glaze slurry;

[0062] ④ Apply the glaze slurry to the ceramic surface, dry it and then fire it in an oxidizing flame in a roller kiln. The firing temperature is 1100-1140°C, the firing cycle is 40-50 minutes, and the holding time at the firing temperature is 6-8 minutes to obtain the ceramic.

[0063] Example 2

[0064] This embodiment provides an antibacterial ceramic, and the specific preparation method is as follows:

[0065] (1) Preparation of antibacterial masterbatch:

[0066] ① Take the crushed sepiolite, first use hydrogen peroxide to remove the surface organic matter, then take 5% hydrochloric acid and sepiolite at a liquid-solid ratio of 35:1 and mix them evenly, react for 2 hours, filter, wash with water, and dry the filter cake to obtain sepiolite powder;

[0067] ② Take the dried sepiolite powder and make a suspension, mix the sepiolite powder suspension with 0.3 mol / L sodium phosphate in a weight ratio of 24:3, keep in a constant temperature water bath at 70°C, react for 8 hours, filter and dry to obtain phosphoric acid-treated sepiolite;

[0068] ③ Evenly mix the phosphoric acid-treated sepiolite and 0.2 mol / L silver nitrate solution in a weight ratio of 21:1.5, keep in a constant temperature water bath at 70°C, react for 16 hours, filter, wash, dry, and grind into powder to obtain an antibacterial masterbatch.

[0069] (2) Preparation of antibacterial ceramics:

[0070] ① Dry-mix and grind the antibacterial masterbatch, kaolin, silica sand, potassium feldspar and sodium feldspar in a weight ratio of antibacterial masterbatch: kaolin: silica sand: potassium feldspar: sodium feldspar = 5:25:20:17:19, sieve to obtain a mixture, keep the mixture at 1270-1290° C. for 20-40 min, take out and pour into water to quench to obtain a frit, grind the frit to obtain a basic glaze;

[0071] ② Prepare the raw materials according to the following weight ratio: 60 parts of basic glaze, 45 parts of solvent, 0.3 parts of defoamer, 0.6 parts of leveling agent, 6 parts of dispersant, wherein the solvent is one or more of ethanol, isopropanol, acetone, cyclohexanone, and butyl acetate; the defoamer adopts BYK-052N polyurethane varnish defoamer produced by Guangdong Yuanfeng New Materials Co., Ltd.; the leveling agent adopts Levaslip8629 flow leveling agent produced by Hunan Jiaxinzhi New Materials Technology Co., Ltd.; the dispersant adopts BYK142 dispersant produced by Shanghai Puhao Chemical Co., Ltd.;

[0072] ③ The basic glaze, solvent, defoamer, leveling agent and dispersant are mixed according to the proportions in step S2, and stirred to form a glaze slurry;

[0073] ④ Apply the glaze slurry to the ceramic surface, dry it and then fire it in an oxidizing flame in a roller kiln. The firing temperature is 1100-1140°C, the firing cycle is 40-50 minutes, and the holding time at the firing temperature is 6-8 minutes to obtain the ceramic.

[0074] Example 3

[0075] This embodiment provides an antibacterial ceramic, and the specific preparation method is as follows:

[0076] (1) Preparation of antibacterial masterbatch:

[0077] ① Take the crushed sepiolite, first use hydrogen peroxide to remove the surface organic matter, then take 6% hydrochloric acid and sepiolite at a liquid-solid ratio of 36:1.5 and mix them evenly, react for 2 hours, filter, wash with water, and dry the filter cake to obtain sepiolite powder;

[0078] ② Take the dried sepiolite powder and make a suspension, mix the sepiolite powder suspension with 0.3 mol / L sodium phosphate in a weight ratio of 24:3, keep in a constant temperature water bath at 70°C, react for 8 hours, filter and dry to obtain phosphoric acid-treated sepiolite;

[0079] ③ Evenly mix the phosphoric acid-treated sepiolite and 0.3 mol / L silver nitrate solution in a weight ratio of 22:2, keep in a constant temperature water bath at 70°C, react for 16 hours, filter, wash, dry, and grind into powder to obtain an antibacterial masterbatch.

[0080] (2) Preparation of antibacterial ceramics:

[0081] ① Dry-mix and grind the antibacterial masterbatch, kaolin, silica sand, potassium feldspar and sodium feldspar in a weight ratio of antibacterial masterbatch: kaolin: silica sand: potassium feldspar: sodium feldspar = 6:26:21:18:20, sieve to obtain a mixture, keep the mixture at 1270-1290° C. for 20-40 min, take out and pour into water to quench to obtain a frit, grind the frit to obtain a basic glaze;

[0082] ② Prepare the raw materials according to the following weight ratio: 65 parts of basic glaze, 50 parts of solvent, 0.5 parts of defoamer, 0.8 parts of leveling agent, 8 parts of dispersant, wherein the solvent is one or more of ethanol, isopropanol, acetone, cyclohexanone, and butyl acetate; the defoamer is BYK-052N polyurethane varnish defoamer produced by Guangdong Yuanfeng New Materials Co., Ltd.; the leveling agent is Levaslip8629 flow leveling agent produced by Hunan Jiaxinzhi New Materials Technology Co., Ltd.; the dispersant is BYK142 dispersant produced by Shanghai Puhao Chemical Co., Ltd.;

[0083] ③ The basic glaze, solvent, defoamer, leveling agent and dispersant are mixed according to the proportions in step S2, and stirred to form a glaze slurry;

[0084] ④ Apply the glaze slurry to the ceramic surface, dry it and then fire it in an oxidizing flame in a roller kiln. The firing temperature is 1100-1140°C, the firing cycle is 40-50 minutes, and the holding time at the firing temperature is 6-8 minutes to obtain the ceramic.

[0085] Example 4

[0086] The difference between Example 4 and Example 1 is that:

[0087] The sepiolite powder suspension and 0.5 mol / L sodium phosphate were mixed in a ratio of 25:4 for reaction.

[0088] Example 5

[0089] The difference between Example 5 and Example 1 is that:

[0090] The sepiolite powder suspension and 0.7 mol / L sodium phosphate were mixed in a ratio of 26:5.

[0091] Comparative Example 1

[0092] The difference between Comparative Example 1 and Examples 1-3 is that:

[0093] The antibacterial ceramic glaze is prepared according to the following weight ratio of raw materials: 50 parts of basic glaze, 50 parts of solvent, 0.5 parts of defoaming agent, 0.8 parts of leveling agent, and 8 parts of dispersant.

[0094] Comparative Example 2

[0095] The difference between Comparative Example 2 and Examples 1-3 is that:

[0096] The antibacterial ceramic glaze is prepared according to the following weight ratio of raw materials: 70 parts of basic glaze, 50 parts of solvent, 0.5 parts of defoaming agent, 0.8 parts of leveling agent, and 8 parts of dispersant.

[0097] Comparative Example 3

[0098] The difference between Comparative Example 3 and Example 1 is that:

[0099] In the second step, the sodium phosphate solution is changed to a sodium chloride solution of the same concentration.

[0100] Comparative Example 4

[0101] The difference between Comparative Example 4 and Example 1 is that:

[0102] In the second step, the sepiolite powder suspension is mixed with 0.1 mol / L sodium phosphate in a ratio of 24:3.

[0103] Comparative Example 5

[0104] The difference between Comparative Example 5 and Example 1 is that:

[0105] In the second step, the sepiolite powder suspension is mixed with 0.9 mol / L sodium phosphate in a ratio of 24:3 for reaction.

[0106] Test Example 1

[0107] Escherichia coli and Staphylococcus aureus antibacterial rate test

[0108] Test samples: ceramics provided in Examples 1-5, and ceramics provided in Comparative Examples 1-5;

[0109] Test standard: According to GB15979-2002 standard, sterilization experiments were carried out on Escherichia coli and Staphylococcus aureus. The ceramics prepared in Examples 1-5 and Comparative Examples 1-5 were cleaned with sterile deionized water and then dried. Then 100 mL of sterile deionized water was added to the antibacterial ceramics, and then 1 mL of 1x10 3CFU / g of Escherichia coli and Staphylococcus aureus. After being placed at room temperature for 4 hours, the contents of Escherichia coli and Staphylococcus aureus in the deionized water of Examples 1-5 and Comparative Examples 1-5 were determined, and then the bactericidal rates were determined. The test results are shown in Table 1.

[0110] Table 1

[0111]

[0112]

[0113] It can be seen from the test data in Table 1 that the antibacterial ceramic prepared by the technical solution of the present invention has a better antibacterial effect than the comparative example.

[0114] Referring to Table 1, for the comparison between Examples 1-3 and Comparative Examples 1-2, it can be seen that the proportion of the basic glaze used in Comparative Example 1 is lower than the formula of the present invention, and the proportion of the basic glaze used in Comparative Example 2 is higher than the formula of the present invention. The antibacterial rates of the antibacterial ceramics prepared in Comparative Examples 1-2 against Escherichia coli and Staphylococcus aureus are both lower than 99%, while the antibacterial rates of the antibacterial ceramics prepared by the technical solution of the present invention against Escherichia coli and Staphylococcus aureus are both above 99%, which has better antibacterial effect than Comparative Examples 1-2.

[0115] From the comparison between Example 1 and Comparative Example 3, it can be seen that Example 1 uses sodium phosphate to treat sepiolite, and Comparative Example 3 uses sodium chloride to treat sepiolite. The antibacterial rate of Comparative Example 3 against Escherichia coli and Staphylococcus aureus is lower than 90%, while the antibacterial rates of the embodiments are all greater than 99%, indicating that in the process of treating sepiolite, the antibacterial effect of sodium phosphate is better than that of sodium chloride.

[0116] Phosphates can utilize active sites such as oxides and hydroxyls on the surface of sepiolite, making the adsorption effect of sepiolite and phosphate better, so that more silver ions are adsorbed, with better antibacterial effect. After phosphate treatment, it is mixed with silver nitrate and heated, and then the silver ions are more stably chelated on the sepiolite, further enhancing the antibacterial effect. Silver chloride has weaker adsorption than phosphate. The sepiolite treated with silver chloride adsorbs less silver ions, resulting in less silver content in the final antibacterial masterbatch and weaker antibacterial effect.

[0117] From the comparison between Example 1 and Comparative Examples 4-5, it can be seen that the concentration of sodium phosphate used in Comparative Examples 4-5 is not within the range defined by the present invention, and the antibacterial rate of the antibacterial ceramics prepared against Escherichia coli and Staphylococcus aureus is less than 99%, while the antibacterial rates of the antibacterial ceramics prepared by the technical solution of the present invention against Escherichia coli and Staphylococcus aureus are both above 99%, which has better antibacterial effect than Comparative Examples 4-5. Therefore, the concentration of sodium phosphate lower than 0.3 mol / L and higher than 0.7 mol / L will lead to a poor antibacterial effect of the prepared ceramics, and sodium phosphate has a better antibacterial effect within the concentration range of 0.3-0.7 mol / L specified in the present invention.

[0118] In summary, the sepiolite treated with phosphate adsorbs more silver ions with antibacterial effect than the sepiolite treated with silver chloride, so that the ceramics made from sepiolite have better antibacterial effect. The antibacterial rates of the ceramics prepared using the technical scheme of the present invention against Escherichia coli and Staphylococcus aureus are both above 99%, which has a good antibacterial effect compared to comparative examples 1-5.

[0119] Test Example 2

[0120] Discoloration resistance test

[0121] Test samples: ceramics provided in Examples 1-5, and ceramics provided in Comparative Examples 1-5;

[0122] Test standard: The ceramic antibacterial agents described in Examples 1-5 and Comparative Examples 1-5 were irradiated with ultraviolet light for 48 hours, and placed under natural conditions for 1 month, and their colors were observed. The test results are shown in Tables 2 and Figure 3 .

[0123] Table 2

[0124] Discoloration resistance Embodiment 1 Color remains unchanged Embodiment 2 Color remains unchanged Embodiment 3 Color remains unchanged Embodiment 4 Color remains unchanged Embodiment 5 Color remains unchanged Comparative Example 1 Color remains unchanged Comparative Example 2 Color remains unchanged Comparative Example 3 Slight discoloration Comparative Example 4 Color remains unchanged Comparative Example 5 Color remains unchanged

[0125] It can be seen from the data in Table 2 above that the ceramics prepared by the technical solution of the present invention have good anti-discoloration properties.

[0126] From the comparison between Example 1 and Comparative Example 3, it can be seen that sodium chloride is used to treat the sepiolite in the comparative example, and sodium chloride has a weaker adsorption force on the sepiolite than sodium phosphate, which ultimately makes the silver ions attached to the sepiolite easily discolored and inactivated, and the anti-discoloration property is poor.

[0127] The ceramic of the present invention improves the raw materials, adds an antibacterial masterbatch into the ceramic glaze, utilizes the adsorption property of sepiolite in the antibacterial masterbatch to adsorb silver ions with antibacterial effect, so that the finally prepared ceramic has antibacterial property. More specifically, the sepiolite in the antibacterial masterbatch is treated with sodium phosphate, and the sodium phosphate utilizes active sites such as oxides and hydroxyl groups on the surface of the sepiolite, so that both the sodium phosphate and the sepiolite have a more stable adsorption structure, so that the silver ions with antibacterial effect are more stably fixed on the sepiolite, and have a long-term and efficient bactericidal effect. In addition, the sepiolite carrier with a hollow structure avoids the problem of easy inactivation of silver ions, thereby making the silver ions more stably adsorbed on the sepiolite, solving the problem of discoloration of the silver ions, and making the prepared antibacterial ceramic have good anti-discoloration property.

[0128] Obviously, the above embodiments of the present invention are merely examples for clearly illustrating the technical solution of the present invention, and are not intended to limit the specific implementation methods of the present invention. Any modifications, equivalent substitutions and improvements made within the spirit and principles of the claims of the present invention shall be included in the protection scope of the claims of the present invention.

Claims

1. An antibacterial masterbatch, characterized in that: The preparation steps of the antibacterial masterbatch include: S1, taking the crushed sepiolite, mixing it evenly with a hydrochloric acid solution, filtering it after the reaction, washing and drying it to obtain a sepiolite powder; S2, taking sepiolite powder, adding water to make a suspension, mixing the sepiolite powder suspension with a phosphate solution, filtering and drying to obtain phosphoric acid-treated sepiolite; S3, mixing the sepiolite treated with phosphoric acid and the silver nitrate solution uniformly, filtering after the reaction, washing and drying, grinding into powder, and obtaining an antibacterial masterbatch.

2. The antibacterial masterbatch according to claim 1, characterized in that: The concentration of the hydrochloric acid in step S1 is 4-6%.

3. An antibacterial masterbatch according to claim 2, characterized in that: In step S1, the hydrochloric acid and sepiolite are mixed and reacted in a liquid-to-solid ratio of 34-36:0.5-1.

5.

4. The antibacterial masterbatch according to claim 1, characterized in that: In step S2, the phosphate in step S2 is sodium phosphate, and the concentration of the sodium phosphate solution is 0.3-0.7 mol / L.

5. The antibacterial masterbatch according to claim 4, characterized in that: In step S2, the sodium phosphate solution and the sepiolite powder suspension are mixed and reacted in a weight ratio of 24-26:3-5.

6. The antibacterial masterbatch according to claim 1, characterized in that: The concentration of the silver nitrate solution in step S3 is 0.1-0.3 mol / L.

7. The antibacterial masterbatch according to claim 6, characterized in that: In step S3, the silver nitrate solution and the phosphoric acid-treated sepiolite are mixed and reacted in a weight ratio of 20-22:1-2.

8. An antibacterial ceramic glaze, characterized in that: The antibacterial ceramic glaze comprises the following components in parts by weight: 4-6 parts of the antibacterial masterbatch according to any one of claims 1-7, 24-26 parts of kaolin, 19-20 parts of silica sand, 16-18 parts of potassium feldspar, and 18-20 parts of sodium feldspar.

9. An antibacterial ceramic, characterized in that: The preparation method of the antibacterial ceramic comprises the following steps: P1. Dry-mix and grind the antibacterial ceramic glaze according to claim 8, sieve to obtain a mixture, keep the mixture at 1270-1290° C. for 20-40 min, take it out and pour it into water, quench it to obtain a frit, and grind the frit to obtain a basic glaze; P2. Prepare raw materials according to the following weight ratio: 55-65 parts of basic glaze, 40-50 parts of solvent, 0.1-0.5 parts of defoamer, 0.4-0.8 parts of leveling agent, 5-8 parts of dispersant. Mix the basic glaze, solvent, defoamer, leveling agent and dispersant according to the ratio, stir and mix to prepare glaze slurry; P3. Apply glaze slurry to the surface of the body, dry it and then fire it in a kiln. The firing temperature is 1100-1140°C, the firing cycle is 40-50 minutes, and the holding time at the firing temperature is 6-8 minutes to obtain ceramics.

10. The antibacterial ceramic according to claim 9, characterized in that: The solvent is any one or more of ethanol, isopropanol, acetone, cyclohexanone and butyl acetate.

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