阅读说明：本技术 一种抗菌陶瓷砖及其制备方法 (Antibacterial ceramic tile and preparation method thereof ) 是由 柯善军 田维 蒙臻明 马超 于 2019-12-13 设计创作，主要内容包括：本发明公开了一种抗菌陶瓷砖,其包括设置在陶瓷砖上表面的抗菌釉层,所述抗菌釉层由基础透明釉和磷酸锆负载复合抗菌剂组成,所述磷酸锆负载复合抗菌剂包括磷酸锆载体和复合抗菌剂,所述磷酸锆负载复合抗菌剂积聚于抗菌釉层上部,所述复合抗菌剂的抗菌有效成分为抗菌氧化物和抗菌离子。本发明在陶瓷砖表面的抗菌釉层中引入磷酸锆,利用磷酸锆密度低的特点,经高温烧成后积聚在釉层上部形成具有多孔结构的表面,从而作为复合抗菌剂附着的载体,强化了抗菌材料与陶瓷砖的结合力,赋予了该陶瓷砖更长效、更优异的抗菌性能,同时不影响陶瓷砖表面外观装饰效果。本发明还公开了该抗菌陶瓷砖的制备工艺,其步骤简单,可控性强,有利于大规模工业化生产。(The invention discloses an antibacterial ceramic tile which comprises an antibacterial glaze layer arranged on the upper surface of the ceramic tile, wherein the antibacterial glaze layer is composed of basic transparent glaze and a zirconium phosphate loaded composite antibacterial agent, the zirconium phosphate loaded composite antibacterial agent comprises a zirconium phosphate carrier and a composite antibacterial agent, the zirconium phosphate loaded composite antibacterial agent is accumulated on the upper part of the antibacterial glaze layer, and the antibacterial effective components of the composite antibacterial agent are antibacterial oxide and antibacterial ions. According to the invention, zirconium phosphate is introduced into the antibacterial glaze layer on the surface of the ceramic tile, and the zirconium phosphate is sintered at high temperature by utilizing the characteristic of low density of the zirconium phosphate and then accumulated on the upper part of the glaze layer to form the surface with a porous structure, so that the zirconium phosphate is used as a carrier attached with the composite antibacterial agent, the binding force of the antibacterial material and the ceramic tile is enhanced, the ceramic tile is endowed with longer-acting and more excellent antibacterial performance, and the appearance decoration effect of the surface of the ceramic tile is not influenced. The invention also discloses a preparation process of the antibacterial ceramic tile, which has simple steps and strong controllability and is beneficial to large-scale industrial production.)

1. An antibacterial ceramic tile is characterized in that: the antibacterial glaze layer is composed of basic transparent glaze and a zirconium phosphate loaded composite antibacterial agent, the zirconium phosphate loaded composite antibacterial agent comprises a zirconium phosphate carrier and a composite antibacterial agent, the zirconium phosphate loaded composite antibacterial agent is accumulated on the upper portion of the antibacterial glaze layer, and the antibacterial effective ingredients of the composite antibacterial agent are antibacterial oxide and antibacterial ions.

2. The antibacterial ceramic tile of claim 1, wherein the zirconium phosphate-loaded composite antibacterial agent is 0.5 ~ 2% by mass of the antibacterial glaze layer, and the calcium phosphate carrier is 0.5 ~ 1% by mass of the zirconium phosphate carrier.

3. The antibacterial ceramic tile of claim 1, wherein the zirconium phosphate carrier in the zirconium phosphate-loaded composite antibacterial agent is alpha-zirconium phosphate prepared by a hydrothermal method, and the specific surface area of the alpha-zirconium phosphate carrier is 100 ~ 200m²/g。

4. The antibacterial ceramic tile as claimed in claim 1, wherein the antibacterial oxide is zinc oxide with a particle size of 10 ~ 30nm, and the content of the zinc oxide in the composite antibacterial agent is 3 ~ 5%.

5. The antibacterial ceramic tile as claimed in claim 1, wherein the antibacterial ions are zinc ions, and the concentration of the zinc ions in the composite antibacterial agent is 0.01 ~ 0.03.03 mol/L.

6. The antibacterial ceramic tile as claimed in claim 1, wherein the chemical composition of the base transparent glaze is 40 ~ 41.5.5% by weight of SiO₂11 ~ 12% Al₂O₃5 ~ 5.5.5% of B₂O₃、8~ 9% CaO, 1.5 ~ 2.5.5% MgO, 6 ~ 7% ZnO, 4 ~ 4.5.5% BaO, 2 ~ 3% SrO, 9 ~ 10.5.5% K₂O, 5 ~ 7% Na₂O, 0.1 ~ 0.25.25% and others.

7. A method for preparing an antibacterial ceramic tile according to any one of claims 1 ~ 6, characterized by comprising the following process steps:

1) preparing a common ceramic tile blank with a ground glaze layer and a decorative pattern layer, applying a transparent glaze layer, mixing basic transparent glaze and a zirconium phosphate carrier to form the transparent glaze layer, and sintering at high temperature to obtain a semi-finished product;

2) spraying a composite antibacterial agent on the surface of the semi-finished product obtained in the step 1), polishing and grinding by a grinding disc, and carrying out heat treatment to obtain a finished antibacterial ceramic tile product.

8. The preparation method of the antibacterial ceramic tile according to claim 7, wherein the firing temperature of the high-temperature firing in the step 1) is 1150 ~ 1200 ℃ and the firing period is 45 ~ 55 min.

9. The method for preparing antibacterial ceramic tile according to claim 7, characterized in that: in the step 2), the grinding disc is made of wool felt.

10. The method for preparing antibacterial ceramic tiles according to claim 7, wherein the heat treatment temperature of the heat treatment in the step 2) is 80 ~ 120 ℃ and the heat treatment time is 10 ~ 20 s.

Technical Field

The invention relates to the field of building ceramics, in particular to an antibacterial ceramic tile.

Background

The first method is to directly add an antibacterial material into the ceramic tile to mix and burn the antibacterial material into the ceramic tile, for example, Chinese patent CN103641439A discloses an antibacterial ceramic tile and a preparation method thereof, the antibacterial ceramic tile mainly comprises 60 ~ parts of kaolin, 30 ~ parts of ceramic clay, 1 ~ parts of quartz, 1 ~ parts of potash feldspar, 0.1 ~ parts of silver phosphate and 1 ~ parts of copper oxide, the preparation method is to uniformly mix the substances according to the proportion, the powder is pressed to form and burnt, the antibacterial ceramic product is obtained, the second method is to burn the antibacterial material on the surface of the ceramic tile, for example, CN discloses a method for preparing a ceramic tile with a weak antibacterial glaze surface, the antibacterial glaze, the ceramic tile has a weak antibacterial glaze, the binding force of a silver-containing antibacterial ceramic glaze solution is reduced by spraying the antibacterial ceramic glaze solution on the surface of the ceramic tile, the antibacterial glaze solution is reduced by spraying the antibacterial ceramic green body, the antibacterial glaze solution is applied to the ceramic tile surface of a ceramic tile, the antibacterial glaze is a low-temperature antibacterial glaze solution, and the antibacterial glaze solution is applicable to the ceramic tile surface of the ceramic tile, the antibacterial glaze product, the antibacterial glaze is not only the ceramic tile, but the antibacterial glaze is not applicable to the antibacterial ceramic tile, the antibacterial glaze solution, the antibacterial glaze product, the antibacterial glaze solution, the antibacterial glaze is not applicable to the ceramic tile surface of the ceramic tile, the ceramic tile is not only the antibacterial glaze is not applicable to the antibacterial glaze product, the antibacterial glaze is not applicable to the ceramic tile, the antibacterial glaze, the ceramic tile, the antibacterial glaze is not applicable to the ceramic tile, the antibacterial glaze, the ceramic tile, the.

Disclosure of Invention

The invention aims to provide an antibacterial ceramic tile and a preparation method thereof, aiming at the defects of the prior art.

The technical scheme adopted by the invention is as follows: the antibacterial ceramic tile comprises an antibacterial glaze layer arranged on the upper surface of the ceramic tile, wherein the antibacterial glaze layer is composed of basic transparent glaze and a zirconium phosphate loaded composite antibacterial agent, the zirconium phosphate loaded composite antibacterial agent comprises a zirconium phosphate carrier and a composite antibacterial agent, the zirconium phosphate loaded composite antibacterial agent is accumulated on the upper portion of the antibacterial glaze layer, and the antibacterial effective components of the composite antibacterial agent are antibacterial oxides and antibacterial ions.

Specifically, the zirconium phosphate carrier with a porous structure is introduced into the transparent glaze layer on the outermost surface of the ceramic tile, and the zirconium phosphate carrier is used for loading the composite antibacterial agent, so that the zirconium phosphate carrier is accumulated on the upper part of the antibacterial glaze layer after being sintered at high temperature by utilizing the characteristic that the density of the zirconium phosphate carrier is lower than that of the basic transparent glaze, and the aim of fixedly loading the antibacterial active ingredients on the upper surface of the antibacterial glaze layer is fulfilled, namely the binding force between the antibacterial material and the ceramic tile is effectively strengthened. The antibacterial glaze layer does not need polishing treatment, and a porous microstructure is formed on the surface of the glaze layer after the antibacterial glaze layer is fired at high temperature, namely the porous microstructure mainly consists of a porous structure on the surface of the zirconium phosphate carrier, so that an antibacterial active ingredient in the composite antibacterial agent can be filled and permeated into the porous structure of the zirconium phosphate carrier after subsequent spraying and heat treatment, and the antibacterial glaze layer is endowed with a lasting and excellent antibacterial effect.

Actually, the antibacterial ceramic tile of the present invention further comprises a body layer, a ground glaze layer and a decorative pattern layer arranged from bottom to top, and the antibacterial glaze layer of the present invention is arranged on the decorative pattern layer and is located on the outermost surface layer of the antibacterial ceramic tile, i.e. the zirconium phosphate loaded composite antibacterial agent of the present invention is located on the outermost surface of the antibacterial ceramic tile.

The raw material of the ceramic tile body for forming the body layer is the conventional raw material of the common body of the ceramic tile, the ground glaze for forming the ground glaze layer is the conventional common ground glaze for the ceramic tile, and the method and the process for forming the decorative pattern layer by the conventional ceramic tile decoration, such as screen printing, inkjet printing and the like, are not described herein again.

As a further improvement of the above scheme, the zirconium phosphate supported composite antibacterial agent is 0.5 ~ 2% by mass of the antibacterial glaze layer, and the calcium phosphate carrier is 0.5 ~ 1% by mass of the zirconium phosphate carrier, specifically, in the actual operation process, the composite antibacterial agent is supported in the porous structure of the calcium phosphate carrier in a spraying and polishing manner, so the amount of the composite antibacterial agent in the antibacterial glaze layer is the loading amount of the zirconium phosphate carrier.

As a further improvement of the scheme, the carrier zirconium phosphate in the zirconium phosphate-loaded composite antibacterial agent is alpha-zirconium phosphate prepared by a hydrothermal method, and the specific surface area of the alpha-zirconium phosphate is 100 ~ 200m²(ii) in terms of/g. Specifically, the zirconium phosphate prepared by the hydrothermal method has a three-dimensional network porous structure, the specific surface area is further increased, the adhesion of antibacterial active ingredients is facilitated, and meanwhile, the migration of antibacterial ions is facilitated, so that the antibacterial effect is further improved.

The antibacterial oxide is characterized in that the antibacterial oxide is zinc oxide with the particle size of 10 ~ nm, the content of the zinc oxide in the composite antibacterial agent is 3 ~%, specifically, the antibacterial oxide not only has an antibacterial effect in cooperation with antibacterial ions, but also can be filled and clamped in a porous structure on the surface of carrier zirconium phosphate due to obvious granularity, so that the antibacterial effect of the ceramic tile can be filled and clamped on the surface of the antibacterial glaze layer of the ceramic tile, the surface of the ceramic tile does not need to be polished and has antifouling and antibacterial properties, the antibacterial oxide is selected from zinc oxide, the particle size of the zinc oxide is limited to 10 ~ nm, the content of the zinc oxide is 3 ~%, the antibacterial effect of the zinc oxide is obvious, the zinc oxide is wide in source and is lower in cost compared with antibacterial silver, meanwhile, when the antibacterial effect of the zinc oxide is exerted, a zinc ion-rich environment is formed around zinc oxide particles, the finer particle size is easier to dissolve out, but the zinc oxide with the particle size of less than 10nm is easy to agglomerate, the particle size of the zinc oxide is limited to 10nm, the zinc oxide content of the zinc oxide is limited to 10nm, and the brick surface is easy to be excessively low, the brick pollution-preventing effect, and the brick is influenced by over-filling effect, and the brick is high.

In addition, the concentration of the zinc ions is not low, the bacteriostatic effect is low and is over the upper limit of exchange adsorption of the zirconium phosphate carrier, so that the antibacterial agent cannot be fully absorbed and utilized.

As a further improvement of the proposal, the chemical composition of the basic transparent glaze is 40 ~ 41.5.5 percent of SiO by weight percentage₂11 ~ 12% Al₂O₃5 ~ 5.5.5% of B₂O₃8 ~ 9% CaO, 1.5 ~ 2.5% MgO, 6 ~ 7% ZnO, 4 ~ 4.5.5% BaO, 2 ~ 3% SrO, 9 ~ 10.5.5% K₂O, 5 ~ 7% Na₂The invention only limits the chemical components of the basic transparent glaze, and actually the raw material components and the mixture ratio of the ceramic tile transparent glaze with the specific chemical components can be various so as to have the chemical component composition of the basic transparent glaze.

The invention adopts another technical scheme that the preparation method of the antibacterial ceramic tile comprises the following process steps:

1) preparing a common ceramic tile blank with a ground glaze layer and a decorative pattern layer, applying a transparent glaze layer, mixing basic transparent glaze and a zirconium phosphate carrier to form the transparent glaze layer, and sintering at high temperature to obtain a semi-finished product;

2) spraying a composite antibacterial agent on the surface of the semi-finished product obtained in the step 1), polishing and grinding by a grinding disc, and carrying out heat treatment to obtain a finished antibacterial ceramic tile product.

Specifically, the zirconium phosphate carrier in the transparent glaze layer has certain antibacterial performance, and due to the low density, the zirconium phosphate carrier is accumulated on the upper part of the transparent glaze layer after being sintered at high temperature in the step 1), and forms a mutual permeation structure with the basic transparent glaze at the interface of the zirconium phosphate carrier and the basic transparent glaze. Namely, the zirconium phosphate carrier which is actually accumulated on the upper part of the transparent glaze layer endows the surface of the ceramic tile with certain antibacterial performance. However, the surface of the conventional porous structure requires a polishing process due to extremely poor flatness and antifouling property. The application utilizes the porous structure of zirconium phosphate, adopts a non-high-temperature treatment mode of spraying, polishing and grinding and heat treatment to load the composite antibacterial agent, not only solves the defects of extremely poor surface smoothness and antifouling property of the porous structure, but also combines the composite antibacterial agent and the antibacterial porous material and simultaneously avoids the antibacterial active ingredients of the composite antibacterial agent from being damaged by high-temperature treatment, thereby endowing the surface of the ceramic tile with long-acting and excellent antibacterial performance, and also avoiding the phenomenon of multi-defect appearance decorative effect after the traditional antibacterial ceramic tile finished product is fired at high temperature.

The preparation method of the composite antibacterial agent comprises the steps of firstly stirring and mixing antibacterial oxide powder, water and a dispersing agent at a high speed, performing mechanical superfine grinding to control the content to be 18 ~ 20% to obtain nano antibacterial oxide slurry, then stirring and mixing acetate containing the antibacterial ions, water and a chelating agent at a high speed to control the concentration of the chelating agent to be 0.2 ~ 0.6.6 mol/L to obtain a solution containing the antibacterial ions, and finally mixing the obtained nano antibacterial oxide slurry and the solution containing the antibacterial ions, and performing mechanical superfine grinding to obtain the composite antibacterial agent, wherein the chelating agent is ethylenediamine tetraacetic acid which has a polyhydroxy structure and is used for chelating the antibacterial ions so that the antibacterial materials are uniformly dispersed in the solution, and the stability of the antibacterial effect is facilitated.

As a further improvement of the scheme, the firing temperature of the high-temperature firing in the step 1) is 1150 ~ 1200 ℃, the firing period is 45 ~ 55min, specifically, the firing temperature is too low, bubbles are easily formed in the glaze layer, the firing temperature is too high, the glaze layer is easy to boil, the flatness is not good, and the like.

As a further improvement of the scheme, the grinding disc in the step 2) is made of wool felt. In particular, the wool felt is soft and has good toughness, which is beneficial to the full contact of the composite antibacterial agent and the surface of the ceramic tile semi-finished product.

As a further improvement of the scheme, the heat treatment temperature of the heat treatment in the step 2) is 80 ~ 120 ℃, and the heat treatment time is 10 ~ 20 s.

The invention has the beneficial effects that:

(1) according to the invention, zirconium phosphate is introduced into the antibacterial glaze layer on the surface of the ceramic tile, and the zirconium phosphate is sintered at high temperature by utilizing the characteristic of low density of the zirconium phosphate and then accumulated on the upper part of the glaze layer to form the surface with a porous structure, so that the zirconium phosphate is used as a carrier attached with the composite antibacterial agent, the binding force of the antibacterial material and the ceramic tile is enhanced, the ceramic tile is endowed with longer-acting and more excellent antibacterial performance, and the appearance decoration effect of the surface of the ceramic tile is not influenced.

(2) The invention adopts the composite antibacterial agent, wherein the antibacterial active ingredients comprise antibacterial oxides and antibacterial ions with different forms, the antibacterial oxides fill the porous structure of the zirconium phosphate carrier and have the antibacterial and antifouling functions, and the antibacterial ions permeate and bury the porous structure of the zirconium phosphate carrier and play the antibacterial function with the antibacterial oxides in a synergistic manner, so that the ceramic tile has a lasting and efficient antibacterial effect.

(3) The invention adjusts the preparation process to be matched with the antibacterial glaze layer, wherein the composite antibacterial agent is not treated at high temperature, the antibacterial activity of the antibacterial material is maintained to the maximum extent, and the antibacterial effective components are effectively exposed on the surface of the ceramic tile through spraying and polishing treatment, so that the antibacterial effect is more excellent.

(4) The preparation process has simple steps and strong controllability, and is beneficial to large-scale industrial production.

Detailed Description

The present invention is specifically described below with reference to examples in order to facilitate understanding of the present invention by those skilled in the art. It should be particularly noted that the examples are given solely for the purpose of illustration and are not to be construed as limitations on the scope of the invention, as non-essential improvements and modifications to the invention may occur to those skilled in the art, which fall within the scope of the invention as defined by the appended claims. Meanwhile, the raw materials mentioned below are not specified in detail and are all commercial products; the process steps or preparation methods not mentioned in detail are all process steps or preparation methods known to the person skilled in the art.