阅读说明：本技术 一种强抗菌功能性抛釉砖及其制备方法 (Highly-antibacterial functional glazed brick and preparation method thereof ) 是由 吴永鑫 钟元杰 康朝晖 林文端 于 2020-07-22 设计创作，主要内容包括：本发明涉及一种强抗菌功能性抛釉砖及其制备方法,所述强抗菌功能性抛釉砖包括陶瓷基体,所述陶瓷基体的表面覆盖抗菌釉层,所述抗菌釉层由基础釉和立方体磷酸锆载银锌抗菌粉组成,所述抗菌釉层表面覆盖全抛釉层,所述全抛釉层由基础釉和稀土金属氧化物组成,所述全抛釉层表面覆盖抗菌蜡层,所述抗菌蜡层包含银锌系抗菌剂和端羟基聚硅氧烷。本发明还提供所述强抗菌功能性抛釉砖的制备方法,包括粉料压制成型,干燥后得到胚体；胚体进行吹尘和喷水、施底釉；印花装饰,之后施全抛釉；烧制得到瓷砖粗品和打蜡处理。所述强抗菌功能性抛釉砖具有超强的抗菌功效,同时抗菌元素稳固性能好,可持久发挥抗菌效果,具有较好的市场运用前景。(The invention relates to a highly antibacterial functional glazed brick and a preparation method thereof, wherein the highly antibacterial functional glazed brick comprises a ceramic substrate, the surface of the ceramic substrate is covered with an antibacterial glaze layer, the antibacterial glaze layer consists of a base glaze and cubic zirconium phosphate silver-zinc-loaded antibacterial powder, the surface of the antibacterial glaze layer is covered with a full glaze layer, the full glaze layer consists of a base glaze and a rare earth metal oxide, the surface of the full glaze layer is covered with an antibacterial wax layer, and the antibacterial wax layer comprises a silver-zinc antibacterial agent and hydroxyl-terminated polysiloxane. The invention also provides a preparation method of the glazed brick with strong antibacterial function, which comprises the steps of pressing and molding powder, and drying to obtain a blank; blowing dust and spraying water to the blank body, and applying base coat; printing and decorating, and then applying full-polished glaze; firing to obtain a crude product of the ceramic tile and waxing. The glazed brick with the strong antibacterial function has the advantages of super-strong antibacterial effect, good stability of antibacterial elements, lasting antibacterial effect and good market application prospect.)

1. The utility model provides a strong antibiotic functional glazed brick which characterized in that: the high-antibacterial-function glazed brick comprises a ceramic substrate, wherein an antibacterial glaze layer is covered on the surface of the ceramic substrate, the antibacterial glaze layer consists of base glaze and cubic zirconium phosphate silver-zinc-loaded antibacterial powder, and the cubic zirconium phosphate silver-zinc-loaded antibacterial powder is uniformly dispersed in the antibacterial glaze layer; the surface of the antibacterial glaze layer is covered with a full-glazed layer, the full-glazed layer consists of base glaze and rare earth metal oxide, and the rare earth metal oxide is uniformly dispersed in the full-glazed layer; the surface of the full-polished glaze layer is covered with an antibacterial wax layer, and the antibacterial wax layer contains a silver-zinc antibacterial agent and hydroxyl-terminated polysiloxane.

2. The glazed brick with strong antibacterial function according to claim 1, wherein: the silver-carrying amount of the cubic zirconium phosphate silver-carrying zinc antibacterial powder is 0.06-3.3 wt%, and the zinc-carrying amount is 6-20 wt%; preferably, the silver loading amount is 2.6-3.2 wt%, and the zinc loading content is 6.5-10 wt%;

optionally, the cubic zirconium phosphate silver-zinc-carrying antibacterial powder accounts for 0.1-5% of the total weight of the antibacterial glaze layer, and preferably 0.1-1%.

3. The glazed brick with strong antibacterial function according to claim 1, wherein: the basic glaze comprises 10-20 parts of kaolin, 3-5 parts of potassium feldspar, 15-20 parts of albite, 15-20 parts of quartz powder, 4-8 parts of calcite and 3-5 parts of calcined soil.

4. The glazed brick with strong antibacterial function according to claim 1, wherein: the rare earth metal oxide is cerium oxide or lanthanum oxide, and the specific surface area of the rare earth metal oxide is 50-200m²/g；

Optionally, the rare earth metal oxide accounts for 0.1-1% of the total weight of the full-glazed layer.

5. The glazed brick with strong antibacterial function according to claim 1, wherein: the hydroxyl-terminated polysiloxane is at least one of hydroxyl-terminated polydimethylsiloxane and hydroxyl-terminated polymethylphenylsiloxane;

optionally, the silver-zinc antibacterial agent accounts for 0.5-2% of the total weight of the antibacterial wax layer;

Optionally, the hydroxyl-terminated polysiloxane accounts for 15-25% of the total weight of the antibacterial wax layer.

6. A method for preparing the glazed brick with strong antibacterial function according to any one of claims 1 to 5, which is characterized in that: the method comprises the following steps:

step 1: pressing and molding the powder, and drying to obtain a blank;

step 2: carrying out dust blowing and water spraying on the blank body, and then applying a ground coat on one surface of the sprayed water, wherein the ground coat comprises antibacterial glaze powder formed by mixing basic glaze and cubic zirconium phosphate silver-zinc-loaded antibacterial powder, so as to obtain a brick blank covered with the ground coat;

and step 3: printing decoration is carried out on the ground glaze through a silk screen plate or an offset printing roller or an ink-jet printing machine, and then full-polishing glaze is applied, wherein the full-polishing glaze is functional glaze powder consisting of base glaze and rare earth metal oxide, and a glazed brick blank is obtained;

and 4, step 4: firing the blank with the glaze brick obtained in the step 3 to obtain a crude product of the ceramic tile;

and 5: and (4) waxing the crude product of the ceramic tile obtained in the step (4), wherein wax water containing the silver-zinc antibacterial agent and hydroxyl-terminated polysiloxane is used for waxing to form an antibacterial wax layer.

7. The method for preparing the glazed brick with strong antibacterial function according to claim 6, wherein the method comprises the following steps: the cubic zirconium phosphate silver-zinc-carrying antibacterial powder accounts for 0.1-5% of the total weight of the ground glaze, and preferably accounts for 0.1-1%;

Optionally, the rare earth metal oxide accounts for 0.3-1.5% of the total weight of the full glaze.

8. The method for preparing the glazed brick with strong antibacterial function according to claim 6, wherein the method comprises the following steps: the water content of the full-polished glaze in the step 3 is 10-18 wt%.

9. The method for preparing the glazed brick with strong antibacterial function according to claim 6, wherein the method comprises the following steps: the firing temperature in the step 4 is 1100-1300 ℃.

10. The method for preparing the glazed brick with strong antibacterial function according to claim 6, wherein the method comprises the following steps: and the wax water adopted in the waxing in the step 5 consists of hydroxyl-terminated polysiloxane, a silver-zinc antibacterial agent, a volatile solvent, a curing agent and an auxiliary agent.

Technical Field

The invention relates to the technical field of ceramic preparation, in particular to a glazed brick with strong antibacterial function and a preparation method thereof.

Background

With the improvement of living standard, people pay more and more attention to safety problems such as home furnishing, diet and the like, and particularly, the products with antibacterial functions are more popular among consumers when viruses and diseases are spread. Ceramic products are widely applied to life and production, the raw materials of the ceramic products are natural, the ceramic generally has good chemical stability and corrosion resistance, but has no resistance to bacteria and viruses, some sanitary ceramics such as a toilet bowl, a bathtub, a porcelain basin, a ceramic tile and the like are frequently contacted with a human body, if germs are bred on the sanitary ceramics, diseases can be infected, and the health of the human body is seriously harmed; in addition, tiles used for paving on the bottom surface are easy to mildew in a humid environment due to long-term contact with stains, and are difficult to remove. Therefore, the development of ceramic products with antibacterial performance has wide application prospect.

In order to combine the antibacterial properties with the characteristics of ceramics, the following problems are generally to be solved: the stable presence of the antibacterial agent in the ceramic body, and the lasting antibacterial effect. There are two ways, one is to introduce the antibacterial agent into the ceramic green body and form it by firing, but this process has high requirement for antibacterial agent, and most antibacterial agents are difficult to endure the firing temperature, resulting in low antibacterial effect, and accordingly, a large dosage of the antibacterial agent needs to be sacrificed to obtain the basic antibacterial effect. The other is to form an antibacterial layer on the surface of the formed ceramic, and the antibacterial layer has poor wear resistance, so that the antibacterial ceramic is difficult to be matched with a use scene with stable wear resistance of the ceramic.

The invention patent CN106348792A discloses a method for manufacturing an antibacterial ceramic tile, which comprises the steps of printing a protective glaze after ink-jet printing; the protective glaze comprises the following raw materials in parts by weight: 11-13 parts of air knife soil, 11-13 parts of calcium carbonate, 4.5-5.5 parts of barium carbonate, 4.5-5.5 parts of calcined bone stone, 28.5-32.5 parts of potassium feldspar, 14-16 parts of glaze frit, 1.7-2.3 parts of zirconium silicate, 15-18 parts of albite, 1.7-2.3 parts of zinc oxide and 7-9 parts of an antibacterial agent; in the firing step, the temperature of the kiln is firstly increased to 835-840 ℃, the temperature is preserved for 1.5-2.5 h, then the temperature is increased to 1200-1210 ℃, the temperature is preserved for 3-4 h, and then the temperature is reduced by cooling. The antibacterial agent is prepared from boron oxide, rare earth ions and talcum powder according to the mass ratio of 10: 3-4: 8-12. The thickness of the protective glaze in the scheme is thin, and the antibacterial effect can be gradually reduced to loss along with the abrasion of the protective glaze in the using process.

Disclosure of Invention

The invention aims to solve the problems of poor and non-durable antibacterial effect of the existing antibacterial ceramic tile and provide a high-antibacterial-function glazed tile.

The invention also provides a preparation method of the glazed brick with strong antibacterial function, which is characterized in that the glaze layer is tightly combined with the ceramic matrix through the control of the technological process, the stabilizing effect on antibacterial particles is good, and the antibacterial component is not easy to run off, so that the antibacterial effect is exerted for a long time.

In the invention, the antibacterial glaze layer covers the surface of the ceramic substrate, preferably the outer surface, so that the antibacterial glaze layer is convenient for molding and processing. The antibacterial glaze layer is composed of base glaze and cubic zirconium phosphate silver-zinc-loaded antibacterial powder, the cubic zirconium phosphate silver-zinc-loaded antibacterial powder is uniformly dispersed in the antibacterial glaze layer, the cubic zirconium phosphate silver-zinc-loaded antibacterial powder and the ceramic matrix are fired together by utilizing the high temperature resistance advantage of the cubic zirconium phosphate silver-zinc-loaded antibacterial powder, and the antibacterial glaze layer is tightly combined with the ceramic matrix. The problem of discoloration caused by firing is avoided by controlling the addition amount of the cubic silver-zinc phosphate antibacterial powder to be not more than 1%. On the other hand, although the cubic zirconium phosphate silver-zinc-loaded antibacterial powder has a good silver and zinc loading effect, the problem of loss of silver and zinc elements still exists when the cubic zirconium phosphate silver-zinc-loaded antibacterial powder is directly fired, in order to protect the antibacterial powder in the antibacterial glaze layer and avoid the loss of the silver and zinc elements in the firing process, the invention applies full-polishing glaze after printing decoration, and adds a small amount of rare earth metal oxide in the full-polishing glaze, thereby forming a protective layer, avoiding the reduction of the antibacterial effect caused by firing, reducing the input of the antibacterial powder and reducing the production cost.

Due to the protection of the full-polished glaze, the rare earth metal oxide has the effect of enhancing the stereoscopic impression of the printed patterns, but ink bleeding is easy to occur, possibly due to oilThe ink pattern is adsorbed on the rare earth metal oxide to cause agglomeration. The preferred rare earth metal oxides of the present invention have a specific surface area of from 50 to 200m²And/g, the pattern effect can be ensured to be firm and vivid by adopting a mode of controlling the specific surface area. Preferably, the water content of the full-polished glaze is 10-18 wt% to protect the pattern effect.

The invention carries out waxing treatment on the crude product of the ceramic tile, and the purpose of waxing comprises the following steps: 1. assisting in antibiosis, and forming a bacteriostasis barrier on the outermost layer by adding the silver-zinc antibacterial agent; 2. the wear resistance is enhanced, and the brightness and the wear resistance of the ceramic tile are improved by the waxing layer; 3. the cubic zirconium phosphate silver-zinc-carrying antibacterial powder in the ground coat is protected to avoid silver migration and diffusion, namely, the hydroxyl-terminated polysiloxane is used for blocking silver ions, and the migrated silver is stabilized by virtue of the hydroxyl-terminated polysiloxane to form a concentration barrier and avoid the formation of silver ion concentration difference.

The specific scheme is as follows:

a high-antibacterial-function glazed brick comprises a ceramic substrate, wherein an antibacterial glaze layer covers the surface of the ceramic substrate, the antibacterial glaze layer consists of a base glaze and cubic zirconium phosphate silver-zinc-loaded antibacterial powder, and the cubic zirconium phosphate silver-zinc-loaded antibacterial powder is uniformly dispersed in the antibacterial glaze layer; the surface of the antibacterial glaze layer is covered with a full-glazed layer, the full-glazed layer consists of base glaze and rare earth metal oxide, and the rare earth metal oxide is uniformly dispersed in the full-glazed layer; the surface of the full-polished glaze layer is covered with an antibacterial wax layer, and the antibacterial wax layer contains a silver-zinc antibacterial agent and hydroxyl-terminated polysiloxane.

Further, the silver-carrying amount (silver element content) in the cubic zirconium phosphate silver-carrying zinc antibacterial powder is 0.06-3.3 wt%, and the zinc-carrying amount (zinc element content) is 6-20 wt%; preferably, the silver loading is 2.6-3.2 wt%, and the zinc loading content is 6.5% -10 wt%.

Optionally, the cubic zirconium phosphate silver-zinc-carrying antibacterial powder accounts for 0.1-5% of the total weight of the antibacterial glaze layer, and preferably 0.1-1%.

Further, the base glaze comprises 10-20 parts of kaolin, 3-5 parts of potassium feldspar, 15-20 parts of albite, 15-20 parts of quartz powder, 4-8 parts of calcite and 3-5 parts of calcined soil.

Further, the rare earth metal oxide is cerium oxide or lanthanum oxide, and the specific surface area of the rare earth metal oxide is 50-200m²/g；

Optionally, the rare earth metal oxide accounts for 0.1-1% of the total weight of the full-glazed layer.

Furthermore, the hydroxyl-terminated polysiloxane is at least one of hydroxyl-terminated polydimethylsiloxane and hydroxyl-terminated polymethylphenylsiloxane;

optionally, the silver-zinc antibacterial agent accounts for 0.5-2% of the total weight of the antibacterial wax layer;

optionally, the hydroxyl-terminated polysiloxane accounts for 15-25% of the total weight of the antibacterial wax layer.

The invention also provides a preparation method of the glazed brick with strong antibacterial function, which comprises the following steps:

Step 1: pressing and molding the powder, and drying to obtain a blank;

step 2: carrying out dust blowing and water spraying on the blank body, and then applying a ground coat on one surface of the sprayed water, wherein the ground coat comprises antibacterial glaze powder formed by mixing basic glaze and cubic zirconium phosphate silver-zinc-loaded antibacterial powder, so as to obtain a brick blank covered with the ground coat;

and step 3: printing decoration is carried out on the ground glaze through a silk screen plate or an offset printing roller or an ink-jet printing machine, and then full-polishing glaze is applied, wherein the full-polishing glaze is functional glaze powder consisting of base glaze and rare earth metal oxide, and a glazed brick blank is obtained;

and 4, step 4: firing the blank with the glaze brick obtained in the step 3 to obtain a crude product of the ceramic tile;

and 5: and (4) waxing the crude product of the ceramic tile obtained in the step (4), wherein wax water containing the silver-zinc antibacterial agent and hydroxyl-terminated polysiloxane is used for waxing to form an antibacterial wax layer.

Further, the cubic zirconium phosphate silver-zinc-carrying antibacterial powder accounts for 0.1-1% of the total weight of the ground glaze;

optionally, the rare earth metal oxide accounts for 0.3-1.5% of the total weight of the full glaze.

Further, the water content of the full-polished glaze in the step 3 is 10-18 wt%.

Further, the firing temperature in the step 4 is 1100-1300 ℃.

Furthermore, the wax water adopted in the waxing in the step 5 consists of hydroxyl-terminated polysiloxane, a silver-zinc antibacterial agent, a volatile solvent, a curing agent and an auxiliary agent.

Has the advantages that:

according to the invention, the antibacterial glaze layer, the full-glazed layer and the antibacterial wax layer are combined together, and the super-strong antibacterial effect is realized by using the lower addition amount of the cubic zirconium phosphate silver-loaded zinc antibacterial powder, wherein the full-glazed layer and the antibacterial wax layer not only improve the antibacterial effect of the product on the basis of adding the cubic zirconium phosphate silver-loaded zinc antibacterial powder, but also protect the antibacterial material in the glaze layer, and avoid the loss and diffusion of silver, zinc and the like in the firing and using processes, so that the product has the lasting antibacterial effect.

According to the preparation method of the glazed brick with the strong antibacterial function, the ground glaze and the full-glazed glaze are integrally fired and molded with the blank body, so that the obtained brick body is good in bonding performance, the compressive strength is 32-35Mpa, and the brick is wear-resistant and compressive; by adopting wax water waxing treatment, the comprehensive performance of the material is improved, and the functional glazed brick is obtained, so that the application prospect is better.

Drawings

In order to illustrate the technical solution of the present invention more clearly, the drawings will be briefly described below, and it is apparent that the drawings in the following description relate only to some embodiments of the present invention and are not intended to limit the present invention.

FIG. 1 is a photograph of the front and back of a highly antibacterial functional glazed tile provided by the present invention.

Detailed Description

Preferred embodiments of the present invention will be described in more detail below. While the following describes preferred embodiments of the present invention, it should be understood that the present invention may be embodied in various forms and should not be limited by the embodiments set forth herein. The examples do not specify particular techniques or conditions, and are performed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available. In the following examples, "%" means weight percent, unless otherwise specified.