CN113860854A - Ceramic plate with stable and durable antibacterial performance and preparation method thereof - Google Patents

Ceramic plate with stable and durable antibacterial performance and preparation method thereof Download PDF

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CN113860854A
CN113860854A CN202111134483.0A CN202111134483A CN113860854A CN 113860854 A CN113860854 A CN 113860854A CN 202111134483 A CN202111134483 A CN 202111134483A CN 113860854 A CN113860854 A CN 113860854A
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antibacterial
ceramic plate
overglaze
nano
glaze
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刘一军
张凡
汪庆刚
吴洋
谢范峰
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Monalisa Group Co Ltd
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Monalisa Group Co Ltd
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Abstract

The invention discloses a ceramic plate with stable and durable antibacterial performance and a preparation method thereof. The preparation method comprises the following steps: pressing the ceramic base material into a green body; applying an antibacterial overglaze on the surface of the blank; printing a design pattern on the surface of the blank after the antibacterial overglaze is applied by ink jet; applying antibacterial glaze polishing on the surface of the blank after the design pattern is printed by ink jet; sintering and polishing the blank body after the antibacterial glazing is applied; and (3) filling the polished ceramic plate with a nano antibacterial material to obtain the ceramic plate with stable and durable antibacterial performance. The preparation method can overcome the defects of unsatisfactory antibacterial effect and unstable and durable antibacterial performance of the conventional antibacterial ceramic.

Description

Ceramic plate with stable and durable antibacterial performance and preparation method thereof
Technical Field
The invention belongs to the technical field of building ceramics, and particularly relates to a ceramic plate with stable and lasting antibacterial performance and a preparation method thereof.
Background
Ceramic tiles are common decorative materials at home, and are increasingly popular and concerned by people due to the characteristics of easy management, rich color patterns, beautiful appearance and elegance. With the rapid development of modern economy and technology, people require more functionality of ceramic tiles to meet the growing material culture needs. Antibacterial ceramic plates are becoming increasingly popular in the market as a result of the combination of antibacterial technology and ceramic plate production technology.
Currently, the antibacterial ceramic products on the market are mainly focused on the following two categories: (1) adding metal ion to glaze or polishing wax water to resist bacteria. The normal metabolic activity of bacteria is destroyed by the action of metal ions such as silver and zinc which are slowly released by a loading agent or adsorbed on the surface of the loading agent, cell membranes of the bacteria and metabolic proteins so as to kill and resist bacteria; (2) the surface of the ceramic tile is provided with a photocatalytic antibacterial layer for antibiosis. Typically, the bacteria are realized by adsorbing water and oxygen molecules in the air by using nano titanium dioxide under the condition of illumination to form ions with extremely strong activity to react with the bacteria so as to destroy the bacteria. However, both of the above two antibacterial methods have certain limitations. For example, metal ions are usually added to the glaze, and the antibacterial effect is greatly reduced by antibacterial ions or high-temperature oxidation or participation in forming other phases under the high-temperature firing condition; the slow-release antibacterial ions are difficult to be uniformly distributed on the surface of the ceramic tile, so that the antibacterial effects at different positions on the surface of the ceramic tile are inconsistent, the fluctuation of the antibacterial detection result is caused, and the stable production is greatly hindered; the antibacterial wax water is coated on the surface of the ceramic tile and is in direct contact with the external environment, and the antibacterial performance is greatly influenced after the ceramic tile is trampled and rubbed for a period of time; the photocatalytic antibacterial product can show remarkable antibacterial property only under the irradiation of an ultraviolet lamp, and an ideal antibacterial effect is difficult to achieve under natural light and a fluorescent lamp.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a ceramic plate with stable and durable antibacterial performance and a preparation method thereof, so as to solve the defects of unsatisfactory antibacterial effect and unstable and durable antibacterial performance of the conventional antibacterial ceramic.
In a first aspect, the present invention provides a method for preparing a ceramic plate having stable and durable antibacterial properties. The preparation method comprises the following steps:
pressing the ceramic base material into a green body;
applying an antibacterial overglaze on the surface of the blank;
printing a design pattern on the surface of the blank after the antibacterial overglaze is applied by ink jet;
applying antibacterial glaze polishing on the surface of the blank after the design pattern is printed by ink jet;
sintering and polishing the blank body after the antibacterial glazing is applied;
and (3) filling the polished ceramic plate with a nano antibacterial material to obtain the ceramic plate with stable and durable antibacterial performance.
Preferably, the raw material composition of the antibacterial overglaze comprises: the silver-zinc composite antibacterial agent comprises, by mass, 1-3% of a silver-zinc composite antibacterial agent, 0.5-2.0% of a rare earth metal oxide, 0.1-0.35% of a suspending agent, 0.15-0.45% of a debonding agent, 50-55% of water and the balance of a basic overglaze.
Preferably, the application mode of the antibacterial overglaze is glaze spraying; the specific gravity of the antibacterial overglaze is 1.50-1.65 g/cm3The flow rate is 30-50 s, and the glazing amount is 45-60 g/cm2。
Preferably, the raw material composition of the antibacterial glazing comprises: the polishing solution comprises, by mass, 3-5% of a silver-zinc composite antibacterial agent, 0.15-0.45% of a suspending agent, 0.2-0.5% of a debonding agent, 45-55% of water and the balance of basic polishing.
Preferably, the application mode of the antibacterial polished glaze is glaze spraying; the specific gravity of the antibacterial polished glaze is 1.45-1.60 g/cm3The flow rate is 35-60 s, and the glazing amount is 70-85 g/cm2。
Preferably, the filling treatment is antibacterial wax ultra-clean treatment by using a nano antibacterial filling material; the nano antibacterial filling material consists of nano zinc oxide dispersion liquid and ultra-clean wax liquid; the nano zinc oxide dispersion liquid accounts for 3-8 wt% of the nano antibacterial filling material.
Preferably, the nano zinc oxide dispersion liquid is a dispersion liquid of nano zinc oxide in an aqueous medium; the nano zinc oxide accounts for 1.5-5 wt% of the dispersion liquid; the particle size of the nano zinc oxide is 20-40 nm.
Preferably, the coating amount of the nano antibacterial filling material on the surface of the ceramic plate is 10-25 g/m2。
Preferably, the raw material composition of the ceramic base material comprises: by mass percentage, calcined kaolin 15-22%, water washing mud 12-17%, quartz sand 18-25%, potassium sand 2-6%, wollastonite 2.5-4.5%, potash-soda feldspar 15-21%, calcined talc 3-8%, fine mud 1-5%, bentonite 1-5%, rare earth oxide 2-4%, suspending agent 0.1-0.4%, and debonding agent 0.25-0.45%; the rare earth oxide is La2O3、CeO2And Sm2O3At least one of (1).
In a second aspect, the present invention provides a ceramic plate having stable and durable antibacterial properties, which is obtained by the preparation method described in any one of the above. The antibacterial rate of the ceramic plate to escherichia coli and staphylococcus aureus is more than 99%; after the surface of the ceramic plate is brushed for 500 times by using a sodium hypochlorite disinfectant with the mass fraction of 5%, the antibacterial rate of the ceramic plate to escherichia coli and staphylococcus aureus is kept above 99%.
Drawings
FIG. 1 is a schematic structural diagram of a ceramic plate with stable and durable antibacterial performance, 1-an antibacterial material filling layer, 2-an antibacterial glaze-polishing layer, 3-an ink-jet printing layer, 4-an antibacterial glaze-facing layer, and 5-a ceramic plate substrate layer.
Detailed Description
The present invention is further illustrated by the following examples, which are to be understood as merely illustrative of, and not restrictive on, the present invention. Unless otherwise specified, each percentage means a mass percentage.
The method for preparing the ceramic plate having stable and durable antibacterial property according to the present invention is exemplified below with reference to fig. 1.
The ceramic base material is pressed into a green body (which may also be referred to as a "ceramic plate substrate layer"). The raw material composition of the ceramic base material can comprise: 15-22% of calcined kaolin, 12-17% of water washing mud, 18-25% of quartz sand, 2-6% of potassium sand, 2.5-4.5% of wollastonite, 15-21% of potash-soda feldspar, 3-8% of calcined talc, 1-5% of fine mud, 1-5% of bentonite, 2-4% of rare earth oxide, 0.1-0.4% of suspending agent and 0.25-0.45% of debonder. The rare earth oxide is La2O3、CeO2And Sm2O3One kind of (1). The mud raw materials provide good plasticity to facilitate the forming of the blank body, enable the blank body to have certain strength and reduce the breakage rate of the blank body. The sand ridge raw materials form the framework of the green body and reduce the shrinkage of the green body in the drying and sintering processes. The feldspar material as flux can reduce the sintering temperature of the green body and has a wider melting temperature range. The addition of rare earth oxide can make the blank possess a certain far infrared radiation property. The synergistic effect of the far infrared radiation and the antibacterial ions enables the antibacterial effect of the blank to be more obvious and long-lasting.
And drying the green body. Drying in a drying kiln. The drying time can be 57-78 min. Controlling the moisture of the dried blank within 0.45 wt%.
And applying an antibacterial overglaze on the surface of the dried blank to form an antibacterial overglaze layer. The antibacterial overglaze has the functions of covering the ground color and flaws of the blank body, providing a proper place for the ink-jet printing layer, and providing a foundation for endowing the ceramic plate with excellent antibacterial effect and antibacterial stability through dissolution of antibacterial components from the overglaze layer and the infrared radiation effect of the rare earth metal oxide. The antibacterial overglaze comprises the following raw materials: the silver-zinc composite antibacterial agent comprises, by mass, 1-3% of a silver-zinc composite antibacterial agent, 0.5-2.0% of a rare earth metal oxide, 0.1-0.35% of a suspending agent, 0.15-0.45% of a debonding agent, 50-55% of water and the balance of a basic overglaze. The particle size of the silver-zinc composite antibacterial agent is 200-350 nm. The rare earth metal oxide is La2O3、CeO2、Sm2O3、Nd2O3In (1)One or a mixture of several.
The chemical composition of the basic overglaze is not limited, and the basic overglaze commonly used in the field can be adopted. For example, the chemical composition of the base overglaze may include, in mass percent: IL: 1.55-2.76%; SiO 22：54.74～62.16％；Al2O3：24.52～30.15％；Fe2O3：0.18～0.35％；TiO2：0.02～0.05％；CaO：2.45～3.68％；MgO：0.13～0.32％；K2O：4.68～6.18％；Na2O：2.75～4.15％；ZrO2：0.02～0.05％；Rb2O：0.02～0.06％。
The preparation method of the antibacterial overglaze comprises the following steps: and uniformly mixing the silver-zinc composite antibacterial agent, the rare earth metal oxide, the suspending agent, the dispergator and the basic overglaze, adding water, ball-milling for 8-10 h, and sieving to obtain the antibacterial overglaze. The suspending agent is at least one of carboxymethyl cellulose and polyvinyl alcohol. The dispergator is at least one of sodium tripolyphosphate and sodium metasilicate. The screen allowance of the antibacterial overglaze passing through a 325-mesh screen is 1.8-2.5 wt%.
The application mode of the antibacterial overglaze can be glaze spraying. The specific gravity of the antibacterial overglaze is 1.50-1.65 g/cm3The flow rate is 30-50 s, and the glazing amount is 45-60 g/cm2. The flow cup has a mouth with an inner diameter of 68mm and an outer diameter of 75 mm.
And carrying out ink-jet printing on the surface of the blank body after the antibacterial overglaze is applied to form a design pattern so as to form an ink-jet printing layer. The texture and color of the ink-jet printed design pattern are adaptively changed according to the layout effect. For example, the surface of the blank after the antibacterial overglaze is applied is printed with colorful and vivid-grained patterns by ink-jet printing.
And applying antibacterial (protective) glaze polishing on the surface of the blank after the design pattern is printed by ink jet to form an antibacterial glaze polishing layer. The antibacterial glaze polishing comprises the following raw materials: the polishing solution comprises, by mass, 3-5% of a silver-zinc composite antibacterial agent, 0.15-0.45% of a suspending agent, 0.2-0.5% of a debonding agent, 45-55% of water and the balance of basic polishing. The particle size of the silver-zinc composite antibacterial agent is 200-350 nm.
The chemical composition of the basic glaze is not limitedAnd (3) preparing the glaze by adopting the basic glaze polishing commonly used in the field. For example, the chemical composition of the base glaze may include, in mass percent: IL: 7.52-9.16%; SiO 22：40.25～50.62％；Al2O3：13.75～16.86％；Fe2O3：0.15～0.28％；TiO2：0.12～0.20％；CaO：4.15～5.25％；MgO：4.12～5.32％；K2O：1.20～2.25％；Na2O：2.85～4.20％；BaO：4.52～6.50％；ZnO：2.15～3.80％；SrO：2.25～3.20％；P2O5：0.03～0.08％。
The preparation method of the antibacterial polished glaze comprises the following steps: and uniformly mixing the silver-zinc composite antibacterial agent, the suspending agent, the dispergator and the basic glaze, adding water, ball-milling for 6-8 hours, and sieving to obtain the antibacterial glaze. The suspending agent is at least one of carboxymethyl cellulose and polyvinyl alcohol. The dispergator is at least one of sodium tripolyphosphate and sodium metasilicate. The screen allowance of the antibacterial overglaze passing through a 325-mesh screen is 2.0-2.4 wt%.
The application mode of the antibacterial polishing glaze can be glaze spraying. The specific gravity of the antibacterial polished glaze is 1.45-1.60 g/cm3The flow rate is 35-60 s, and the glazing amount is 70-85 g/cm2。
And sintering the blank body after the antibacterial polishing. Can be put into a kiln for sintering. The maximum firing temperature is 1180-1220 ℃, and the firing period is 68-85 min.
And polishing and edging the fired ceramic plate. And (3) performing antibacterial wax water ultra-clean treatment on the polished ceramic plate to obtain the ceramic plate with stable and lasting antibacterial performance.
And (3) performing ultra-clean treatment on the antibacterial wax by using the nano antibacterial filling material to form an antibacterial material filling layer. The nano antibacterial filling material consists of nano zinc oxide dispersion liquid and ultra-clean wax. The nano zinc oxide dispersion liquid accounts for 3-8 wt% of the nano antibacterial filling material. The composition of ultra clear wax is conventional in the art and is commercially available. The nano zinc oxide dispersion liquid is a dispersion liquid of nano zinc oxide in an aqueous medium (such as water). The nano zinc oxide accounts for 1.5-5 wt% of the dispersion liquid. The particle size of the nano zinc oxide is 20-40 nm. The purpose of using the nano antibacterial filling material to carry out the super-clean treatment of the antibacterial wax water is to fill finer zinc oxide particles in the surface micropores of the ceramic plate so as to achieve better antibacterial effect.
The preparation method of the nano antibacterial filling material comprises the following steps: and dispersing the nano zinc oxide into a dispersion liquid with uniform liquid quality by ultrasonic waves, and uniformly mixing the dispersion liquid with ultra-clean wax water to obtain the nano antibacterial filling material.
The coating amount of the nano antibacterial filling material on the surface of the ceramic plate is 10-25 g/m2. The antibacterial rate of more than 99 percent is difficult to achieve when the coating amount is small; the coating amount is too large, the antibacterial ratio has reached the upper limit, and the cost is increased.
The ceramic plate with stable and lasting antibacterial performance comprises a nano antibacterial material filling layer, an antibacterial glaze-throwing layer, an ink-jet printing layer, an antibacterial surface glaze layer and a ceramic plate substrate layer from top to bottom.
The antibacterial ceramic plate obtained by the preparation method disclosed by the invention has excellent antibacterial property on the basis of keeping the physical property of the ceramic plate, and antibacterial ions are dissolved out from the antibacterial agent modified ultra-clean polishing wax or antibacterial glaze and can be fully contacted with bacteria adsorbed on the surface of the ceramic plate, so that the antibacterial rate of the ceramic plate product on escherichia coli and staphylococcus aureus reaches more than 99%.
In addition, in the process of filling the nano antibacterial filling material, the nano antibacterial material is filled into micropores exposed by polishing on the surface of the ceramic plate through friction between the felt and the surface of the ceramic plate, so that antibacterial ions can be uniformly distributed on the surface of the ceramic plate. After the antibacterial material filling layer on the surface of the ceramic plate is worn for a period of time, antibacterial ions in the glaze can be dissolved out to supplement the loss part, and the stability and the lasting property of antibacterial performance are ensured. After repeated tests, the antibacterial rate of the ceramic plate can be stabilized at more than 95% for a long time, and the antibacterial durability of the ceramic plate also reaches more than 90%.
The antibacterial material is only filled in the micropores on the surface of the ceramic tile, so that the antibacterial component is lost to a certain extent after the surface layer is abraded, the antibacterial component below the glaze layer is not precipitated and supplemented after the glaze layer is abraded, and the antibacterial durability cannot be guaranteed. Only the antibacterial component is introduced into the antibacterial glaze layer, the antibacterial component needs to be separated out from the glaze layer until the surface of the glaze layer is contacted with bacteria to show the antibacterial effect, and the dissolution of antibacterial ions is slow, so that the separated antibacterial ions cannot be uniformly dispersed on the surface of the ceramic tile. The invention carries out antibacterial functional treatment on the body layer, the overglaze layer, the glaze-polished layer and the surface micropores, antibacterial components from the overglaze layer can be separated out and supplemented after the surface glaze layer is worn, and the antibacterial ceramic tile has excellent antibacterial performance and good antibacterial durability under the action of infrared radiation of rare earth oxide.
The present invention will be described in detail by way of examples. It is also to be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the invention, and that certain insubstantial modifications and adaptations of the invention by those skilled in the art may be made in light of the above teachings. The specific process parameters and the like of the following examples are also only one example of suitable ranges, i.e., those skilled in the art can select the appropriate ranges through the description herein, and are not limited to the specific values exemplified below.
Example 1
The preparation method of the antibacterial stable and durable ceramic plate comprises the following steps:
s1, preparing a ceramic plate blank and uniformly spraying an antibacterial overglaze on the surface; 1.5 percent of silver-zinc composite antibacterial agent and La oxide of rare earth metal according to mass percentage2O31.0 percent of sodium tripolyphosphate, 0.2 percent of carboxymethyl cellulose and 0.3 percent of sodium tripolyphosphate are respectively added into 47 percent of basic overglaze to be uniformly mixed, and 50 percent of water is added for ball milling for 8 hours to obtain the mixture with the specific gravity of 1.55g/cm3The flow rate is 40s, and the surplus sieve is 1.9wt percent of the antibacterial overglaze; the glazing amount of the antibacterial overglaze is 50g/m2；
S2, printing patterns with rich colors and bright textures on the surface of the blank body in an ink jet mode;
s3, continuously spraying antibacterial glaze polishing on the surface of the blank; respectively adding 3.5 percent of silver-zinc composite antibacterial agent, 0.2 percent of carboxymethyl cellulose and 0.3 percent of sodium tripolyphosphate into 41 percent of basic glaze polish according to the mass percent, and uniformly mixingHomogenizing, adding 55% water, ball milling for 8 hr to obtain specific gravity of 1.46g/cm3The flow rate is 45s, and the surplus is 2.1 wt%; the glazing amount of the antibacterial polishing glaze is 75g/m2；
S4, firing the blank in a kiln; the highest sintering temperature is 1190 ℃, and the sintering period is 70 min;
s5, polishing, edging and ultra-clean and bright treatment of the antibacterial wax; dispersing nano zinc oxide into dispersion liquid with uniform liquid quality and solid content of 5%, and uniformly mixing the 2.0% dispersion liquid with 98% ultra-clean wax water to obtain a nano antibacterial filling material; uniformly coating the nano antibacterial filling material on the surface of the polished and edged ceramic plate by a felt polishing process; the coating amount of the nano antibacterial filling material is 15g/m2(ii) a And curing the wax water layer to obtain the ceramic plate.
Example 2
The preparation method of the antibacterial stable and durable ceramic plate comprises the following steps:
s1, preparing a ceramic plate blank and uniformly spraying an antibacterial overglaze on the surface; 2.5 percent of silver-zinc composite antibacterial agent and rare earth metal oxidized CeO21.5 percent of sodium tripolyphosphate, 0.25 percent of carboxymethyl cellulose and 0.35 percent of sodium tripolyphosphate are respectively added into 45.4 percent of basic overglaze to be uniformly mixed, and 50 percent of water is added for ball milling for 9 hours to obtain the mixture with the specific gravity of 1.52g/cm3The flow rate is 35s, and the surplus sieve is 2.2wt percent of the antibacterial overglaze; the glazing amount of the antibacterial overglaze is 45g/m2；
S2, printing patterns with rich colors and bright textures on the surface of the blank body in an ink jet mode;
s3, continuously spraying antibacterial glaze polishing on the surface of the blank; respectively adding 5 percent of silver-zinc composite antibacterial agent, 0.25 percent of carboxymethyl cellulose and 0.4 percent of sodium tripolyphosphate into 42.35 percent of basic polishing glaze according to the mass percent, uniformly mixing, adding 52 percent of water, and ball-milling for 7.5 hours to obtain the silver-zinc composite antibacterial agent with the specific gravity of 1.49g/cm3The flow rate is 40s, and the surplus is 2.3wt percent; the glazing amount of the antibacterial polishing glaze is 80g/m2；
S4, firing the blank in a kiln; the highest sintering temperature is 1195 ℃, and the sintering period is 70 min;
s5, polishing, edging and ultra-clean and bright treatment of the antibacterial wax; subjecting nanometer zinc oxide to ultrasonic treatmentDispersing the waves into a dispersion liquid with uniform liquid quality and solid content of 7%, and uniformly mixing the dispersion liquid with 4% and 96% of ultra-clean wax water to obtain a nano antibacterial filling material; uniformly coating the nano antibacterial filling material on the surface of the polished and edged ceramic plate by a felt polishing process; the coating amount of the nano antibacterial filling material is 20g/m2(ii) a And curing the wax water layer to obtain the ceramic plate.
Example 3
The preparation method of the antibacterial stable and durable ceramic plate comprises the following steps:
s1, preparing a ceramic plate blank and uniformly spraying an antibacterial overglaze on the surface; according to the mass percentage, 3 percent of silver-zinc composite antibacterial agent and rare earth metal oxide CeO 21% of rare earth metal oxide Sm2O31 percent, 0.35 percent of carboxymethyl cellulose and 0.45 percent of sodium tripolyphosphate are respectively added into 44.2 percent of basic overglaze to be evenly mixed, and 50 percent of water is added for ball milling for 9.5 hours to obtain the mixture with the specific gravity of 1.63g/cm3The flow rate is 45s, and the surplus sieve is 2.4wt percent of the antibacterial overglaze; the glazing amount of the antibacterial overglaze is 60g/m2；
S2, printing patterns with rich colors and bright textures on the surface of the blank body in an ink jet mode;
s3, continuously spraying antibacterial glaze polishing on the surface of the blank; respectively adding 4.5 percent of silver-zinc composite antibacterial agent, 0.15 percent of carboxymethyl cellulose and 0.2 percent of sodium tripolyphosphate into 50.15 percent of basic glaze polish according to the mass percent, uniformly mixing, adding 45 percent of water, and ball-milling for 7.5 hours to obtain the silver-zinc composite antibacterial agent with the specific gravity of 1.58g/cm3The flow rate is 55s, and the surplus is 2.4 wt%; the glazing amount of the antibacterial polishing glaze is 78g/m2；
S4, firing the blank in a kiln; the highest firing temperature is 1210 ℃, and the firing period is 85 min;
s5, polishing, edging and ultra-clean and bright treatment of the antibacterial wax; dispersing nano zinc oxide into dispersion liquid with uniform liquid quality and solid content of 8%, and uniformly mixing the dispersion liquid with 5% and ultra-clean wax water with 95% to obtain a nano antibacterial filling material; uniformly coating the nano antibacterial filling material on the surface of the polished and edged ceramic plate by a felt polishing process; the coating amount of the nano antibacterial filling material is 25g/m2(ii) a The wax water layer is solidified to obtainThe ceramic plate.
TABLE 1 results of measurement of antibacterial samples prepared in examples 1 to 3
Figure BDA0003281527870000071
The antibacterial rate test method comprises the following steps: respectively inoculating colibacillus and staphylococcus aureus on the surface of the antibacterial ceramic plate, detecting the colony number, culturing for 24 hours, detecting the colony number on the surface of the ceramic plate again, and calculating according to the numerical value of the colony number before and after culturing to obtain the antibacterial rate.
The antibacterial durability detection method comprises the following steps: and (3) simulating a cleaning mode of a product in the using process, repeatedly brushing the surface of the sample for 500 times by using sodium hypochlorite disinfectant with the mass fraction of 5%, and detecting the antibacterial performance of the surface of the sample after brushing.
The detection results show that the antibacterial rate of the antibacterial ceramic plate prepared by the technical scheme of the invention is more than 99%, and the antibacterial durability is good and more than 90%.
Example 4
This embodiment is substantially the same as embodiment 1 except that: the nano antibacterial filling material is ultra-clean and bright wax water, and a nano zinc oxide antibacterial agent is not added.
Example 5
This embodiment is substantially the same as embodiment 2 except that: the overglaze is ordinary overglaze, which comprises carboxymethyl cellulose 0.25%, sodium tripolyphosphate 0.35%, basic overglaze 49.4%, and water 50%.
Example 6
This example is substantially the same as example 3, except that: the glaze polishing is ordinary glaze polishing, and comprises carboxymethyl cellulose 0.15%, sodium tripolyphosphate 0.2%, basic glaze polishing 52.15%, and water 47.5%.
TABLE 2 results of antibacterial tests of examples 4-6
Figure BDA0003281527870000081
From the results of the antibacterial tests in table 2, it can be seen that: whether the super-clean and bright antibacterial wax water is added or not has obvious influence on the antibacterial rate of the sample. As shown in example 4, when the ultra-clean antibacterial wax water is replaced by the ordinary wax water, the antibacterial ratio is reduced to 90% or less compared with example 2, and when the examples 3 and 4 are compared with examples 5 and 6, respectively, it can be seen that one of the antibacterial overglaze and the antibacterial polishing glaze is replaced by the corresponding ordinary glaze, although the antibacterial ratio is above 95%, the antibacterial durability of the sample is reduced to 85% or less, and the durable antibacterial effect cannot be realized. This is because the antibacterial material filling layer on the surface layer is worn to a certain extent after the tile is used for a certain period of time and the surface is repeatedly trodden, cleaned, rubbed, etc., and the antibacterial durability of the tile cannot be ensured without dissolution supplement of antibacterial ions in the antibacterial glaze and infrared radiation action of rare earth oxides. Therefore, the triple cooperation of the antibacterial overglaze, the antibacterial polishing glaze and the ultra-clean and bright antibacterial wax water is a necessary premise for ensuring that the sample can achieve stable and lasting antibacterial property.
Example 7
This embodiment is substantially the same as embodiment 1 except that: the antibacterial overglaze consists of 0.5% of silver-zinc composite antibacterial agent and La oxide of rare earth metal2O30.5 percent of carboxymethyl cellulose, 0.2 percent of sodium tripolyphosphate, 48.5 percent of basic overglaze and 50 percent of water.
Example 8
This embodiment is substantially the same as embodiment 2 except that: the antibacterial polished glaze consists of 2.5% of silver-zinc composite antibacterial agent, 0.25% of carboxymethyl cellulose, 0.4% of sodium tripolyphosphate, 46.85% of basic polished glaze and 50% of water.
Example 9
This example is substantially the same as example 3, except that: the nano antibacterial material is prepared by mixing 2.5% of nano zinc oxide dispersion liquid and 97.5% of ultra-clean wax water.
TABLE 3 results of antibacterial tests of examples 7-9
Figure BDA0003281527870000091
As can be seen from table 3, if the antibacterial component added to the antibacterial overglaze, the antibacterial polishing glaze, and the nano antibacterial material is not within the predetermined range, the antibacterial ratio and the antibacterial durability of the sample do not reach the preferable results.

Claims (10)

1. A preparation method of a ceramic plate with stable and durable antibacterial performance is characterized by comprising the following steps:
pressing the ceramic base material into a green body;
applying an antibacterial overglaze on the surface of the blank;
printing a design pattern on the surface of the blank after the antibacterial overglaze is applied by ink jet;
applying antibacterial glaze polishing on the surface of the blank after the design pattern is printed by ink jet;
sintering and polishing the blank body after the antibacterial glazing is applied;
and (3) filling the polished ceramic plate with a nano antibacterial material to obtain the ceramic plate with stable and durable antibacterial performance.
2. The preparation method according to claim 1, wherein the raw material composition of the antibacterial overglaze comprises: the silver-zinc composite antibacterial agent comprises, by mass, 1-3% of a silver-zinc composite antibacterial agent, 0.5-2.0% of a rare earth metal oxide, 0.1-0.35% of a suspending agent, 0.15-0.45% of a debonding agent, 50-55% of water and the balance of a basic overglaze.
3. The method according to claim 1 or 2, wherein the antibacterial overglaze is applied by spraying glaze; the specific gravity of the antibacterial overglaze is 1.50-1.65 g/cm3The flow rate is 30-50 s, and the glazing amount is 45-60 g/cm2。
4. The preparation method according to any one of claims 1 to 3, wherein the raw material composition of the antibacterial glaze comprises: the polishing solution comprises, by mass, 3-5% of a silver-zinc composite antibacterial agent, 0.15-0.45% of a suspending agent, 0.2-0.5% of a debonding agent, 45-55% of water and the balance of basic polishing.
5. The production method according to any one of claims 1 to 4, wherein the antibacterial glaze is applied by spraying glaze; the specific gravity of the antibacterial polished glaze is 1.45-1.60 g/cm3The flow rate is 35-60 s, and the glazing amount is 70-85 g/cm2。
6. The production method according to any one of claims 1 to 5, wherein the filling treatment is an antibacterial wax water ultra-clear treatment using a nano antibacterial filling material; the nano antibacterial filling material consists of nano zinc oxide dispersion liquid and ultra-clean wax liquid; the nano zinc oxide dispersion liquid accounts for 3-8 wt% of the nano antibacterial filling material.
7. The preparation method according to claim 6, wherein the nano zinc oxide dispersion is a dispersion of nano zinc oxide in an aqueous medium; the nano zinc oxide accounts for 1.5-5 wt% of the dispersion liquid; the particle size of the nano zinc oxide is 20-40 nm.
8. The method according to claim 6 or 7, wherein the nano antibacterial filling material is coated on the surface of the ceramic plate in an amount of 10 to 25g/m2。
9. The method for preparing according to any one of claims 1 to 8, wherein the raw material composition of the ceramic base material comprises: by mass percentage, calcined kaolin 15-22%, water washing mud 12-17%, quartz sand 18-25%, potassium sand 2-6%, wollastonite 2.5-4.5%, potash-soda feldspar 15-21%, calcined talc 3-8%, fine mud 1-5%, bentonite 1-5%, rare earth oxide 2-4%, suspending agent 0.1-0.4%, and debonding agent 0.25-0.45%; the rare earth oxide is La2O3、CeO2And Sm2O3At least one of (1).
10. The ceramic plate with stable and durable antibacterial performance obtained by the preparation method according to any one of claims 1 to 9, wherein the antibacterial rate of the ceramic plate to escherichia coli and staphylococcus aureus is 99% or more; after the surface of the ceramic plate is brushed for 500 times by using a sodium hypochlorite disinfectant with the mass fraction of 5%, the antibacterial rate of the ceramic plate to escherichia coli and staphylococcus aureus is kept above 99%.
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