Method for producing ceramic plate with anti-counterfeiting visual effect

Abstract

The present invention provides a ceramic plate with anti-counterfeiting visual effect and its manufacturing method, which includes the steps of: using blank powder to manufacture a body; applying glaze to the surface of the body; printing a pattern on the surface of the body with the glaze by inkjet; applying protective glaze to the surface of the body with the pattern printed by inkjet; applying anti-counterfeiting material to the surface of the body with the protective glaze, the raw material composition of the anti-counterfeiting material includes, by mass percentage, 20-30% titanite, 3-5% high refractive index oxide, and 60-80% low-temperature glaze powder; firing the body with the anti-counterfeiting material, so that the titanite and the high refractive index oxide are wetted and enveloped in the molten liquid generated by the melting of the low-temperature glaze powder in the firing environment, sinking into the protective glaze but not producing milky turbidity, and then polishing to obtain a ceramic plate with anti-counterfeiting visual effect, and the anti-counterfeiting visual effect is that when the line of sight is aligned with the path of the reflected light, there is a high refraction effect, and when the line of sight is deviated from the path of the reflected light, there is no refraction effect.

Description

[Technical field]

[0001] The present invention relates to the field of architectural ceramics, specifically to a ceramic plate with anti-counterfeiting visual effects and a manufacturing method thereof. [Background technology]

[0002] Counterfeiting of ceramic products not only damages the creative spirit of ceramic enterprises, destroys the image of innovative ceramic enterprises, and disrupts the normal ceramic market, but also tarnishes the reputation of brand ceramic enterprises and seriously threatens the sustainable development of the ceramic industry. Therefore, focusing on the development of ceramic products with anti-counterfeiting function is one of the main directions of ceramic enterprises' current research. Anti-counterfeiting ceramic products can provide standardized ceramic products with a certain identification mark, and this identification mark can provide ceramic products with flexible identification authorization and protection.

[0003] At present, the market generally uses fluorescent or color-changing anti-counterfeiting materials to prevent counterfeiting. For example, polymeric anti-counterfeiting materials with special structures change color under the influence of external environment to realize anti-counterfeiting. Or, thermochromic materials that are colorless at room temperature and show color at critical temperature are used. At present, this type of thermochromic material is relatively common in everyday ceramics. In addition, inorganic color-changing materials such as tungstates and neodymium oxides can achieve color-changing effects, but such inorganic color-changing materials have their own color, which may affect the surface decoration of ceramic products. Luminescent inks are often used as decorative colors on antique surfaces, and have obvious luminous effects on tile surfaces, which cannot prevent counterfeiting.

[0004] Patent Document 1 discloses a ceramic tile with a metallic luster decorative effect and a manufacturing method thereof. The manufacturing method includes obtaining a ceramic tile by applying a high specific gravity and high refractive index glaze to a tile base coated with a matte polished glaze and firing the tile base, and since the melting temperature and specific gravity of the high specific gravity and high refractive index glaze are higher than those of the matte polished glaze, at least a part of the high specific gravity and high refractive index glaze sinks into the molten liquid phase formed by the matte polished glaze during the firing process and is entirely or partially enveloped by the molten liquid phase. The method uses a substance with a high refractive index and further polishes the substance to obtain a glaze with a metallic luster decorative effect. However, the high refractive index substance used in this method has a high content and a small particle size, which causes opacity on the tile surface and is likely to form white lines that appear as metallic luster decoration on the tile surface. Therefore, this method is not applicable to the manufacture of anti-counterfeit ceramic products. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] China Patent Application Publication No. 111732453 Summary of the Invention [Problem to be solved by the invention]

[0006] In response to the above problems, the present invention provides a ceramic plate with anti-counterfeit visual effect and a manufacturing method thereof. When light hits the surface of the ceramic plate, high-intensity reflected light enters the eye, giving a bright visual impression. However, when the line of sight deviates from the path of the reflected light, the reflective effect is not visible to the naked eye. [Means for solving the problem]

[0007] In a first aspect, the present invention provides a method for manufacturing a ceramic plate having an anti-counterfeiting visual effect, the method comprising: Producing a green body using the blank powder; A step of applying a top glaze to the surface of the base material; printing a pattern on the surface of the glazed base by inkjet; applying a protective glaze to the surface of the base material on which the pattern is printed by inkjet; Applying an anti-counterfeiting material to the surface of the base material coated with the protective glaze, the raw material composition of the anti-counterfeiting material includes, in mass percentage, 20-30% titanite, 3-5% high refractive index oxide, and 60-80% low temperature glaze powder; and firing the base material coated with the anti-counterfeiting material, so that the titanite and high refractive index oxide are wetted and enveloped in the molten liquid generated by the melting of the low-temperature glaze powder in the firing environment, and sink into the protective glaze but do not produce milky turbidity, and then polishing to obtain a ceramic plate with anti-counterfeiting visual effect, which is to say that there is a high refraction effect when the line of sight is aligned with the path of the reflected light, and there is no refraction effect when the line of sight is deviated from the path of the reflected light.

[0008] Preferably, the low-temperature glaze powder has a melting start temperature of 1080 to 1130°C.

[0009] Preferably, the chemical composition of the low-temperature glaze powder is, in mass percentage, SiO 2 : 62-70%, Al 2 O 3 : 16-18%, alkaline earth metal oxides: 5.5-8.5%, alkali metal oxides: 2.7-4.5%, ZnO: 1-3%.

[0010] Preferably, the particle size of the high refractive index oxide and titanite are each independently selected from 1 to 2 μm.

[0011] Preferably, the protective glaze is a pseudo-patterned glaze, the chemical composition of which is, in mass percentage, SiO 2 : 62-66%, Al 2 O 3 : 18-20%, alkaline earth metal oxides: 10-14%, alkali metal oxides: 2.7-4.5%, ZnO: 1-3%.

[0012] Preferably, the protective glaze is a polishing glaze and has a chemical composition, in mass percentage, of: SiO 2 : 62-68%, Al 2 O 3 : 16-19%, alkaline earth metals, oxides: 6-11.5%, alkali metal oxides: 3.3-5.4%, ZnO: 2-5%.

[0013] Preferably, the protective glaze is applied by spraying, and the specific gravity of the protective glaze is 1.4 to 1.6 g / cm 3 The amount of glaze applied is 160-250g / m 2 It is.

[0014] Preferably, the method of applying the anti-counterfeiting material is to screen print the anti-counterfeiting material or to sprinkle the anti-counterfeiting material in the form of a frit.

[0015] Preferably, the high refractive index oxide is cerium oxide and / or tin oxide.

[0016] In a second aspect, the present invention provides a ceramic plate having an anti-counterfeiting visual effect, which is obtained by any of the manufacturing methods described above. [Brief description of the drawings]

[0017] [Figure 1] FIG. 1 is a diagram illustrating the effect of a tile surface of a ceramic product according to Example 1 of the present invention. The left side of the diagram illustrates the effect of a tile surface when the line of sight is offset from the path of the reflected light, and the right side illustrates the effect of a tile surface when the line of sight is aligned with the path of the reflected light. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0018] The present invention will be further described through the following embodiments. Note that the following embodiments are for explaining the present invention, but do not limit the present invention. In addition, each "%" means "mass %" unless otherwise specified. Hereinafter, a method for manufacturing a ceramic plate having an anti-counterfeit visual effect (anti-counterfeit ceramic plate) of the present invention will be described by way of example.

[0019] A blank powder is used to manufacture a green body. The chemical composition of the blank powder is, in mass percentage, SiO 2 : 60-67%, Al 2 O 3 :20~23%, CaO:0.3~0.5%, MgO:0.4~0.6%, K 2 O: 2.5-3.5%, Na 2 O: 2.0-2.8%, Fe 2 O 3 : 0.3 to 0.5%, TiO 2 : Contains 0.15 to 0.3%. The manufacturing method of the body includes, but is not limited to, dry press molding.

[0020] Dry the base material. The drying temperature is 150-250℃, and the drying time is 30-40 minutes. The moisture content of the base material after drying is controlled within 0.35-0.5wt%.

[0021] The surface of the dried body is coated with a glaze. The purpose of this is to cover the base color and defects of the body and to promote the color development of the inkjet pattern. The chemical composition of the glaze is, by mass percentage, SiO 2 : 60-65%, Al 2 O 3 : 19-25%, alkaline earth metal oxides: 2.2-4.0%, alkali metal oxides: 5.3-7.1%, ZnO: 3-5%. As an example, the chemical composition of the above-mentioned glaze is, in mass percentage, SiO 2 : 60-65%, Al 2 O 3 :19~25%, CaO:0.4~0.8%, MgO:0.3~0.7%, K 2 O: 2.8-3.6%, Na 2 Contains O: 2.5-3.5%, BaO: 1.5-2.5%, ZnO: 3-5%.

[0022] The method of applying the top glaze is by spraying. The specific gravity of the top glaze is 1.45 to 1.55 g / cm 3 The amount of glaze applied is 200-230g / m 2 It is.

[0023] A pattern is printed on the surface of the glazed base by inkjet printing, and the texture and color of the pattern can be adaptively adjusted according to the design effect of the layout. The pattern can be an anti-counterfeiting mark.

[0024] A protective glaze is applied to the surface of the substrate on which the inkjet pattern is printed. The protective glaze may be a polished glaze or an antique glaze.

[0025] The chemical composition of antique glaze is, by mass percentage, SiO 2 : 62-66%, Al 2 O 3 : 18 to 20%, alkaline earth metal oxides: 10 to 14%, alkali metal oxides: 2.7 to 4.5%, ZnO: 1 to 3%. As an example, the chemical composition of the antique glaze is, in mass percentage, SiO 2 : 62-66%, Al 2 O 3 :18~20%, CaO:4.5~5.5%, MgO:1.5~2.5%, K 2 O: 2.5-3.5%, Na 2 Contains O: 0.2-1.0%, BaO: 3-6%, ZnO: 1-3%.

[0026] The chemical composition of the polishing glaze is, by mass percentage, SiO 2 : 62-68%, Al 2 O 3 : 16 to 19%, alkaline earth metal oxides: 6 to 11.5%, alkali metal oxides: 3.3 to 5.4%, ZnO: 2 to 5%. As an example, the chemical composition of the polishing glaze is, in mass percentage, SiO 2 : 62-68%, Al 2 O 3 :16~19%, CaO:3.5~5.5%, MgO:0.5~1%, K 2 O: 2.8-3.9%, Na 2 Contains O: 0.5-1.5%, BaO: 2-5%, ZnO: 2-5%.

[0027] The protective glaze may be applied by spraying. The specific gravity of the protective glaze is 1.4 to 1.6 g / cm 3 The amount of glaze applied is 160-250g / m 2 The above glazing process is favorable to the sinking of high refractive index oxide and titanite, and promotes the formation of anti-counterfeiting effect.

[0028] The surface of the base material coated with the protective glaze is coated with an anti-counterfeiting material. The anti-counterfeiting material includes titanite, high refractive index oxide, and low temperature glaze powder. In some embodiments, the raw material composition of the anti-counterfeiting material includes, by mass percentage, 20-30% titanite, 3-5% high refractive index oxide, and 60-80% low temperature glaze powder. The refractive index of the high refractive index oxide is about 2.3-2.5. If only high refractive index oxide is used to form the refraction effect, the high refractive index oxide has a high melting point, so that a large number of pores are likely to occur on the polished glaze surface. Similarly, if only titanite is used to form the refraction effect, the refraction effect can be avoided when the titanite is small because the refraction effect of titanite is relatively low, but the refraction effect is not obvious, which affects the anti-counterfeiting effect, and the titanite is prone to cause opalescence when it is excessive, and there is no significant difference in the refraction effect when the line of sight is aligned with the path of the reflected light and when the line of sight is deviated from the path of the reflected light. As a result of research, it was found that the anti-counterfeiting material of the present invention can avoid opacity as much as possible and provide a strong refraction effect in the appropriate line of sight to the surface of the ceramic product by simultaneously introducing titanite and high refractive index oxide and controlling the mass ratio of titanite with a relatively low refractive index to high refractive index oxide with a relatively high refractive index. For example, the mass ratio of the titanite to the high refractive index oxide is (5~10):1. In addition, titanite has a low melting point, so it can be well combined with low-temperature glaze powder and prevent the generation of bubbles.

[0029] The melting start temperature of the low-temperature glaze powder is 1080-1130°C. The most important function of the low-temperature glaze powder is to dissolve high-melting point and high-refractive index materials in the glaze to prevent the occurrence of pores. If the melting start temperature of the low-temperature glaze powder is low, the low-temperature glaze powder will melt first under high temperature, which is bad for exhaust. If the melting start temperature of the low-temperature glaze powder is high, it will not have a good flux effect and will also be prone to pores.

[0030] The chemical composition of the low-temperature glaze powder in Patent Document 1 is, in mass percentage, ignition loss: 0.43 to 0.53%, SiO 2 : 44.67~46.52%, Al 2 O 3 : 8.33~9.72%, Fe 2 O 3 : 0.18~0.23%, TiO 2 :0.09~0.14%, CaO:3.43~4.98%, MgO:0.88~1.98%, K 2 O: 1.74-2.57%, Na 2 O: 2.05-2.94%, ZrO 2 :3.89~4.98%, ZnO:10.02~11.70%, PbO:5.87~6.92%, CeO 2 The chemical composition of the low-temperature glaze powder described in the present invention is, in mass percentage, SiO 2 : 62-70%, Al 2 O 3 : 16-18%, alkaline earth metal oxides: 5.5-8.5%, alkali metal oxides: 2.7-4.5%, ZnO: 1-3%. As an example, the chemical composition of low-temperature glaze powder is, in mass percentage, SiO 2 : 62-70%, Al 2 O 3 :16~18%, CaO:2.0~2.5%, MgO:0.5~1%, K 2 O: 2.5-3.5%, Na 2The low-temperature glaze powder contains 0.2-1.0% O, 3-5% BaO, and 1-3% ZnO. This shows that the low-temperature glaze powder of the present invention does not contain any milky components such as zirconium oxide, in order to avoid the inability to prevent counterfeiting due to milkiness on the glaze surface. In the present invention, the silicon aluminum content and the flux content are controlled so that the glaze has appropriate high-temperature viscosity and high-temperature fluidity. In the inventions of the above-mentioned patents, zirconium oxide and cerium oxide are added in large amounts, and since the melting points of these substances both exceed 1800°C, it is necessary to add a large amount of flux to lower the firing temperature.

[0031] The low-temperature glaze powder of the present invention has a wide melting temperature range, which is advantageous for expelling air bubbles and exhibits a flux effect. In addition, the molten liquid generated by the low-temperature glaze powder at high temperature melting has a suitable viscosity, which contributes to the sinking of titanite and high refractive index oxides in the protective glaze during the firing process, and prevents them from falling off during polishing. The low-temperature glaze powder has good fluidity during the firing process, so it can fully encapsulate titanite and high refractive index oxides to form a transparent high refractive index emission line.

[0032] In some embodiments, the raw material composition of the anti-counterfeiting material includes, by mass percentage, 20-30% titanite, 2-3% cerium oxide, 1-1.8% tin oxide, and 60-80% glaze powder. The titanite, cerium oxide, and tin oxide all have a certain color, and when these three are excessive, the color will appear on the ceramic surface, which will affect the anti-counterfeiting. If the content of cerium oxide or titanite is too high, the glaze surface will be yellow, and if the content of tin oxide is too high, the glaze surface will be red. In addition, as mentioned above, the titanite, cerium oxide, and tin oxide all have a certain refractive index, and if not properly controlled, they are prone to milkiness, in which case there will be a white line on the tile surface, which can show a flashing effect, but cannot achieve anti-counterfeiting. The reason is that the surface of the anti-counterfeiting ceramic product and the surface of the ordinary ceramic product will only show the anti-counterfeiting mark or anti-counterfeiting visual effect under certain circumstances.

[0033] The purpose of making the mass fraction of low-temperature glaze powder in the anti-counterfeiting material 60-80% is to facilitate melting. If the content of low-temperature glaze powder in the anti-counterfeiting material is too low, it is easy to generate pores. If the content of low-temperature glaze powder in the anti-counterfeiting material is too high, the flash effect is not obvious, the refractive index of the glaze surface is low, and no obvious brilliance effect can be seen.

[0034] It is worth noting that when the low-temperature glaze powder is omitted in the anti-counterfeiting material, the titanite and high refractive index material can still sink into the protective glaze, but there is no low-temperature glaze powder to envelop and wet the titanite and high refractive index material, so the glaze surface is prone to pinholes due to poor ventilation, and as a result, the glaze surface is not flat.

[0035] The particle size of cerium oxide, tin oxide and titanite is within the range of 1-2μm. If the particle size of cerium oxide, tin oxide and titanite is too small, the glaze surface is likely to become opaque. If the particle size of cerium oxide, tin oxide and titanite is too large, the glaze surface becomes too hot, which is unfavorable for the discharge of pores.

[0036] The method of applying the anti-counterfeiting material is to screen print the anti-counterfeiting material or to sprinkle the anti-counterfeiting material in frit form. In some embodiments, the application amount of the anti-counterfeiting material is 20-30 g / m 2 It is.

[0037] It is then fired in a kiln. For example, the maximum firing temperature is 1150 to 1180°C, and the firing time is 55 to 65 minutes.

[0038] Polishing. Using the appropriate module combination for polishing can make the differentiation of anti-counterfeiting visual effect more obvious.

[0039] For antique glaze surfaces, the polishing modules are two sets of modules with a mesh size of about 2000 and two sets of modules with a mesh size of about 3000. With antique glaze surfaces, the difference in flash can be clearly seen just by flicking.

[0040] For the polished glaze surface, the polishing modules are arranged from coarse to fine. The module configuration is two sets of 200 mesh modules, four sets of 800 mesh modules, two sets of 1000 mesh modules, two sets of 2000 mesh modules, and two sets of 3000 mesh modules. Deep polishing is easy to damage the anti-counterfeiting pattern, and shallow polishing cannot achieve the appropriate luster.

[0041] The present invention produces a ceramic plate with anti-counterfeit visual effect based on the refraction of light. The specification of the ceramic plate is not limited, nor is it an improvement of the present invention. The present invention applies an anti-counterfeit material containing titanite, high refractive index oxide and low temperature glaze powder to a tile surface with a protective glaze, and in the high temperature firing process, the anti-counterfeit material sinks into the protective glaze due to its high specific gravity, and after polishing, it exhibits a brilliance that can only be seen in the direction of light irradiation. That is, when the viewing direction is deviated from the path of the reflected light, there is no obvious difference in gloss on the surface of the ceramic product, but when the viewing direction is consistent with the path of the reflected light (along the direction of the light), an obvious difference in gloss is observed.

[0042] The present invention will be described in more detail through the following examples. Similarly, the following examples are provided to further explain the present invention and do not limit the scope of the present invention. Non-essential improvements and adjustments made by those skilled in the art based on the above content of the present invention are both within the scope of the present invention. Specific process variables in the following examples are merely examples within the applicable range, that is, those skilled in the art can select within an appropriate range based on the description of the present invention, and are not limited to the specific numerical values ​​in the following examples.

[0043] Example 1 The manufacturing method of the antique glazed anti-counterfeit ceramic plate includes the following steps: Step 1: Blank powder was used to prepare a green body. The green body was dried. Step 2: A top glaze was applied to the tile surface. The chemical composition of the top glaze is, in mass percentage, SiO 2 : 60%, Al2 O 3 :25%, CaO:0.4%, MgO:0.6%, K 2 O: 3.6%, Na 2 The glaze contains 3.4% O, 2.5% BaO, and 4.5% ZnO. The method of application of the top glaze is spraying, and the specific gravity is 1.45 g / cm 3 , glaze amount is 200g / m 2 It is. Step 3: The pattern was printed on the surface of the glazed base using an inkjet printer. Step 4: An antique glaze was applied to the surface of the base material on which the pattern was printed by inkjet. The chemical composition of the antique glaze was, in mass percentage, SiO 2 : 62-66%, Al 2 O 3 :18~20%, CaO:4.5~5.5%, MgO:1.5~2.5%, K 2 O: 2.5-3.5%, Na 2 The glaze contains 0.2-1.0%, BaO: 3-6%, and ZnO: 1-3%. The application method of the antique glaze is spraying, and the specific gravity is 1.55 g / cm 3 , glaze amount is 230g / m 2 It is. Step 5: The surface of the antique glazed base is screen-printed with anti-counterfeiting material. The raw material composition of the anti-counterfeiting material is, by mass percentage, 20% titanite, 2% cerium oxide, 1% tin oxide, and 77% low-temperature glaze powder. The chemical composition of the low-temperature glaze powder is, by mass percentage, SiO 2 : 62-70%, Al 2 O 3 :16~18%, CaO:2.0~2.5%, MgO:0.5~1%, K 2 O: 2.5-3.5%, Na 2 The anti-counterfeiting material contains 0.2-1.0% O, 3-5% BaO, and 1-3% ZnO. The application amount of the anti-counterfeiting material is 20 g / m 2 It is. Step 6: The anti-counterfeiting material was fired at a maximum firing temperature of 1180℃ for a firing time of 55 minutes. Step 7: Polishing. The polishing modules include two sets of 2000 mesh modules and two sets of 3000 mesh modules.

[0044] As can be seen from Fig. 1, when the direction of gaze is aligned with the path of the reflected light, the surface of the ceramic plate shows obvious flashing difference, has a strong refraction effect, and the anti-counterfeiting mark on the tile surface can be observed; when the direction of gaze is deviated from the path of the reflected light, there is no refraction effect, and the anti-counterfeiting mark on the tile surface cannot be observed.

[0045] Example 2 The manufacturing method of anti-counterfeit ceramic plate with polished glaze surface includes the following steps: Step 1: Blank powder was used to prepare a green body. The green body was dried. Step 2: A top glaze was applied to the tile surface. The chemical composition of the top glaze is, in mass percentage, SiO 2 : 65%, Al 2 O 3 :23%, CaO:0.8%, MgO:0.7%, K 2 O: 2.8%, Na 2 The glaze contains 3.2% O, 1.5% BaO, and 3% ZnO. The method of application of the top glaze is spraying, and the specific gravity is 1.55 g / cm 3 , glaze amount is 210g / m 2 It is. Step 3: The pattern was printed on the surface of the glazed base using an inkjet printer. Step 4: A polishing glaze was applied to the surface of the substrate on which the pattern was printed by inkjet. The chemical composition of the polishing glaze was, in mass percentage, SiO 2 : 62-68%, Al 2 O 3 :16~19%, CaO:3.5~5.5%, MgO:0.5~1%, K 2 O: 2.8-3.9%, Na 2 The polishing glaze contains 0.5 to 1.5%, BaO, 2 to 5%, and ZnO, and the polishing glaze is applied by spraying and has a specific gravity of 1.55 g / cm 3 , glaze amount is 200g / m 2 It is. Step 5: The surface of the polished glaze-coated base material is screen-printed with anti-counterfeiting material. The raw material composition of the anti-counterfeiting material is, by mass percentage, 30% titanite, 3% cerium oxide, 1.8% tin oxide, and 65.2% low-temperature glaze powder. The chemical composition of the low-temperature glaze powder is, by mass percentage, SiO 2 : 62-70%, Al 2 O 3 :16~18%, CaO:2.0~2.5%, MgO:0.5~1%, K 2 O: 2.5-3.5%, Na 2 The anti-counterfeiting material contains 0.2-1.0% O, 3-5% BaO, and 1-3% ZnO. The application amount of the anti-counterfeiting material is 30 g / m 2 It is. Step 6: The anti-counterfeit polished glaze is applied to the body and then fired. The maximum firing temperature is 1160℃ and the firing time is 60min. Step 7: Polishing. The polishing modules include two sets of 200 mesh modules, four sets of 800 mesh modules, two sets of 1000 mesh modules, two sets of 2000 mesh modules, and two sets of 3000 mesh modules.

[0046] Comparative Example 1 It is basically the same as Example 1, and the only difference is that the raw material composition of the anti-counterfeiting material contains, by mass percentage, 3% cerium oxide, 2% tin oxide, and 95% low-temperature glaze powder.

[0047] In the comparative example, only high refractive index oxide is used, which easily causes opacity on the tile surface and white lines appear on the tile surface, which eliminates the visual effect of preventing counterfeiting.

[0048] Comparative Example 2 It is basically the same as Example 1, and the only difference is that the raw material composition of the anti-counterfeiting material contains, by mass percentage, 30% titanite and 70% low-temperature glaze powder.

[0049] This comparative example uses only titanite, and when a high amount of titanite is used, it is easy to cause opalescence, and when a low amount is used, the refractive effect is weak.

[0050] Comparative Example 3 It is basically the same as Example 1, and the only difference is that the raw material composition of the anti-counterfeiting material contains, by mass percentage, 40% titanite, 3% cerium oxide, 3% tin oxide, and 54% low-temperature glaze powder.

[0051] If too much high refractive index material is used, the glaze surface becomes opaque.

Claims

1. Producing a green body using the blank powder; A step of applying a top glaze to the surface of the base material; printing a pattern on the surface of the glazed base by inkjet; applying a protective glaze to the surface of the base material on which the pattern is printed by inkjet; The surface of the base material coated with the protective glaze is coated with an anti-counterfeiting material, the raw material composition of the anti-counterfeiting material includes, in mass percentage, 20-30% titanite, 3-5% high refractive index oxide, and 60-80% low-temperature glaze powder, and the chemical composition of the low-temperature glaze powder is, in mass percentage, SiO ２ :62~70%, Al ２ O ３ : 16-18%, alkaline earth metal oxide: 5.5-8.5%, alkali metal oxide: 2.7-4.5%, ZnO: 1-3%, said high refractive index oxide being cerium oxide and / or tin oxide, and the particle size of the high refractive index oxide and titanite being independently selected from 1-2 μm; and firing the base material coated with the anti-counterfeiting material, so that the titanite and the high refractive index oxide are wetted and enveloped in the molten liquid generated by the melting of the low-temperature glaze powder in a firing environment, and sink into the protective glaze but do not produce milky turbidity, and then polishing the same to obtain a ceramic plate with an anti-counterfeiting visual effect, the anti-counterfeiting visual effect being a high refractive effect when the line of sight is aligned with the path of the reflected light, and no refractive effect when the line of sight is deviated from the path of the reflected light.

2. The manufacturing method according to claim 1, wherein the melting start temperature of the low-temperature glaze powder is 1080 to 1130°C.

3. The protective glaze is a pseudo-antique glaze, and its chemical composition, in mass percentage, is: SiO ２ :62~66%, Al ２ O ３ 2. The method according to claim 1, wherein the content of the SiO2 in the SiO2 mixture is 18 to 20%, alkaline earth metal oxides: 10 to 14%, alkali metal oxides: 2.7 to 4.5%, and ZnO: 1 to 3%.

4. The protective glaze is a polishing glaze, and its chemical composition, in mass percentage, is: SiO ２ :62~68%, Al ２ O ３ 2. The method according to claim 1, wherein the content of the SiO2 in the SiO2 mixture is 16 to 19%, alkaline earth metal oxides: 6 to 11.5%, alkali metal oxides: 3.3 to 5.4%, and ZnO: 2 to 5%.

5. The protective glaze is applied by spraying, and the specific gravity of the protective glaze is 1.4 to 1.6 g / cm ３ The amount of glaze applied is 160 to 250 g / m ２ The method according to claim 1,

6. The manufacturing method according to claim 1 , wherein the method of applying the anti-counterfeiting material is to screen-print the anti-counterfeiting material or to spray the anti-counterfeiting material in a frit form.

Images