Ceramic tile with color-changing decorative effect and preparation method thereof

Abstract

The invention belongs to the field of architectural ceramics, and relates to a ceramic tile with a color-changing decorative effect and a preparation method thereof. The preparation method comprises the following steps: applying cover glaze on the surface of a green brick; common ink patterns are printed on the surface of the green brick with the overglaze in an ink-jet mode; photosensitive color-changing fancy glaze is applied to the surface of the tile surface after the ordinary ink pattern is printed in an ink-jet mode, so that a photosensitive color-changing decorative pattern is formed; applying non-color-changing fancy glaze on the surface of the green brick after the photosensitive color-changing fancy glaze is applied to form a non-color-changing decorative pattern; applying protective glaze on the surface of the green brick after the non-color-changing fancy glaze is applied; and sintering the green brick coated with the protective glaze to obtain the ceramic tile with the color-changing decorative effect. According to the preparation method of the color-changing decorative ceramic tile, the photosensitive color-changing fancy glaze and the non-color-changing fancy glaze are introduced, the color-changing effect and ceramic tile decoration are combined by controlling the composition and glossiness of the photosensitive color-changing fancy glaze and the non-color-changing fancy glaze, and decoration function integration is achieved under the condition that the tile surface quality is guaranteed.

Description

TECHNICAL FIELD

[0001] The present application belongs to the field of architectural ceramics, and relates to a ceramic tile with a color-changing decorative effect and a preparation method thereof. BACKGROUND

[0002] The color of the surface of an object that can be seen by the human eye is derived from the selective absorption and reflection of visible light by the surface of the object. In color difference judgment, the human eye can observe a significant difference when the color difference ΔE is greater than 5. Based on this principle, if an object can produce a large color difference under the stimulation of external light sources, the color change effect of the object can be clearly captured by the naked eye.

[0003] Color-changing decoration is a new type of functional surface decoration technology. The color pattern on the surface of architectural ceramics changes color based on the change of light source, and in this case, different surface decoration effects can be achieved by switching the light source. The fundamental reason why color-changing decoration can be achieved is that the coloring element has a rich energy level structure, and under the excitation of external light sources, it can selectively absorb or reflect light waves of different wavebands. Taking rare earth neodymium ions (Nd 3+ ) as an example, the transition of electrons between f-f subshell energy levels can produce multiple spectral terms or line spectra. Under the excitation of external energy, Nd 3+ has narrow absorption peaks in the visible light range, especially strong absorption at 530 nm and 600 nm. Due to the existence of these two narrow absorption peaks, when the wavelength and intensity of the incident light are changed, the wavelength and intensity of the reflected light also change, resulting in a color-changing effect of the neodymium-containing pigment.

[0004] The commonly used light in indoor environments is LED white light. According to changes in indoor environments, different LED lights have different color temperatures. The color temperature of LED white light on the market changes in the range of 2700K to 6500K. In a spacious and bright hall, pure white light is usually selected, with a color temperature of about 6500K; while in a relatively warm indoor environment, the light selected is generally warm, with a color temperature of about 3000K. Only by selecting materials that are sensitive to changes in color temperature and matching them with light can a significant color-changing decorative effect be achieved.

[0005] The emergence of inkjet printing technology has led to serious homogenization of products in the architectural ceramic industry. Therefore, it is necessary to develop ceramic products with special decorative effects to increase their added value. SUMMARY

[0006] The integration of the decoration function of building ceramics is an important direction of the development of the building industry and an important technical means to improve the added value of ceramic products. The preparation method of the ceramic tile with color-changing decoration disclosed in the application introduces a photochromic color-changing glaze and a non-color-changing color glaze, combines the color-changing effect and the decoration of the ceramic tile by controlling the composition and gloss of the two glazes, and realizes the integration of the decoration function under the condition of ensuring the quality of the tile surface. The technical purpose of the application is achieved by the following technical scheme. In the first aspect, the application provides a preparation method of a ceramic tile with color-changing decoration. The preparation method comprises the following steps: Applying a surface glaze to the tile body surface; Inkjet printing a normal ink pattern on the tile body surface after the surface glaze is applied; Applying a photochromic color-changing glaze to the tile body surface after the normal ink pattern is inkjet printed to form a photochromic color-changing decoration pattern; Applying a non-color-changing color glaze to the tile body surface after the photochromic color-changing glaze is applied to form a non-color-changing decoration pattern; Applying a protective glaze to the tile body surface after the non-color-changing color glaze is applied; Firing the tile body after the protective glaze is applied to obtain a ceramic tile with color-changing decoration.

[0007] Preferably, the chemical composition of the photochromic color-changing glaze comprises, in terms of mass percentage, SiO2: 45% to 52%, Al2O3: 12% to 19%, Fe2O3: 0.05% to 0.12%, CaO: 2.1% to 3.5%, MgO: 2.6% to 3.5%, K2O: 3.5% to 4.8%, Na2O: 1.2% to 3.8%, ZnO: 4.2% to 7.9%, B2O3: 5% to 10%, and Nd2O3: 5% to 10%.

[0008] Preferably, the mineral composition of the photochromic color-changing glaze comprises, in terms of mass percentage, water-washed kaolin 5% to 10%, potassium feldspar 35% to 45%, sodium feldspar 15% to 25%, barylite 10% to 20%, aluminum oxide 5% to 12%, neodymium oxide 5% to 10%, and zinc oxide 4% to 8%.

[0009] Preferably, the application method of the photochromic color-changing glaze is screen printing or roller printing; and the specific gravity of the photochromic color-changing glaze is 1.7 to 1.8 g / cm 3 , and the glaze application amount is 60 to 80 g / m 2 .

[0010] Preferably, the non-color-changing decorative glaze comprises non-color-changing pigments and a decorative glaze base glaze; the non-color-changing pigments account for 0.8% to 1.5% of the mass percentage of the decorative glaze base glaze; and the chemical composition of the decorative glaze base glaze comprises, in terms of mass percentage, SiO2: 53% to 68%, Al2O3: 9.8% to 18%, Fe2O3: 0.03% to 0.15%, CaO: 5.8% to 12%, MgO: 0.68% to 1.6%, K2O: 2.5% to 5.8%, Na2O: 0.28% to 2.8%, and ZnO: 2.2% to 4.9%.

[0011] Preferably, the non-color-changing decorative glaze is applied by screen printing or roller printing; the specific gravity of the non-color-changing decorative glaze is 1.75 to 1.85 g / cm 3 , and the glaze application amount is 40 to 60 g / m 2 .

[0012] Preferably, the chemical composition of the protective glaze comprises, in terms of mass percentage, SiO2: 45% to 58%, Al2O3: 21% to 23%, Fe2O3: 0.1% to 0.2%, CaO: 8.5% to 10%, MgO: 1% to 2%, K2O: 0.3% to 5.6%, Na2O: 2.1% to 5.5%, P2O5: 0.2% to 0.5%, and ZnO: 4.3% to 8.8%.

[0013] Preferably, the protective glaze is applied by spraying or showering; the specific gravity of the protective glaze is 1.4 to 1.55 g / cm 3 , and the glaze application amount is 230 to 275 g / m 2 .

[0014] Preferably, the chemical composition of the surface glaze comprises, in terms of mass percentage, SiO2: 51% to 59%, Al2O3: 23% to 28%, Fe2O3: 0.05% to 0.2%, CaO: 0.5% to 0.8%, MgO: 0.1% to 0.5%, K2O: 3.5% to 4.5%, Na2O: 2.8% to 4.2%, P2O5: 0.5% to 0.7%, and ZrO2: 4.8% to 7.5%.

[0015] Preferably, the surface glaze is applied by showering or spraying; the specific gravity of the surface glaze is 1.75 to 1.82 g / cm 3 , and the glaze application amount is 450 to 620 g / m 2 .

[0016] Preferably, the firing temperature is 1130°C to 1180°C, and the firing time is 35 to 50 min.

[0017] Preferably, the gloss of the glaze of the photosensitive color-changing decorative glaze is controlled to be 8°~15° after firing.

[0018] Preferably, the gloss of the glaze of the photosensitive color-changing decorative glaze is less than the gloss of the glaze of the non-color-changing decorative glaze after firing, and the difference between the gloss of the glaze of the photosensitive color-changing decorative glaze and the gloss of the glaze of the non-color-changing decorative glaze is within 5° after firing.

[0019] In a second aspect, the present application provides a ceramic tile with color-changing decorative effect. The ceramic tile with color-changing decorative effect is obtained according to the preparation method. BRIEF DESCRIPTION OF DRAWINGS

[0020] Figure 1 is a face mask color-changing effect diagram of the ceramic tile with color-changing decorative effect prepared in Example 1 under light source; from left to right, the color temperature is 6500K, 4000K, and 3000K, respectively.

[0021] Figure 2 is a window flower color-changing effect diagram of the ceramic tile with color-changing decorative effect prepared in Example 2 under light source; from left to right, the color temperature is 6500K and 4000K, respectively.

[0022] Figure 3 is a surface defect diagram of Comparative Example 1.

[0023] Figure 4 is a surface defect diagram of Comparative Example 2.

[0024] Figure 5 is a surface defect diagram of Comparative Example 3. DETAILED DESCRIPTION

[0025] The present application is further illustrated by the following examples, which should not be construed as limiting the present application. The following exemplary illustrates the preparation method of the ceramic tile with color-changing decorative effect.

[0026] A green tile is prepared. The chemical composition of the green tile is not limited. A ceramic green tile commonly used in the art can be used. For example, the chemical composition of the green tile includes, in mass percentage, loss on ignition: 4%~6%, SiO2: 60%~70%, Al2O3: 19%~25%, Fe2O3: 0.5%~1.5%, TiO2: 0.2%~0.5%, CaO: 0.2%~0.8%, MgO: 0.3%~0.8%, K2O: 2%~4%, and Na2O: 1.5%~3.5%. Mineral raw materials are weighed according to the chemical composition of the green tile, ball-milled uniformly with water, screened to remove iron, and spray granulated to obtain a body powder. The body powder is pressed and formed to obtain a green tile. The forming method is not limited. The forming method includes but is not limited to dry pressing.

[0027] The green tile is dried. The drying can be performed in a drying kiln.

[0028] The face glaze is applied on the surface of the dried green brick. By applying the face glaze on the surface of the green brick, the body defects can be covered and the inkjet pattern can be developed.

[0029] In an optional embodiment, the chemical composition of the face glaze comprises, in mass percentage, SiO2: 51%~59%, Al2O3: 23%~28%, Fe2O3: 0.05%~0.2%, CaO: 0.5%~0.8%, MgO: 0.1%~0.5%, K2O: 3.5%~4.5%, Na2O: 2.8%~4.2%, P2O5: 0.5%~0.7%, ZrO2: 4.8%~7.5%.

[0030] It should be understood that any mineral composition that makes the chemical composition of the face glaze fall within the above ranges is suitable for the face glaze of the present application. As an example but not limited to, the mineral composition of the face glaze comprises, in mass percentage, water-washed kaolin 3%~10%, sodium feldspar 15%~20%, potassium feldspar 35%~45%, quartz 10%~15%, chamotte 10%~20%, zirconium silicate 6%~10%, wollastonite 1%~5%.

[0031] The face glaze slip is prepared. In an optional embodiment, the raw material composition of the face glaze slip comprises, in parts by weight, the mineral composition of the face glaze 100 parts by weight, water 35~40 parts by weight, sodium tripolyphosphate 0.4 parts by weight, sodium carboxymethyl cellulose 0.15~0.2 parts by weight. The raw materials are weighed according to the raw material composition of the face glaze slip, ball-milled and mixed uniformly, and sieved to obtain the face glaze slip. The ball-milling time can be 10~30 minutes. The fineness of the face glaze slip can be within 0.3%~0.5% of the mass residue passing through a 325 mesh sieve. Water can be further added to adjust the specific gravity of the slip to obtain the final required specific gravity of the face glaze when applying the face glaze.

[0032] The face glaze is applied by spraying or pouring. The specific gravity of the face glaze is 1.75~1.9 g / cm 3 , and the application amount is 450~620 g / m 2 . Preferably, the specific gravity of the face glaze is 1.75~1.82 g / cm 3 .

[0033] The inkjet printing of the conventional color ink pattern is performed on the surface of the green brick after the face glaze is applied. The color and texture of the inkjet printing of the conventional color ink pattern can be changed as needed. The conventional color ink includes yellow, brown, blue, wrapped red, black, and other commonly used ceramic inks in architectural ceramics.

[0034] The photosensitive color-changing decorative glaze is prepared by applying the photosensitive color-changing decorative glaze on the surface of the green brick after the green brick is printed with the common ink pattern. In an optional embodiment, the chemical composition of the photosensitive color-changing decorative glaze includes, in percentage by mass, SiO2: 45% to 52%, Al2O3: 12% to 19%, Fe2O3: 0.05% to 0.12%, CaO: 2.1% to 3.5%, MgO: 2.6% to 3.5%, K2O: 3.5% to 4.8%, Na2O: 1.2% to 3.8%, ZnO: 4.2% to 7.9%, B2O3: 5% to 10%, and Nd2O3: 5% to 10%.

[0035] The glossiness of the photosensitive color-changing decorative glaze after firing is tested by using a glossiness tester to be 8° to 15°. At this time, a better photosensitive color-changing effect can be achieved. If the glossiness of the photosensitive color-changing decorative glaze after firing is less than 8°, the photosensitive color-changing decorative glaze is not completely sintered, and the protective glaze will penetrate into the photosensitive color-changing decorative glaze, affecting the color-changing effect. If the glossiness of the photosensitive color-changing decorative glaze after firing is greater than 15°, the high-temperature fluidity of the photosensitive color-changing decorative glaze increases, and the color-changing material is prone to enrichment, thereby generating a large number of white spots in the color-changing decorative glaze, thereby affecting the final color-changing effect. When the glossiness of the photosensitive color-changing decorative glaze is too high, the neodymium oxide is prone to water absorption to become an alkali carbonate, and reacts with the protective glaze, thereby easily introducing a large number of air bubbles into the photosensitive color-changing decorative glaze layer, thereby affecting the color decoration.

[0036] It should be understood that any mineral composition that causes the chemical composition of the photosensitive color-changing decorative glaze to fall within the above range is suitable for the present application. For example, the mineral composition of the photosensitive color-changing decorative glaze includes: water-washed kaolin 5% to 10%, potassium feldspar 35% to 45%, sodium feldspar 15% to 25%, barylite 10% to 20%, aluminum oxide 5% to 12%, neodymium oxide 5% to 10%, and zinc oxide 4% to 8%.

[0037] The photochromic jun glaze of Chinese patent CN112299717B introduces borax, but there is no obvious color-changing coloring ion, but the difference in color is caused by the difference in light refraction caused by the control of the thickness of the glaze layer or the air bubbles in the glaze layer, which is substantially different from the photosensitive color-changing of the present application. In the present application, the appropriate amount of aluminum oxide introduced into the photosensitive color-changing decorative glaze helps to improve the initial melting temperature of the glaze. In addition, during the firing process, the reaction between aluminum oxide and neodymium oxide generates neodymium aluminate, which effectively improves the color-changing effect. Moreover, the introduction of barylite promotes the reaction between aluminum oxide and barylite to generate neodymium borate, which significantly promotes the red tone after color-changing.

[0038] The photosensitive color-changing decorative glaze slip is prepared. In an optional embodiment, the raw material composition of the photosensitive color-changing decorative glaze slip includes, by weight fraction, 100 parts by weight of photosensitive color-changing decorative glaze minerals, 35-40 parts by weight of water, 0.4 parts by weight of sodium tripolyphosphate, and 0.15-0.2 parts by weight of sodium carboxymethyl cellulose. The raw materials are weighed according to the raw material composition of the photosensitive color-changing decorative glaze slip, ball-milled and mixed uniformly, and sieved to obtain the photosensitive color-changing decorative glaze slip. The ball-milling time can be 10-30 minutes. The fineness of the photosensitive color-changing decorative glaze slip can be within 0.3%-0.5% of the mass residue passing through a 325-mesh sieve. When the photosensitive color-changing decorative glaze is applied, water can be further added to adjust the slip specific gravity to obtain the final required photosensitive color-changing decorative glaze specific gravity.

[0039] The photosensitive color-changing decorative glaze is applied by screen printing or roller printing. The color-changing pattern texture can be engraved on the screen or roller. In an optional embodiment, the specific gravity of the photosensitive color-changing decorative glaze is 1.7-1.8 g / cm 3 , and the glazing amount is 60-80 g / m 2 .

[0040] A non-color-changing decorative glaze layer is prepared on the surface of the green brick after the photosensitive color-changing decorative glaze is applied.

[0041] The non-color-changing decorative glaze includes non-color-changing pigments and a decorative glaze base glaze. The chemical composition of the decorative glaze base glaze includes, by mass fraction, SiO2: 53%-68%, Al2O3: 9.8%-18%, Fe2O3: 0.03%-0.15%, CaO: 5.8%-12%, MgO: 0.68%-1.6%, K2O: 2.5%-5.8%, Na2O: 0.28%-2.8%, and ZnO: 2.2%-4.9%. The decorative glaze base glaze can promote the color development of the non-color-changing decorative pattern layer.

[0042] It should be understood that any mineral composition that causes the chemical composition of the decorative glaze base glaze to fall within the above ranges is suitable for the decorative glaze base glaze of the present application. As an example but not limited to, the mineral composition of the decorative glaze base glaze includes, by mass fraction, kaolin 10%-20%, sodium feldspar 10%-20%, potassium feldspar 20%-35%, wollastonite 20%-25%, calcined talc 5%-10%, zinc oxide 2%-5%, and quartz 5%-10%. The non-color-changing pigments do not change color significantly under light. Similarly, the non-color-changing pigments can ensure stable color development in the non-color-changing decorative glaze base glaze. Preferably, the mass addition amount of the non-color-changing pigments in the decorative glaze base glaze is 0.8%-1.5%.

[0043] The non-variable color pigments are stable color pigments. The non-variable color pigments can be inclusion pigments and / or spinel stable pigments. The non-variable color pigments include Pr-ZrSiO4, CdSeS@ZrSiO4, Fe-ZrSiO4, CoAl2O4, etc. These pigments exhibit single color in glazes, and the coloring ions thereof exhibit single reflection peak or absorption peak in the visible light band. When the external light source changes, the color does not change significantly due to the relatively fixed position of the absorption peak or reflection peak of the pigments in the visible light band. The inclusion pigments include, but are not limited to, inclusion red (CdSeS@ZrSiO4), inclusion yellow (Pr-ZrSiO4), cobalt blue (CoAl2O4), etc. In particular, the crystal structure of the zirconium-based inclusion type ceramic pigments or spinel type ceramic pigments is very stable, and exhibits good physical and chemical stability during use.

[0044] The aforementioned variable color pattern layer and non-variable color pattern layer need to have the same color principle. In the case of using blue tone pigments as variable color pigments, the non-variable color pattern layer should also be blue and exhibit stable color. In an optional embodiment, the composition of the blue tone non-variable color pigments includes, by weight, 0.3-0.7 parts by weight of cobalt blue pigments, 0.1-0.3 parts by weight of inclusion red pigments, and 0-3 parts by weight of zirconium silicate. The blue tone pigments thus composed can produce color effects of superimposed colors.

[0045] The non-variable color glaze slip is prepared. In an optional embodiment, the raw material composition of the non-variable color glaze slip includes, by weight, 100 parts by weight of the mineral composition of the non-variable color glaze, 35-40 parts by weight of water, 0.4 parts by weight of sodium tripolyphosphate, and 0.15-0.2 parts by weight of sodium carboxymethyl cellulose. The raw materials are weighed according to the raw material composition of the non-variable color glaze slip, ball-milled and uniformly mixed, and sieved to obtain the non-variable color glaze slip. The ball-milling time can be 10-30 minutes. The fineness of the non-variable color glaze slip can be within 0.3%-0.5% of the mass residue passing through a 325 mesh sieve. Water can be further added when the non-variable color glaze is applied to adjust the specific gravity of the glaze slip to obtain the final required specific gravity of the non-variable color glaze.

[0046] The non-variable color glaze can be applied by screen printing or roller printing. The non-variable color pattern texture can be engraved on the screen or roller. In an optional embodiment, the specific gravity of the non-variable color glaze is 1.75-1.85 g / cm 3 , and the glaze application amount is 40-60 g / m 2 .

[0047] Preferably, the gloss of the glaze surface of the non-variable color glaze after firing is greater than that of the photosensitive variable color glaze after firing. More preferably, the difference between the gloss of the surfaces of the photosensitive variable color glaze and the non-variable color glaze after firing is preferably controlled to be within 5°, so as to prevent defects such as glaze shrinkage on the tile surface. In an optional embodiment, the gloss of the surface of the non-variable color glaze after firing is 13°-18°.

[0048] A protective glaze is applied to the surface of the green brick after the application of the non-color-changing flower glaze. In an optional embodiment, the chemical composition of the protective glaze comprises, in mass percentage, SiO2: 45%~58%, Al2O3: 21%~23%, Fe2O3: 0.1%~0.2%, CaO: 8.5%~10%, MgO: 1%~2%, K2O: 0.3%~5.6%, Na2O: 2.1%~5.5%, P2O5: 0.2%~0.5%, and ZnO: 4.3%~8.8%.

[0049] It should be understood that any mineral composition that causes the chemical composition of the protective glaze to fall within the above ranges is suitable for the protective glaze of the present application. In an optional embodiment, the mineral composition of the protective glaze comprises, in mass percentage, washed kaolin 5%~10%, albite 10%~15%, potassium feldspar 25%~30%, quartz 10%~15%, chamotte 5%~10%, wollastonite 15%~25%, calcined talc 10%~20%, and zinc oxide 5%~10%.

[0050] A protective glaze slip is prepared. In an optional embodiment, the raw material composition of the protective glaze slip comprises, in parts by weight, the mineral composition of the protective glaze 100 parts by weight, water 35~40 parts by weight, sodium tripolyphosphate 0.4 parts by weight, and sodium carboxymethyl cellulose 0.15~0.2 parts by weight. The raw materials are weighed according to the raw material composition of the protective glaze slip, ball-milled and mixed uniformly, and sieved to obtain the protective glaze slip. The ball-milling time can be 10~30 minutes. The fineness of the protective glaze slip can be within 0.3%~0.5% of the mass residue passing through a 325 mesh sieve. Water can be further added to adjust the specific gravity of the slip to obtain the final desired specific gravity of the protective glaze when the protective glaze is applied.

[0051] The protective glaze can be applied by dipping or spraying. For example, the specific gravity of the protective glaze is 1.4~1.55 g / cm 3 , and the application amount is 230~275 g / m 2 .

[0052] After drying, the green brick is fired in a kiln. The firing temperature is 1130℃~1180℃, and the firing time is 35~50 minutes. For example, the firing time is 40 minutes.

[0053] Edge grinding.

[0054] The decorative pattern of the color-changing ceramic tile is different from the traditional inkjet printing decorative pattern. In the present application, the non-color-changing decorative pattern serves as a reference sample for the color-changing decorative pattern, and the two together constitute the decorative pattern. Moreover, the non-color-changing pattern has the same color under the irradiation of a 6500K (ordinary white light) light source. In this way, when the color-changing pattern changes color while the non-color-changing pattern remains unchanged as the color temperature of the light source changes, the naked eye can quickly capture the significant color difference. That is, the non-color-changing pattern layer serves as a reference sample for the color-changing pattern layer and needs to remain unchanged under the switching of external light sources, so the non-color-changing pigment has high stability and does not change color with changes in external light sources or produces a color difference that the naked eye cannot clearly distinguish.

[0055] The setting of the light control system is a conventional technical means in the art. For example, different lights are integrated on one light bead or multiple light columns. The color temperature of the light can vary from 2700K to 6500K. The light change process can use stepless light change or waveband change. Preferably, different color temperature lights can be connected together by Zigbee, and the lighting time or delay time of each light is set respectively. The light system is combined with the ceramic tile to achieve automatic dynamic decoration effect. As an example but not limited to, a color-changing tile is used to present a light control system that changes from blue to purple under different color temperature lights. The light system is combined with the ceramic tile to achieve automatic dynamic decoration effect.

[0056] In summary, the present application uses a photosensitive color-changing glaze that is sensitive to external light sources and changes color under different light source color temperatures, and a non-color-changing decorative glaze that has stable color presentation, in the form of a reference, to amplify the decorative effect of the color-changing material. In the present application, different color temperature lights are combined to achieve a ceramic tile with dynamic color-changing decorative effect.

[0057] The following examples are further listed to illustrate the present application in detail. It should also be understood that the following examples are only used to further illustrate the present application and cannot be understood as limiting the scope of protection of the present application. Some non-essential improvements and adjustments made by those skilled in the art based on the above content of the present application all belong to the protection scope of the present application. The specific process parameters in the following examples are only one example in the appropriate range, that is, those skilled in the art can select within the appropriate range through the description herein, and not limited to the specific values in the following examples.

[0058] Example 1

[0059] The preparation method of the ceramic tile with color-changing decorative effect comprises the following steps: Step 1. The green body powder is pressed into shape and dried to obtain a tile blank.

[0060] Step 2. Apply a surface glaze on the dried brick surface. The chemical composition of the surface glaze includes, in mass percentage, SiO2: 56.95%, Al2O3: 25%, Fe2O3: 0.05%, CaO: 0.8%, MgO: 0.5%, K2O: 4.5%, Na2O: 4.2%, P2O5: 0.5%, ZrO2: 7.5%. The surface glaze is applied by spraying. The specific gravity of the surface glaze is 1.75 g / cm3, and the glaze application amount is 450 g / m2. 3 2 .

[0061] Step 3. Inkjet print a normal ink pattern on the surface of the brick after applying the surface glaze.

[0062] Step 4. Screen print a photosensitive color-changing decorative glaze on the surface of the brick after inkjet printing the normal ink pattern. The chemical composition of the photosensitive color-changing decorative glaze includes, in mass percentage, SiO2: 52%, Al2O3: 16.38%, Fe2O3: 0.05%, CaO: 2.25%, MgO: 2.62%, K2O: 3.54%, Na2O: 2.28%, ZnO: 5.28%, B2O3: 5.6%, Nd2O3: 10%. The mineral composition of the photosensitive color-changing decorative glaze includes, in mass percentage, kaolin 8%, potassium feldspar 35%, sodium feldspar 20%, borocalcite 14.72%, aluminum oxide 5%, neodymium oxide 10%, zinc oxide 7.28%. The gloss of the fired glaze surface of the photosensitive color-changing decorative glaze is 10°. The specific gravity of the photosensitive color-changing decorative glaze is 1.7 g / cm3, and the glaze application amount is 60 g / m2. 3 2 .

[0063] Step 5. Screen print a non-color-changing decorative glaze on the surface of the brick after screen printing the photosensitive color-changing decorative glaze. The non-color-changing decorative glaze includes a decorative glaze base and a non-color-changing pigment. The chemical composition of the decorative glaze base includes, in mass percentage, SiO2: 63.5%, Al2O3: 15.84%, Fe2O3: 0.03%, CaO: 9.85%, MgO: 0.68%, K2O: 4.54%, Na2O: 1.28%, ZnO: 4.28%. The non-color-changing pigment includes, in mass percentage, encapsulated red (CdSeS@ZrSiO4) 0.1 parts by weight, encapsulated yellow (Pr-ZrSiO4) 3 parts by weight, cobalt blue (CoAl2O4) 0.3 parts by weight. The gloss of the fired glaze surface of the non-color-changing decorative glaze is 13°. The mass ratio of the non-color-changing pigment to the decorative glaze base is 0.8%. The specific gravity of the non-color-changing decorative glaze is 1.75 g / cm3, and the glaze application amount is 40 g / m2. 3 2 .

[0064] ​​​Step 6. A protective glaze is applied on the surface of the green body after screen printing the non-variable color glaze. The chemical composition of the protective glaze includes, in mass percentage, SiO2: 52.9%, Al2O3: 21.41%, Fe2O3: 0.12%, CaO: 9.86%, MgO: 1.08%, K2O: 5.28%, Na2O: 2.18%, P2O5: 0.28%, ZnO: 6.89%. The protective glaze is applied by spraying. The specific gravity of the protective glaze is 1.41 g / cm3, and the application amount of the protective glaze is 230 g / m2. 3 2 .

[0065] Step 7. The green body after applying the protective glaze is dried and then fired in a kiln. The firing temperature is 1150°C, and the firing time is 40 min.

[0066] Step 8. Edging.

[0067] As shown in Figure 1 , it presents a blue tone under light color temperature 6500K, a purple red tone under light color temperature 4000K, and a red tone under light color temperature 3000K.

[0068] Example 2

[0069] The same as Example 1, except that the photosensitive variable color glaze and the non-variable color glaze are applied by roller printing. The pattern engraved by the roller is a window pattern.

[0070] As shown in Figure 2 , it presents a blue tone under light color temperature 6500K, and a red tone under light color temperature 4000K.

[0071] Comparative Example 1 The same as Example 1, except that the chemical composition of the photosensitive variable color glaze includes, in mass percentage, SiO2: 49.8%, Al2O3: 20.5%, Fe2O3: 0.07%, CaO: 0.3%, MgO: 1.3%, K2O: 4.05%, Na2O: 3.58%, ZnO: 7.28%, B2O3: 4.12%, Nd2O3: 9%. The gloss of the fired glaze surface of the photosensitive variable color glaze is 5°.

[0072] The surface defect pattern of the comparative example is shown in Figure 3 . It can be seen that a large number of granular protrusions are obviously generated on the pattern surface, affecting the decorative effect. At this time, the photosensitive variable color glaze is not fired, and the protective glaze penetrates into the photosensitive white color glaze, resulting in whitening.

[0073] Comparative Example 2 ​The chemical composition of the photosensitive color-changing flower glaze includes, in mass percentage, SiO2: 57.96%, Al2O3: 8.5%, Fe2O3: 0.08%, CaO: 1%, MgO: 1.35%, K2O: 4.15%, Na2O: 2.78%, ZnO: 7.28%, B2O3: 8%, and Nd2O3: 8.9%. The gloss of the photosensitive color-changing flower glaze after firing is 18°.

[0074] The surface defect of the photosensitive color-changing flower glaze is shown in FIG. 4. It can be seen that a large number of bubbles are generated on the surface of the photosensitive color-changing flower glaze after irradiation under the light of 4000 K. Figure 4

[0075] Comparative Example 3 The chemical composition of the photosensitive color-changing flower glaze includes, in mass percentage, SiO2: 50.58%, Al2O3: 16.62%, Fe2O3: 0.05%, CaO: 2.2%, MgO: 2.6%, K2O: 4.28%, Na2O: 3.18%, ZnO: 5.89%, B2O3: 5.6%, and Nd2O3: 9%. The gloss of the photosensitive color-changing flower glaze after firing is 8°. The chemical composition of the non-color-changing flower glaze includes, in mass percentage, SiO2: 65.5%, Al2O3: 8.54%, Fe2O3: 0.05%, CaO: 11.85%, MgO: 2.68%, K2O: 3.58%, Na2O: 2.52%, and ZnO: 5.28%. The non-color-changing pigment includes, in parts by weight, 0.1 parts by weight of red-encapsulated (CdSeS@ZrSiO4), 3 parts by weight of yellow-encapsulated (Pr-ZrSiO4), and 0.3 parts by weight of cobalt blue (CoAl2O4). The mass addition amount of the non-color-changing pigment in the flower glaze base glaze is 0.6%. The gloss of the non-color-changing flower glaze after firing is 25°.

[0076] The surface defect of the photosensitive color-changing flower glaze is shown in FIG. 4. It can be seen that a large number of bubbles are generated on the surface of the photosensitive color-changing flower glaze after irradiation under the light of 4000 K.

[0077] Figure 5 It can be seen that obvious glaze shrinkage defects are generated on the surface of the brick. This is because the difference between the surface gloss of the photosensitive color-changing flower glaze and the non-color-changing flower glaze after firing is too large, causing surface glaze shrinkage.​​

Claims

1. A method for preparing ceramic tiles with color-changing decorative effects, characterized in that, The preparation method includes the following steps: Apply a surface glaze to the brick blank; Ordinary ink patterns are printed on the surface of the glazed brick blank using inkjet printing. A photosensitive color-changing glaze is applied to the surface of the brick after inkjet printing a pattern with ordinary ink to form a photosensitive color-changing decorative pattern; the chemical composition of the photosensitive color-changing glaze includes, by mass percentage: SiO2: 45%~52%, Al2O3: 12%~19%, Fe2O3: 0.05%~0.12%, CaO: 2.1%~3.5%, MgO: 2.6%~3.5%, K2O: 3.5%~4.8%, Na2O: 1.2%~3.8%, ZnO: 4.2%~7.9%, B2O3: 5%~10%, Nd2O3: 5%~10%; Applying a non-color-changing glaze to the surface of the brick blank after applying a photosensitive color-changing glaze creates a non-color-changing decorative pattern. Apply a protective glaze to the surface of the brick blank after applying a non-color-changing glaze; After applying a protective glaze, the brick blank is fired to obtain ceramic bricks with color-changing decorative effects.

2. The preparation method according to claim 1, characterized in that, The mineral composition of the photosensitive color-changing glaze includes, by mass percentage: 5%~10% washed kaolin, 35%~45% potassium feldspar, 15%~25% sodium feldspar, 10%~20% borate, 5%~12% alumina, 5%~10% neodymium oxide, and 4%~8% zinc oxide.

3. The preparation method according to claim 1, characterized in that, The photosensitive color-changing glaze is applied by screen printing or roller printing; the specific gravity of the photosensitive color-changing glaze is 1.7~1.8 g / cm³. 3 The glaze application rate is 60~80 g / m². 2 .

4. The preparation method according to claim 1, characterized in that, The non-color-changing glaze comprises non-color-changing pigments and a glaze base glaze; the non-color-changing pigments account for 0.8%~1.5% of the glaze base glaze by mass percentage; wherein, the chemical composition of the glaze base glaze comprises, by mass percentage: SiO2: 53%~68%, Al2O3: 9.8%~18%, Fe2O3: 0.03%~0.15%, CaO: 5.8%~12%, MgO: 0.68%~1.6%, K2O: 2.5%~5.8%, Na2O: 0.28%~2.8%, ZnO: 2.2%~4.9%.

5. The preparation method according to claim 1, characterized in that, The non-color-changing glaze is applied by screen printing or roller printing; the specific gravity of the non-color-changing glaze is 1.75~1.85 g / cm³. 3 The glaze application rate is 40~60 g / m². 2 .

6. The preparation method according to claim 1, characterized in that, The chemical composition of the protective glaze includes, by mass percentage: SiO2: 45%~58%, Al2O3: 21%~23%, Fe2O3: 0.1%~0.2%, CaO: 8.5%~10%, MgO: 1%~2%, K2O: 0.3%~5.6%, Na2O: 2.1%~5.5%, P2O5: 0.2%~0.5%, ZnO: 4.3%~8.8%.

7. The preparation method according to claim 1, characterized in that, The protective glaze is applied by spraying or pouring; the specific gravity of the protective glaze is 1.4~1.55 g / cm³. 3 The glaze application rate is 230~275 g / m². 2 .

8. The preparation method according to claim 1, characterized in that, The chemical composition of the surface glaze includes, by mass percentage: SiO2: 51%~59%, Al2O3: 23%~28%, Fe2O3: 0.05%~0.2%, CaO: 0.5%~0.8%, MgO: 0.1%~0.5%, K2O: 3.5%~4.5%, Na2O: 2.8%~4.2%, P2O5: 0.5%~0.7%, ZrO2: 4.8%~7.5%.

9. The preparation method according to claim 1, characterized in that, The glaze is applied by pouring or spraying; the specific gravity of the glaze is 1.75~1.82 g / cm³. 3 The glaze application rate is 450~620 g / m². 2 .

10. The preparation method according to claim 1, characterized in that, The firing temperature is 1130℃~1180℃, and the firing time is 35~50 min.

11. The preparation method according to claim 1, characterized in that, The gloss level of the photosensitive color-changing glaze is controlled at 8°~15° after firing.

12. The preparation method according to claim 1, characterized in that, The gloss of the photosensitive color-changing glaze after firing is less than that of the non-color-changing glaze after firing, and the difference in gloss between the photosensitive color-changing glaze and the non-color-changing glaze after firing is within 5°.

13. A ceramic tile with a color-changing decorative effect, characterized in that, The ceramic tile with color-changing decorative effect is obtained by the preparation method according to any one of claims 1 to 12.

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