Ceramic tile with color-changing decorative effect and method for manufacturing the same

Abstract

This invention belongs to the field of architectural ceramics and relates to ceramic tiles with color-changing decorative effects and their preparation method. The preparation method includes the following steps: applying a surface glaze to the surface of the tile blank; inkjet printing a regular ink pattern onto the surface of the glazed tile blank; applying a photosensitive color-changing glaze to the surface of the tile blank after inkjet printing the regular ink pattern to form a photosensitive color-changing decorative pattern; applying a non-color-changing glaze to the surface of the tile blank after applying the photosensitive color-changing glaze to form a non-color-changing decorative pattern; applying a protective glaze to the surface of the tile blank after applying the non-color-changing glaze; and firing the tile blank after applying the protective glaze to obtain a ceramic tile with color-changing decorative effects. The preparation method of the color-changing decorative ceramic tile of this invention introduces photosensitive color-changing glaze and non-color-changing glaze, and by controlling their composition and gloss, combines the color-changing effect with ceramic tile decoration, achieving integrated decorative function while ensuring tile surface quality.

Description

Technical Field

[0001] This invention belongs to the field of building ceramics and relates to ceramic bricks with color-changing decorative effects and their preparation methods. Background Technology

[0002] The human eye can see the color of an object's surface because the object's surface selectively absorbs and reflects visible light. In color difference judgment, the human eye can usually observe a significant difference when the color difference ΔE > 5. Based on this principle, if an object can produce a large color difference under the stimulation of an external light source, its color change effect can be clearly captured by the naked eye.

[0003] Color-changing decoration is a novel functional surface decoration technology. The color patterns on the surface of architectural ceramics change color based on variations in the light source, thus achieving different surface decoration effects by switching the light source. The fundamental reason for this color-changing effect lies in the rich energy level structure of the coloring elements, which, under the excitation of an external light source, can selectively absorb or reflect light waves of different wavelengths. This is exemplified by rare earth neodymium ions (Nd...). 3+ For example, electron transitions between the ff subshell energy levels can produce various spectral terms or line lines. Under external energy excitation, Nd... 3+ Narrow absorption peaks appear in the visible light region, especially strong absorption at 530nm and 600nm. Due to the presence 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, causing the neodymium-containing pigment to produce a color-changing effect.

[0004] LED white light is commonly used for indoor lighting. Different LED lights have different color temperatures depending on the indoor environment. The color temperature of LED white light on the market varies within the range of 2700K to 6500K. In spacious, bright halls, pure white light with a color temperature of around 6500K is usually chosen; while in warmer indoor spaces, warmer lighting with a color temperature of around 3000K is generally used. Only by selecting materials that are sensitive to color temperature changes and pairing them with the lighting can a noticeable color-changing decorative effect be achieved.

[0005] The emergence of inkjet printing technology has led to severe product homogenization in the architectural ceramics industry. Therefore, it is essential to develop ceramic products with unique decorative effects to increase added value. Summary of the Invention

[0006] The integration of decorative and architectural ceramics is an important direction for the development of the construction industry and a crucial technical means to enhance the added value of ceramic products. The method for preparing color-changing decorative ceramic tiles described in this invention introduces photosensitive color-changing glazes and non-color-changing glazes. By controlling their composition and gloss, the color-changing effect is combined with ceramic tile decoration, achieving integrated decorative and architectural functions while ensuring tile surface quality. The technical objective of this invention is achieved through the following technical solution:

[0007] In a first aspect, the present invention provides a method for preparing ceramic tiles with color-changing decorative effects. The preparation method includes the following steps:

[0008] Apply a surface glaze to the brick blank;

[0009] Ordinary ink patterns are printed on the surface of the glazed brick blank using inkjet printing.

[0010] Apply photosensitive color-changing glaze to the surface of the brick blank after inkjet printing a pattern with ordinary ink to form a photosensitive color-changing decorative pattern.

[0011] 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.

[0012] Apply a protective glaze to the surface of the brick blank after applying a non-color-changing glaze;

[0013] After applying a protective glaze, the brick blank is fired to obtain ceramic bricks with color-changing decorative effects.

[0014] Preferably, 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%.

[0015] Preferably, 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.

[0016] Preferably, 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 .

[0017] Preferably, the non-color-changing glaze comprises non-color-changing pigments and a glaze base glaze; the non-color-changing pigments account for 0.8% to 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% 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%, ZnO: 2.2% to 4.9%.

[0018] Preferably, 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 .

[0019] Preferably, 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%.

[0020] Preferably, 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 .

[0021] Preferably, 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%, and ZrO2: 4.8%~7.5%.

[0022] Preferably, 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 .

[0023] Preferably, the firing temperature is 1130℃~1180℃ and the firing time is 35~50 min.

[0024] Ideally, the gloss of the photosensitive color-changing glaze should be controlled between 8° and 15° after firing.

[0025] Preferably, 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°.

[0026] Secondly, the present invention provides a ceramic tile with a color-changing decorative effect. The ceramic tile with the color-changing decorative effect is obtained according to the preparation method described above. Attached Figure Description

[0027] Figure 1 The image shows the color-changing effect of the ceramic tile with color-changing decorative effect prepared in Example 1 under a light source; from left to right, the color temperatures are 6500K, 4000K, and 3000K.

[0028] Figure 2 The image shows the color-changing effect of the ceramic tile with color-changing decorative effect prepared in Example 2 under a light source; from left to right, the values ​​are 6500K and 4000K.

[0029] Figure 3 This is a surface defect diagram of Comparative Example 1.

[0030] Figure 4 This is a surface defect diagram of Comparative Example 2.

[0031] Figure 5 This is a surface defect diagram of Comparative Example 3. Detailed Implementation

[0032] The present invention is further illustrated by the following embodiments. It should be understood that the following embodiments are for illustrative purposes only and are not intended to limit the present invention. The following exemplary description illustrates a method for preparing ceramic tiles with color-changing decorative effects.

[0033] Prepare brick blanks. The chemical composition of the brick blanks is not limited. Commonly used ceramic brick blanks in the art can be used. For example, the chemical composition of the brick blanks includes, by 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%, Na2O: 1.5%~3.5%. Weigh the mineral raw materials according to the chemical composition of the brick blanks, add water and ball mill evenly, sieve to remove iron, spray granulate to obtain the blank powder. Press the blank powder into brick blanks. The molding method is not limited. Molding methods include, but are not limited to, dry pressing.

[0034] Dry the brick blanks. Drying can be carried out in a drying kiln.

[0035] Apply a glaze to the surface of the dried brick blank. By applying a glaze to the surface of the brick blank, it can cover up defects in the blank and promote the color development of inkjet patterns.

[0036] In an optional embodiment, 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%.

[0037] It should be understood that any mineral composition that causes the chemical composition of the glaze to fall within the above-mentioned range is applicable to the glaze of the present invention. As an example, but not limited thereto, the mineral composition of the glaze includes, by mass percentage: 3%~10% water-washed kaolin, 15%~20% albite, 35%~45% potassium feldspar, 10%~15% quartz, 10%~20% calcined clay, 6%~10% zirconium silicate, and 1%~5% wollastonite.

[0038] Preparation of the surface glaze slurry. In an optional embodiment, the raw material composition of the surface glaze slurry includes: 100 parts by weight of surface glaze mineral composition, 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. Weigh each raw material according to the raw material composition of the surface glaze slurry, ball mill and mix evenly, and sieve to obtain the surface glaze slurry. The ball milling time can be 10-30 minutes. The fineness of the surface glaze slurry can be such that the mass residue on a 325-mesh sieve is within 0.3%-0.5%. When applying the surface glaze, water can be further added to adjust the specific gravity of the slurry to obtain the final desired surface glaze specific gravity.

[0039] The surface glaze is applied by pouring or spraying. The specific gravity of the surface glaze is 1.75~1.9 g / cm³. 3 The glaze application rate is 450~620 g / m². 2 Preferably, the specific gravity of the surface glaze is 1.75~1.82 g / cm³. 3 .

[0040] The surface of the tile after glazing is inkjet printed with conventional color ink patterns. The colors and textures of the inkjet printed conventional color ink patterns can be varied as needed. Conventional color inks include yellow, brown, blue, red, black, and other commonly used ceramic inks for architectural ceramics.

[0041] A photosensitive color-changing glaze is applied to the surface of a brick blank after inkjet printing a pattern with ordinary ink to prepare a photosensitive color-changing pattern layer. In an optional embodiment, 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%.

[0042] The gloss level of the photosensitive color-changing glaze after firing, as measured by a gloss meter, was between 8° and 15°. This range indicates a good photosensitive color-changing effect. If the gloss level is below 8° after firing, the glaze is not fully sintered, and the protective glaze will penetrate, affecting the color-changing effect. If the gloss level is above 15°, the high-temperature fluidity of the glaze increases, and the color-changing material tends to accumulate, resulting in numerous white spots and affecting the final color-changing effect. When the gloss level is too high, neodymium oxide readily absorbs water, turning into basic carbonates that react with the protective glaze, easily introducing numerous air bubbles into the glaze layer and affecting the color decoration.

[0043] It should be understood that any mineral composition that causes the chemical composition of the photosensitive color-changing glaze to fall within the above-mentioned range is applicable to the present invention. For example, the mineral composition of the photosensitive color-changing glaze includes: 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.

[0044] Although the photochromic Jun porcelain glaze in Chinese Patent CN112299717B incorporates borax, it does not contain obvious color-changing ions. Instead, it achieves color variations by controlling the glaze thickness or air bubbles to create differences in light refraction, which is substantially different from the photosensitive color-changing effect of this invention. This invention introduces an appropriate amount of alumina into the photosensitive color-changing glaze, which helps to increase the initial melting temperature of the glaze. Furthermore, during firing, the reaction between alumina and neodymium oxide to form neodymium aluminate effectively enhances the color-changing effect. Moreover, the introduction of borate promotes the reaction between alumina and borate to form neodymium borate, significantly promoting the red hue after color change.

[0045] Prepare a photosensitive color-changing glaze slurry. In an optional embodiment, the raw material composition of the photosensitive color-changing glaze slurry includes: 100 parts by weight of photosensitive color-changing glaze mineral composition, 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. Weigh each raw material according to the raw material composition of the photosensitive color-changing glaze slurry, ball mill and mix evenly, and sieve to obtain the photosensitive color-changing glaze slurry. The ball milling time can be 10-30 minutes. The fineness of the photosensitive color-changing glaze slurry can be such that the mass residue on a 325-mesh sieve is within 0.3%-0.5%. When applying the photosensitive color-changing glaze, water can be further added to adjust the specific gravity of the glaze slurry to obtain the final desired specific gravity.

[0046] The photosensitive color-changing enamel 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 enamel is 1.7~1.8 g / cm³. 3 The glaze application rate is 60~80 g / m². 2 .

[0047] A non-color-changing pattern layer is prepared by applying a non-color-changing glaze to the surface of the brick blank after applying a photosensitive color-changing glaze.

[0048] Non-color-changing glazes consist of non-color-changing pigments and a base glaze. The chemical composition of the base glaze includes, 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%. The base glaze promotes the color development of the non-color-changing decorative layer.

[0049] It should be understood that any mineral composition that causes the chemical composition of the glaze base to fall within the above-mentioned range is applicable to the glaze base of the present invention. As an example, but not limited to, the mineral composition of the glaze base includes, by mass percentage: 10%–20% kaolin, 10%–20% albite, 20%–35% potassium feldspar, 20%–25% wollastonite, 5%–10% calcined talc, 2%–5% zinc oxide, and 5%–10% quartz. The non-color-changing pigment does not show significant color change with light. Similarly, the non-color-changing pigment ensures stable color in the non-color-changing glaze base. Preferably, the mass addition amount of the non-color-changing pigment in the glaze base is 0.8%–1.5%.

[0050] Non-color-changing pigments are stable colorants. They can be encapsulated pigments and / or spinel-stabilized pigments. Examples of non-color-changing pigments include Pr-ZrSiO4, CdSeS@ZrSiO4, Fe-ZrSiO4, and CoAl2O4. These pigments exhibit a single color in the glaze, with their coloring ions displaying a single reflection or absorption peak in the visible light band. When the external light source changes, the color does not change significantly because the positions of the absorption or reflection peaks in the visible light band remain relatively fixed. Encapsulated pigments include, but are not limited to, encapsulated red (CdSeS@ZrSiO4), encapsulated yellow (Pr-ZrSiO4), and cobalt blue (CoAl2O4). In particular, zirconium-based encapsulated ceramic pigments or spinel-based ceramic pigments have very stable crystal structures and exhibit excellent physicochemical stability during use.

[0051] As mentioned earlier, the color-changing pattern layer and the non-color-changing pattern layer need to have the same color. When the color-changing pigment is a blue-toned pigment, the non-color-changing pattern layer should also be blue and have a stable color. In an optional embodiment, the blue-toned non-color-changing pigment comprises: 0.3-0.7 parts by weight of cobalt blue pigment, 0.1-0.3 parts by weight of encapsulated red pigment, and 0-3 parts by weight of zirconium silicate. This composition of blue-toned pigment can produce a layered color effect.

[0052] Preparation of a non-color-changing glaze slurry. In an optional embodiment, the raw material composition of the non-color-changing glaze slurry includes: 100 parts by weight of non-color-changing 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. Weigh each raw material according to the raw material composition of the non-color-changing glaze slurry, ball mill and mix evenly, and sieve to obtain the non-color-changing glaze slurry. The ball milling time can be 10-30 minutes. The fineness of the non-color-changing glaze slurry can be such that the mass residue on a 325-mesh sieve is within 0.3%-0.5%. When applying the non-color-changing glaze, water can be further added to adjust the specific gravity of the glaze slurry to obtain the final desired specific gravity of the non-color-changing glaze.

[0053] The non-color-changing glaze can be applied by screen printing or roller printing. The non-color-changing pattern or texture can be engraved on the screen or roller. In an optional embodiment, 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 .

[0054] Preferably, the gloss of the non-color-changing glaze after firing is greater than that of the photosensitive color-changing glaze. More preferably, the difference in surface gloss between the photosensitive and non-color-changing glazes after firing is preferably controlled within 5°, which can prevent defects such as glaze shrinkage from appearing on the brick surface. In an optional embodiment, the surface gloss of the non-color-changing glaze after firing is 13°~18°.

[0055] A protective glaze is applied to the surface of the brick blank after the application of a non-color-changing glaze. In an optional embodiment, 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%.

[0056] It should be understood that any mineral composition that causes the chemical composition of the protective glaze to fall within the above-mentioned range is applicable to the protective glaze of the present invention. In an optional embodiment, the mineral composition of the protective glaze includes, by mass percentage: 5%~10% water-washed kaolin, 10%~15% albite, 25%~30% potassium feldspar, 10%~15% quartz, 5%~10% calcined clay, 15%~25% wollastonite, 10%~20% calcined talc, and 5%~10% zinc oxide.

[0057] Prepare the protective glaze slurry. In an optional embodiment, the raw material composition of the protective glaze slurry includes: 100 parts by weight of protective glaze mineral composition, 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. Weigh each raw material according to the raw material composition of the protective glaze slurry, ball mill and mix evenly, and sieve to obtain the protective glaze slurry. The ball milling time can be 10-30 minutes. The fineness of the protective glaze slurry can be such that the mass residue on a 325-mesh sieve is within 0.3%-0.5%. When applying the protective glaze, water can be further added to adjust the specific gravity of the slurry to obtain the final desired specific gravity of the protective glaze.

[0058] The protective glaze can be applied by pouring or spraying. For example, 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 .

[0059] After drying, it is fired in a kiln. The firing temperature is 1130℃~1180℃, and the firing time is 35~50 min. For example, the firing time is 40 min.

[0060] Edge grinding.

[0061] The decorative patterns on color-changing ceramic tiles differ from those of traditional inkjet-printed patterns. In this invention, a non-color-changing decorative pattern serves as a reference for the color-changing decorative pattern, and the two together constitute the decorative pattern. Furthermore, the non-color-changing pattern and the photosensitive color-changing pattern exhibit the same color under 6500K (ordinary white light) illumination. Thus, as the color temperature of the light changes, the color-changing pattern changes color while the non-color-changing pattern remains unchanged; the difference is readily noticeable to the naked eye. In other words, the non-color-changing pattern layer, serving as the reference for the color-changing pattern layer, needs to remain unchanged under varying external light sources. Therefore, the non-color-changing pigments possess high stability and do not exhibit color differences with changes in external light sources, or produce very small color differences that are not readily discernible to the naked eye.

[0062] The lighting control system is set up using conventional techniques in this field. For example, different lights are integrated onto a single LED or multiple light columns. The color temperature of the light can vary from 2700 to 6500K. The light variation process can employ stepless dimming or band-based variation. Preferably, lights of different color temperatures can be connected in series using Zigbee, and the lighting time or delay time of each light can be set separately. By combining the lighting system with ceramic tiles, an automatic dynamic decorative effect can be achieved. As an example, but not limited to, a lighting control system using color-changing tiles that changes from blue to purple under different color temperature lights can be implemented. By combining the lighting system with ceramic tiles, an automatic dynamic decorative effect can be achieved.

[0063] In summary, this invention employs photosensitive color-changing glazes that change color with different light sources at different color temperatures, and color-stable non-color-changing decorative glazes in the decorative pattern layer, amplifying the decorative effect of the color-changing materials as a reference. This invention combines lighting of different color temperatures to achieve ceramic tiles with a dynamic color-changing decorative effect.

[0064] The following examples further illustrate the present invention in detail. It should also be understood that the following examples are only for further explanation of the present invention and should not be construed as limiting the scope of protection of the present invention. Any non-essential improvements and adjustments made by those skilled in the art based on the above description of the present invention are within the scope of protection of the present invention. The specific process parameters, etc., in the following examples are merely examples within a suitable range; that is, those skilled in the art can make appropriate selections within the appropriate range based on the description herein, and are not intended to be limited to the specific values ​​in the examples below.

[0065] Example 1

[0066] The preparation method of ceramic tiles with color-changing decorative effects includes the following steps:

[0067] Step 1. Press the green body powder into shape and dry it to obtain brick blanks.

[0068] Step 2. Apply a surface glaze to the dried brick surface. The chemical composition of the surface glaze includes, by 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 pouring. The specific gravity of the surface glaze is 1.75 g / cm³. 3 The amount of glaze applied is 450 g / m². 2 .

[0069] Step 3. Print a regular ink pattern on the surface of the glazed brick using inkjet printing.

[0070] Step 4. Screen-print a photosensitive color-changing glaze onto the surface of the brick blank after inkjet printing a pattern with ordinary ink. The chemical composition of the photosensitive color-changing glaze includes, by 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 glaze includes, by mass percentage: kaolin 8%, potassium feldspar 35%, sodium feldspar 20%, borate 14.72%, alumina 5%, neodymium oxide 10%, zinc oxide 7.28%. The gloss of the glaze surface after firing is 10°. The specific gravity of the photosensitive color-changing glaze is 1.7 g / cm³. 3 Glazing amount is 60 g / m 2 .

[0071] Step 5. Screen print a non-color-changing glaze onto the surface of the brick after screen printing the photosensitive color-changing glaze. The non-color-changing glaze includes a glaze base and non-color-changing pigments. The chemical composition of the glaze base is as follows (by weight 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 pigments include, by weight percentage: 0.1 parts by weight of coated red (CdSeS@ZrSiO4), 3 parts by weight of coated yellow (Pr-ZrSiO4), and 0.3 parts by weight of cobalt blue (CoAl2O4). The gloss of the non-color-changing glaze after firing is 13°. The non-color-changing pigments account for 0.8% of the glaze base by weight. The specific gravity of the non-color-changing glaze is 1.75 g / cm³. 3 Glazing amount is 40g / m 2 .

[0072] Step 6. Apply a protective glaze to the surface of the brick after screen printing the non-color-changing glaze. The chemical composition of the protective glaze includes, by 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. 3 The amount of the protective glaze applied is 230 g / m³. 2 .

[0073] Step 7. After drying the brick blanks with the protective glaze, fire them in a kiln. The firing temperature is 1150℃ and the firing time is 40 minutes.

[0074] Step 8. Grind the edges.

[0075] like Figure 1 As shown, it appears blue under a light color temperature of 6500K, purple-red under a light color temperature of 4000K, and red under a light color temperature of 3000K.

[0076] Example 2

[0077] The process is essentially the same as in Example 1, except that photosensitive and non-photosensitive glazes are applied using roller printing. Furthermore, the roller-engraved pattern is a window lattice pattern.

[0078] like Figure 2 As shown, it appears blue under light with a color temperature of 6500K and red under light with a color temperature of 4000K.

[0079] Comparative Example 1

[0080] The process is essentially the same as in Example 1, except that the chemical composition of the photosensitive color-changing glaze includes, by 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 level of the photosensitive color-changing glaze after firing is 5°.

[0081] The surface defect diagram of the comparison is as follows: Figure 3 As shown, it can be seen that a large number of granular protrusions are clearly generated on the surface of the pattern, which affects the decorative effect. At this time, because the photosensitive color-changing glaze was not fully fired, the protective glaze penetrated into the photosensitive white glaze, causing it to turn white.

[0082] Comparative Example 2

[0083] The process is essentially the same as in Example 1, except that the chemical composition of the photosensitive color-changing glaze includes, by 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%, Nd2O3: 8.9%. The gloss of the glaze surface after firing is 18°.

[0084] The surface defect diagram of the comparison is as follows: Figure 4 As shown, under 4000K light, the photosensitive color-changing glaze reacts with the protective glaze, producing a large number of bubbles that remain in the glaze layer.

[0085] Comparative Example 3

[0086] It is basically the same as Example 1, except that:

[0087] The chemical composition of the photosensitive color-changing glaze includes, by 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%, Nd2O3: 9%. The gloss of the glaze surface after firing is 8°.

[0088] The chemical composition of the non-color-changing glaze includes, by mass percentage: SiO2: 65.5%, Al2O3: 8.54%, Fe2O3: 0.05%, CaO: 11.85%, MgO: 2.68%, K2O: 3.58%, Na2O: 2.52%, ZnO: 5.28%. The non-color-changing pigments include, by weight, 0.1 parts of coated red (CdSeS@ZrSiO4), 3 parts of coated yellow (Pr-ZrSiO4), and 0.3 parts of cobalt blue (CoAl2O4). The amount of non-color-changing pigments added to the glaze base is 0.6%. The gloss of the glaze surface after firing is 25°.

[0089] The surface defects in this proportion are as follows Figure 5 As shown, obvious glaze shrinkage defects can be seen on the brick surface. This is due to the significant difference in surface gloss between photosensitive color-changing glaze and non-color-changing glaze after firing, 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 photosensitive color-changing glaze is applied by screen printing or roller printing; the color-changing pattern texture is engraved on the screen or roller; 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 oxide... Zinc 4%~8%; 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%; A non-color-changing glaze is applied to the surface of the brick blank after photosensitive color-changing glaze is applied to form a non-color-changing decorative pattern; the non-color-changing glaze is applied by screen printing or roller printing; the non-color-changing pattern texture is engraved on the screen or roller; the non-color-changing glaze includes 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; the non-color-changing pigments are encapsulated colorants and / or spinel-stabilized colorants; wherein, the chemical composition of the glaze base glaze includes, 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%; A protective glaze is applied to the surface of the brick blank after the application of a non-color-changing glaze; 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%; After applying a protective glaze, the brick blank is fired to obtain a ceramic tile with a color-changing decorative effect; the non-color-changing decorative pattern serves as a reference for the color-changing decorative pattern, and the two together constitute the decorative pattern; as the color temperature of the light changes, the color-changing pattern changes color while the non-color-changing pattern remains unchanged. The gloss of the photosensitive color-changing glaze is controlled at 8°~15° after firing. 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°.

2. The preparation method according to claim 1, characterized in that, 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 .

3. The preparation method according to claim 1, characterized in that, 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 .

4. 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 .

5. 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%.

6. 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 .

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

8. 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 7.

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