Fluorescent ceramic ink and deep gray decorative pattern ceramic tile using same

Abstract

The invention discloses fluorescent ceramic ink and a deep gray decorative pattern ceramic tile using the same, and belongs to the field of ceramics. According to the fluorescent ceramic ink disclosed by the invention, inorganic powder prepared by a specific process is used as luminous powder, and specific types of dispersing agents and surfactants are matched to improve the dispersity of the whole components and the compatibility of water-based glaze, so that high luminous intensity under the irradiation of an ultraviolet light source can be realized; the method has the advantages that the method is simple and easy to operate, the recognition rate of invisible anti-counterfeiting codes under the superposition of deep-gray-scale decorative patterns is obviously increased, meanwhile, the method is effectively compatible with high-glossiness polished glaze, low-glossiness antique glaze and other water-based glaze series, the concave glaze phenomenon is avoided, and the flatness and aesthetic decoration effect of the surface of the ceramic tile are not affected.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of ceramics, in particular to a fluorescent ceramic ink and a deep gray decorative pattern ceramic tile using the same. BACKGROUND

[0002] In order to effectively crack down on counterfeit products, people gradually began to set up anti-counterfeiting marks in the field of building ceramic tiles, such as setting up trademarks or invisible anti-counterfeiting codes in the product, among which setting up invisible anti-counterfeiting codes has stronger concealment, and a two-dimensional code can be set up in the anti-counterfeiting code, and production traceability can be realized according to the two-dimensional code, which has stronger practicability.

[0003] When setting up anti-counterfeiting codes, people generally use ceramic ink to set up, but the existing products have obvious technical defects when applied to ceramic tiles. On the one hand, such ink mainly relies on luminescent powder for identification, but the luminescent intensity of such powder under special light source is weak, and the identification rate is difficult to improve. If there is a deep gray decorative pattern on the ceramic tile, the identification rate is lower, and it is difficult to achieve more than 95%; on the other hand, the anti-counterfeiting ceramic ink is generally prepared with oily solvent and set on the ceramic tile product by inkjet printing, and the decorative pattern on the ceramic tile is also set by using similar components and process, and once the two are set together, the local oily component content will be too high, which will cause obvious repulsion with the water-based glaze in the product, and finally affect the flatness and appearance of the ceramic tile due to the concave glaze phenomenon. SUMMARY

[0004] Based on the defects of the prior art, the purpose of the present application is to provide a fluorescent ceramic ink, which uses inorganic powder prepared by a specific process as luminescent powder, and is matched with specific types of dispersants and surfactants to improve the dispersibility of the overall composition and the compatibility of the water-based glaze. Not only can it achieve high luminescent intensity under ultraviolet light source, but also significantly improve the identification rate of invisible two-dimensional code under the superposition of deep gray decorative pattern, and it can also effectively compatible with water-based glaze series such as high-glossiness polished glaze and low-glossiness antique glaze, avoid concave glaze phenomenon, and do not affect the flatness and aesthetic decoration effect of the ceramic tile surface.

[0005] In order to achieve the above purpose, the technical scheme adopted by the present application is as follows:

[0006] A fluorescent ceramic ink, comprising the following components by weight:

[0007] 25-36 parts of inorganic luminescent powder, 54-73 parts of oily solvent, 0.5-5 parts of dispersant and 1.5-5 parts of surfactant;

[0008] The preparation raw materials of the inorganic luminescent powder include oxide A, oxide B, oxide C and oxide D;

[0009] The oxide A includes at least one of aluminum oxide, zirconium oxide, yttrium oxide, the oxide B includes at least one of lanthanum oxide, dysprosium oxide, erbium oxide, the oxide C includes at least one of praseodymium oxide, rubidium oxide, terbium oxide, and the oxide D includes at least one of manganese oxide, samarium oxide, bismuth oxide.

[0010] The dispersant includes at least one of polyacrylic acid, ammonium polyacrylate, methylene bis naphthalene sulfonic acid sodium, methacrylic acid, ethylene imine, butyral.

[0011] The surfactant includes at least one of sodium monoalkyl sulfosuccinate, sodium dialkyl sulfosuccinate.

[0012] The existing ceramic ink for setting invisible anti-counterfeit codes is similar to the decorative pattern in formulation and use, both of which are set by using oily solvent and through inkjet printing. However, the luminescent powder for anti-counterfeiting in the existing fluorescent ceramic ink has low light intensity under ultraviolet light source, and can only be clearly identified in transparent glaze or light-colored decorative pattern ceramic tiles. Once applied to deep gray decorative pattern ceramic tile products such as antique glaze ceramic tiles, the identification rate will be greatly reduced. At the same time, due to the immiscibility of the oily solvent used in the ceramic ink and the water-based glaze, the glaze on the upper layer of the invisible anti-counterfeit code printed by the fluorescent ceramic ink will be pushed away by the oily solvent, which is prone to glaze concave phenomenon and affects the aesthetic decorative effect of the ceramic tile. In addition, if the ingredients of the ceramic ink are not suitable, it will also react with the glaze during preparation, eventually causing both to fail, affecting the anti-counterfeiting effect and product quality. Therefore, in the technical scheme of the present application, the inventors have found that the above four specific metal oxide combinations are used as raw materials to prepare the luminescent powder, and the fluorescent ceramic ink prepared from the powder is sprayed on the bottom glaze under the decorative pattern, and then high-temperature firing is performed. The chemical stability is high, and no chemical reaction with the glaze occurs, and the glaze surface is not affected. At the same time, the invisible anti-counterfeit code formed has excellent light intensity under light, even if the ceramic tile has a deep gray decorative pattern superimposed, it can still maintain a high light intensity, that is, a high identification rate. If other conventional oxides or rare earth oxides are used instead, although a powder product with luminescent effect can be obtained, the identification rate of the product under the influence of the deep gray decorative pattern cannot reach the expected level, and even the product quality is affected. On the other hand, the specific dispersants and surfactants are selected in the fluorescent ceramic ink of the present application on the basis of the oily solvent, in which the polyacrylic acid, polyacrylammonium, methylene bis naphthalene sulfonic acid sodium, methacrylic acid, ethylene imine, and butyl formaldehyde can improve the dispersibility of inorganic powder through active groups in the oily solvent, avoid the phenomenon of local aggregation of the fluorescent ceramic ink during inkjet printing and the process of superimposing the decorative pattern, and further improve the printing effect of the invisible anti-counterfeit code with high clarity. The two sodium salts of monoalkyl sulfosuccinic acid and dialkyl sulfosuccinic acid can reduce the tension of inorganic powder in the solvent based on the action of sulfosuccinic acid root, and improve the compatibility of the whole material when in contact with the water-based glaze, effectively inhibit the concave glaze phenomenon of the ceramic tile product after firing due to the repulsion reaction between the ceramic ink and the water-based glaze, and the product has high flatness and appearance that meets the design expectation. If other types of dispersants or surfactants are selected, it is difficult to achieve the same effect.

[0013] Preferably, the inorganic luminescent powder comprises the following weight parts of preparation raw materials: 79-99 parts of oxide A, 1-5 parts of oxide B, 0.5-5 parts of oxide C, and 0.1-1 parts of oxide D.

[0014] More preferably, the oxide A comprises at least one of zirconium oxide, aluminum oxide, the oxide B comprises lanthanum oxide, the oxide C comprises praseodymium oxide, and the oxide D comprises at least one of manganese oxide, bismuth oxide.

[0015] The inventors have found that when the above-mentioned preferred oxides are used to prepare the inorganic luminescent powder, the finished product can exhibit better luminescent effect when sprayed on the glaze, the recognition rate is higher, the degree of repulsion of the fluorescent ceramic ink after contacting with the water-based glaze is lower, the flatness of the ceramic tile surface after firing is higher, and the aesthetic decoration effect is better.

[0016] Preferably, the oily solvent comprises at least one of butanol, ethylene glycol, n-hexanol, isopropyl alcohol, ethyl acetate, butyl acetate, and octyl polyoxyethylene ether.

[0017] More preferably, the oily solvent comprises ethylene glycol and / or n-hexanol.

[0018] The inventors have found that when ethylene glycol and / or n-hexanol are used as solvents for ceramic ink, the dispersibility of the inorganic luminescent powder can be better guaranteed, the compatibility with water-based glaze is better, the flatness of the product surface after contacting and firing is higher, and the appearance of the product is less affected.

[0019] Preferably, the inorganic luminescent powder can be prepared by, but not limited to, the following preparation method:

[0020] The oxide A, the oxide B, the oxide C, and the oxide D are dissolved in an acid solution, then the obtained solution is mixed uniformly, a precipitant is added dropwise and a precipitation reaction is carried out, solid-liquid separation is performed, and the obtained powder is washed, dried, and calcined to obtain the inorganic luminescent powder.

[0021] More preferably, the acid in the acid solution comprises at least two of phosphoric acid, oxalic acid, citric acid, acetic acid, and hydrochloric acid.

[0022] More preferably, the concentration of the acid solution is 0.1-0.5 mol / L.

[0023] More preferably, the precipitant comprises at least one of tetramethylammonium hydroxide, ammonia, ethylenediamine, urea, sodium bicarbonate, and sodium hydroxide.

[0024] More preferably, the temperature of the precipitation reaction is 50-80°C, and the time is 1-5 h.

[0025] More preferably, the temperature of the calcination is 1200-1300°C, and the time is 0.5-5 h.

[0026] Preferably, the melting temperature of the inorganic luminescent powder is greater than or equal to 1400 DEG C.

[0027] Preferably, the average particle size of the inorganic luminescent powder is less than or equal to 1 micrometer.

[0028] The inorganic luminescent powder can be prepared by a wet chemical precipitation-calcination method, which is simple to operate, has a high processing temperature based on the selection of four types of oxides, is good in temperature resistance, fully meets the firing temperature of 1000-1350 DEG C of ceramic tiles, has high chemical inertness, and can be used for inkjet printing without additional modification treatment.

[0029] Another object of the present application is to provide the application of the fluorescent ceramic ink in the preparation of ceramic tiles.

[0030] Still another object of the present application is to provide a deep gray decorative pattern ceramic tile, which comprises a body layer, a base glaze layer, a security code layer, a decorative pattern layer and a topmost glaze layer arranged in sequence.

[0031] The security code layer is arranged by the fluorescent ceramic ink.

[0032] Preferably, the body layer comprises the following preparation raw materials in parts by weight:

[0033] SiO2 55-65%, Al2O3 17-20%, Fe2O3 0.7-1.5%, TiO2 0.1-0.3%, Na2O 2-2.5%, K2O 2-3.5%, CaO 0.5-1%, MgO 1.5-2%, and the rest is ignition loss.

[0034] Preferably, the base glaze layer comprises the following preparation raw materials in parts by weight:

[0035] SiO2 50-55%, Al2O3 18-22%, Fe2O3 0.1-0.3%, TiO2 0.05-0.15%, CaO 2-3.5%, MgO 0.4-1%, K2O 0.5-3%, Na2O 2-4%, ZrO2 5-7%, ZnO 1-3%, and the rest is ignition loss.

[0036] Preferably, the decorative pattern is arranged by inkjet printing of pattern ink, and the gray scale of the pattern ink is greater than or equal to 70.

[0037] Preferably, the topmost glaze layer comprises the following preparation raw materials in parts by weight:

[0038] SiO2 44-52.5%, Al2O3 18-19.5%, Fe2O3 0.1-0.3%, TiO2 0.05-0.15%, CaO 10-14.5%, MgO 1.4-3%, K2O 0.5-3%, the rest is loss on ignition.

[0039] It should be noted that the raw materials used in the preparation of the body layer, the bottom glaze layer, the topmost glaze layer and other ceramic tiles of the present application have no special restrictions. Based on the high compatibility and stability of the fluorescent ceramic ink of the present application, no interlayer interference or even chemical reaction occurs during the firing and processing of the ceramic tile, which avoids affecting the appearance effect of the ceramic tile. At the same time, the luminous intensity is large, and the identification rate of the anti-counterfeiting code is high. Based on the appearance effect and use function required by the ceramic tile, the person skilled in the art can use different preparation raw materials for the preparation of each structure layer.

[0040] However, due to the formula setting of the fluorescent ceramic ink in the anti-counterfeiting code layer, if the decorative pattern layer is set in advance and then the anti-counterfeiting code layer is set, the identification effect of the anti-counterfeiting code layer and the decorative effect of the decorative pattern will be affected due to the interlayer interference. Therefore, when the fluorescent ceramic ink of the present application is applied to deep gray decorative pattern ceramic tile products such as antique ceramic tile products, the anti-counterfeiting code layer needs to be set below the decorative pattern.

[0041] Another object of the present application is to provide a preparation method of the deep gray decorative pattern ceramic tile, comprising the following steps:

[0042] The body layer is pressed and dried to a water content of ≤0.3%;

[0043] The bottom glaze layer is set on the body layer;

[0044] The anti-counterfeiting code layer is set by inkjet printing the fluorescent ceramic ink on the face glaze layer;

[0045] The decorative pattern is inkjet printed on the anti-counterfeiting code layer and is baked at 150-250°C;

[0046] The topmost layer of polishing glaze or antique glaze is set on the decorative pattern layer to obtain a to-be-fired blank;

[0047] The to-be-fired blank is fired, and then polished and edged to obtain the deep gray decorative pattern ceramic tile.

[0048] Preferably, the bottom glaze layer is set by bell jar spraying, and the preparation raw materials of the bottom glaze layer are configured into slurry during setting. The glaze slurry ratio is 1.80-1.95 g / mL, and the glaze application amount is 300-600 g / m 2 .

[0049] Preferably, the topmost glaze is set by bell jar spraying or spraying in a spraying glaze cabinet, and the preparation raw materials of the top glaze layer are configured into a slurry with a glaze slurry ratio of 1.3-1.95 g / mL, and the glaze application amount is 150-600 g / m 2 .

[0050] Preferably, the temperature of the to-be-fired body during firing is 1200-1250 DEG C, and the time is 30-50 min.

[0051] The present application has the beneficial effect that the present application provides a fluorescent ceramic ink, by using inorganic powder prepared by a specific process as a luminescent powder, and by matching with a specific type of dispersant and surfactant to improve the dispersibility of the overall composition and the compatibility of the water-based glaze, not only can high luminous intensity under ultraviolet light source irradiation be achieved, but also the recognition rate of the invisible two-dimensional code under the superposition of deep gray decorative patterns is significantly improved, and the water-based glaze series such as high-glossiness glaze, low-glossiness antique glaze, etc. can be effectively compatible, avoiding the concave glaze phenomenon, and not affecting the flatness and aesthetic decoration effect of the ceramic tile surface. BRIEF DESCRIPTION OF DRAWINGS

[0052] Figure 1 The schematic diagram (a) under visible light and the schematic diagram (b) under ultraviolet light irradiation of the fluorescent ceramic ink described in Example 1 of the present application for preparing the anti-counterfeit code layer of the ceramic tile.

[0053] Figure 2 The particle size distribution diagram of the inorganic luminescent powder described in Example 1 of the present application.

[0054] Figure 3 The schematic diagram of the anti-counterfeit code layer of the ceramic tile described in Comparative Example 1 of the present application under ultraviolet light irradiation.

[0055] Figure 4 The schematic diagram of the anti-counterfeit code layer of the ceramic tile described in Comparative Example 2 of the present application under ultraviolet light irradiation. DETAILED DESCRIPTION

[0056] In order to better illustrate the purpose, technical scheme and advantages of the present application, the present application will be further described below in combination with specific examples and comparative examples, the purpose of which is to understand the content of the present application in detail, rather than to limit the present application. All other examples obtained by those of ordinary skill in the art without creative labor fall within the protection scope of the present application. The experimental reagents and instruments involved in the implementation of the present application are common ordinary reagents and instruments unless otherwise specified.

[0057] Example 1

[0058] An embodiment of the fluorescent ceramic ink and its application to a deep gray scale decorative pattern ceramic tile, the preparation method, comprising the following preparation steps:

[0059] (1) The green body layer is pressed and dried to a water content of ≤0.3%, and the strength of the green body layer is ≥1.8MPa;

[0060] The green body layer comprises the following preparation raw materials by weight:

[0061] SiO2 65%, Al2O3 20%, Fe2O3 1.5%, TiO2 0.3%, Na2O 2.5%, K2O 3.5%, CaO 1%, MgO 2%, and the rest is ignition loss;

[0062] The green body layer is obtained by mixing the preparation raw materials and drying at 200℃ for 40min;

[0063] (2) A bottom glaze layer is arranged on the green body layer;

[0064] The bottom glaze layer is arranged on the green body layer by spraying a bottom slurry, which comprises the preparation raw materials of the bottom glaze layer, water, and an appropriate amount of processing aids, and the glaze slurry ratio is 1.90g / mL, the clock cover spraying is performed at a flow rate of 33-38s / 100mL, and the glaze application amount is 400g / m 2 ;

[0065] The bottom glaze layer preparation raw materials comprise the following ingredients by weight: SiO2 55%, Al2O3 22%, Fe2O3 0.3%, TiO2 0.15%, CaO 3.5%, MgO 1%, K2O 3%, Na2O 4%, ZrO2 7%, ZnO 3%, and the rest is ignition loss;

[0066] (3) Inorganic luminescent powder is prepared;

[0067] The preparation method of the inorganic luminescent powder is as follows: 90 parts of zirconium oxide and 8.4 parts of aluminum oxide are added into a mixed solution of phosphoric acid and hydrochloric acid (molar ratio 1:1, total acid concentration 0.2 mol / L) to stir and dissolve completely to obtain a dissolving solution of oxide A; 1 part of lanthanum oxide is added into a mixed solution of phosphoric acid and hydrochloric acid (molar ratio 1:1, total acid concentration 0.2 mol / L) to stir and dissolve completely to obtain a dissolving solution of oxide B; 0.5 parts of praseodymium oxide is added into a mixed solution of phosphoric acid and hydrochloric acid (molar ratio 1:1, total acid concentration 0.2 mol / L) to stir and dissolve completely to obtain a dissolving solution of oxide C; 0.3 parts of manganese oxide and 0.7 parts of bismuth oxide are added into a mixed solution of phosphoric acid and hydrochloric acid (molar ratio 1:1, total acid concentration 0.2 mol / L) to stir and dissolve completely to obtain a dissolving solution of oxide D; the dissolving solutions of the oxides are mixed, 1 part of ethylenediamine and 1 part of urea are added dropwise, and reaction is carried out in a water bath at 60℃ for 2 hours; the obtained mixed solution is centrifuged, washed, and dried, and then the obtained powder is fired at 1350℃ in an air atmosphere for 30 minutes to obtain the inorganic powder;

[0068] (4) Preparation of fluorescent ceramic ink: according to the following weight proportions: inorganic luminescent powder 30 parts, solvent 60 parts, dispersant 5 parts, surfactant 5 parts;

[0069] The solvent includes ethylene glycol and n-hexanol, and the mass ratio of the two is 1:1; the dispersant includes polyacrylic acid, polyacrylamide, and methylene bisnaphthalene sulfonic acid sodium, and the mass ratio of the three is 2:2:1; the surfactant includes sodium monoalkyl sulfosuccinate and sodium dialkyl sulfosuccinate, and the mass ratio of the two is 1:1;

[0070] (5) The anti-counterfeiting code layer is set on the base glaze layer by inkjet printing of the fluorescent ceramic ink;

[0071] (6) The decoration pattern layer is printed on the anti-counterfeiting code layer by inkjet printing, and the gray scale of the pattern ink is 70, and then 200℃ drying is carried out for 1 minute;

[0072] (7) The topmost glaze is set as a polishing glaze on the decoration pattern layer to obtain a to-be-fired blank;

[0073] The topmost glaze comprises the following preparation raw materials in parts by weight:

[0074] SiO2 52.5%, Al2O3 19.5%, Fe2O3 0.3%, TiO2 0.15%, CaO 14.5%, MgO 3%, K2O 3%, and the rest is ignition loss;

[0075] The top glaze is prepared by spraying a slurry of the top glaze onto the decorative pattern layer, the slurry including raw materials for preparing the top glaze, water and an appropriate amount of processing aids, the glaze slurry ratio being 1.90 g / mL, the spraying being performed at a flow rate of 33-38 s / 100 mL, and the glaze application amount being 450 g / m 2 ;

[0076] (8) firing the to-be-fired body at 1220℃ for 40 min, and then performing a polishing and edging treatment, to obtain the ceramic tile;

[0077] Example 2

[0078] An embodiment of the deep gray decorative pattern ceramic tile using the fluorescent ceramic ink and its application according to the present application is different from the embodiment 1 only in that the top glaze on the decorative pattern layer is an antique glaze, and the top glaze layer is prepared by spraying a slurry of the top glaze onto the decorative pattern layer, the slurry including raw materials for preparing the top glaze, water and an appropriate amount of processing aids, the glaze slurry ratio being 1.30 g / mL, the spraying being performed at a flow rate of 33-38 s / 100 mL, and the glaze application amount being 150 g / m 2 ; the top glaze includes the following raw materials by weight:

[0079] SiO2 50%, Al2O3 18.5%, Fe2O3 0.2%, TiO2 0.1%, CaO 12.5%, MgO 1.43%, K2O 3%, and the rest being ignition loss.

[0080] Example 3

[0081] An embodiment of the deep gray decorative pattern ceramic tile using the fluorescent ceramic ink and its application according to the present application is different from the embodiment 1 only in that the fluorescent ceramic ink is prepared according to the following weight proportions: inorganic luminescent powder 25 parts, solvent 55 parts, dispersant 1 part, and surfactant 1 part.

[0082] Example 4

[0083] An embodiment of the deep gray decorative pattern ceramic tile using the fluorescent ceramic ink and its application according to the present application is different from the embodiment 1 only in that the ceramic ink is prepared according to the following weight proportions: inorganic luminescent powder 35 parts, solvent 70 parts, dispersant 5 parts, and surfactant 5 parts.

[0084] Example 5

[0085] An embodiment of the deep gray decorative pattern ceramic tile using the fluorescent ceramic ink and its application according to the present application is different from the embodiment 1 only in that 90 parts of zirconium oxide and 8.4 parts of aluminum oxide are respectively replaced by equal weight portions of aluminum oxide and yttrium oxide.

[0086] Example 6

[0087] One embodiment of the fluorescent ceramic ink and the deep gray decorative pattern ceramic tile using the same according to the present application differs from Example 1 only in that the lanthanum oxide is replaced with an equal weight portion of erbium oxide.

[0088] Example 7

[0089] One embodiment of the fluorescent ceramic ink and the deep gray decorative pattern ceramic tile using the same according to the present application differs from Example 1 only in that the praseodymium oxide is replaced with an equal weight portion of rubidium oxide.

[0090] Example 8

[0091] One embodiment of the fluorescent ceramic ink and the deep gray decorative pattern ceramic tile using the same according to the present application differs from Example 1 only in that the manganese oxide and the bismuth oxide are replaced with an equal weight portion of samarium oxide.

[0092] Example 9

[0093] One embodiment of the fluorescent ceramic ink and the deep gray decorative pattern ceramic tile using the same according to the present application differs from Example 1 only in that the oily solvent is replaced with an equal weight portion of ethyl acetate.

[0094] Example 10

[0095] One embodiment of the fluorescent ceramic ink and the deep gray decorative pattern ceramic tile using the same according to the present application differs from Example 1 only in that the oily solvent is replaced with a mixture of an equal weight portion of octyl polyoxyethylene ether and butanol, the mass ratio of which is 1:1.

[0096] Comparative Example 1

[0097] One embodiment of the fluorescent ceramic ink and the deep gray decorative pattern ceramic tile using the same according to the present application differs from Example 1 only in that the inorganic luminescent powder is not prepared by adding the dissolved solution of the oxide A.

[0098] Comparative Example 2

[0099] One embodiment of the fluorescent ceramic ink and the deep gray decorative pattern ceramic tile using the same according to the present application differs from Example 1 only in that the inorganic luminescent powder is not prepared by adding the dissolved solution of the oxide C.

[0100] Comparative Example 3

[0101] One embodiment of the fluorescent ceramic ink and the deep gray decorative pattern ceramic tile using the same according to the present application differs from Example 1 only in that the inorganic powder is prepared by replacing the zirconium oxide and the aluminum oxide with an equal weight portion of manganese oxide.

[0102] Comparative Example 4

[0103] A fluorescent ceramic ink and a deep gray decorative pattern ceramic tile using the same, which differs from Example 1 only in that the manganese oxide and bismuth oxide are respectively replaced with equal parts by weight of titanium oxide and zinc oxide at the time of formulation.

[0104] Comparative Example 5

[0105] A fluorescent ceramic ink and a deep gray decorative pattern ceramic tile using the same, which differs from Example 1 only in that the dispersant is replaced with diethylene glycol butyl ether acetate.

[0106] Comparative Example 6

[0107] A fluorescent ceramic ink and a deep gray decorative pattern ceramic tile using the same, which differs from Example 1 only in that the dispersant is replaced with lignosulfonate.

[0108] Comparative Example 7

[0109] A fluorescent ceramic ink and a deep gray decorative pattern ceramic tile using the same, which differs from Example 1 only in that the surfactant is replaced with polyether-modified polydimethylsiloxane.

[0110] Example 1

[0111] In order to verify the use effect of the product according to the present application, the products prepared in each of the examples and comparative examples were tested as follows:

[0112] (1) An optical camera was used to take pictures of the surface of the ceramic tiles obtained in each of the examples and comparative examples, and then it was observed whether there was a significant concave glaze phenomenon;

[0113] (2) Anti-counterfeiting code layer position flatness test: 10 test personnel were selected, and a blank control ceramic tile product without an anti-counterfeiting code layer was prepared on the basis of Example 1. First, the blank control sample was observed, and then it was observed whether there was an uneven phenomenon such as a concave glaze on the glaze surface at the position of the anti-counterfeiting layer under visible light. The score was 1-10 (integer points), and the greater the score, the closer the flatness of the glaze surface printed by the anti-counterfeiting code layer to the blank control product, and the smaller the influence of the anti-counterfeiting code layer on the glaze layer. At the same time, in order to avoid subjectivity and randomness, the test personnel were only informed of the sample order throughout the process, and after completing one round of testing and recording the average score, the order was changed and the same test was performed again, and the test was repeated twice. The average score of the three rounds of testing was recorded and only the middle score was recorded (for example, the three-round average scores of a certain sample were 9.0, 9.5 and 9.8, and the middle score of 9.5 was recorded).

[0114] (3) Anti-counterfeiting code recognition rate test: 100 parallel anti-counterfeiting codes (QR codes) were set for each embodiment and comparative product. As a statistical basis, ceramic bricks with invisible anti-counterfeiting layers were transported on a conveyor belt at 32m / min. The anti-counterfeiting code layer was irradiated with ultraviolet light to realize dynamic recognition and calculate the anti-counterfeiting code recognition rate.

[0115] The test results are shown in Table 1.

[0116] Table 1

[0117]

[0118]

[0119] As can be seen from Table 1, the fluorescent ceramic ink of this invention is based on the interaction of specific inorganic luminescent powders, dispersants, and surfactants, such as... Figure 1 As shown, it can achieve high luminous intensity under ultraviolet light irradiation, and the corresponding anti-counterfeiting code recognition rate is as high as 95% or more under dynamic conditions. It is also effectively compatible with high-gloss polished glaze and low-gloss antique glaze. As shown in Examples 1 and 2, the resulting products did not exhibit any concave glaze phenomenon, and their flatness evaluation was high, reaching 9.4 points or above. In contrast, the products described in Comparative Examples 1-4 had inappropriate selection of inorganic luminescent powder raw materials during preparation, resulting in insufficient anti-counterfeiting code recognition rates. Figure 3 and 4 As shown, the dispersants and surfactants used in the products described in Comparative Examples 5 to 7 were inappropriate, resulting in obvious concave glaze phenomena. These products could not meet the decorative requirements of ceramic tiles at all, and their flatness was low. Therefore, they were not of any use and no anti-counterfeiting code identification test was performed. Figure 2 This is a particle size distribution diagram of the inorganic luminescent powder described in Example 1 of the present invention. The synthesized inorganic luminescent powder has an overall particle size of less than 1 μm, and can be used to prepare fluorescent ceramic inks without preprocessing, which can reduce the energy consumption of ceramic ink preparation.

[0120] Furthermore, when the oxide A includes at least one of zirconium oxide and aluminum oxide, the oxide B includes lanthanum oxide, the oxide C includes praseodymium oxide, and the oxide D includes at least one of manganese oxide and bismuth oxide to prepare inorganic luminescent powder, not only can the finished product exhibit better luminescence when sprayed onto the glaze surface, resulting in a higher recognition rate (up to 100%), but the fluorescent ceramic ink also exhibits lower repulsion when in contact with water-based glazes, leading to higher surface smoothness and better aesthetic decoration of the fired ceramic tile. Simultaneously, when the solvent used in the fluorescent ceramic ink is ethylene glycol and / or n-hexanol, not only can the dispersibility of the inorganic luminescent powder be better ensured, but its compatibility with water-based glazes is also better, resulting in higher surface smoothness of the product after contact and firing, while minimizing the impact on the product's appearance.

[0121] Finally, it should be pointed out that the above examples are only used to illustrate the technical solutions of the present application and are not intended to limit the scope of protection of the present application. Although the present application has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that the technical solutions of the present application can be modified or equivalently replaced without departing from the essence and scope of the technical solutions of the present application.

Claims

1. A fluorescent ceramic ink, characterized by, The components include the following weight parts: The inorganic luminescent powder 25-36 parts, the oily solvent 54-73 parts, the dispersant 0.5-5 parts and the surfactant 1.5-5 parts; The preparation raw materials of the inorganic luminescent powder include oxide A, oxide B, oxide C and oxide D; The oxide A includes at least one of aluminum oxide, zirconium oxide and yttrium oxide, the oxide B includes at least one of lanthanum oxide, dysprosium oxide and erbium oxide, the oxide C includes at least one of praseodymium oxide, rubidium oxide and terbium oxide, and the oxide D includes at least one of manganese oxide, samarium oxide and bismuth oxide; The dispersant includes at least one of polyacrylic acid, ammonium polyacrylate, methylene bis naphthalene sulfonic acid sodium, methacrylic acid, ethylene imine and butyl acetal; The surfactant includes at least one of sodium monoalkyl sulfosuccinate and sodium dialkyl sulfosuccinate.

2. The fluorescent ceramic ink according to claim 1, wherein The inorganic luminescent powder includes the following weight parts of preparation raw materials: oxide A 79-99 parts, oxide B 1-5 parts, oxide C 0.5-5 parts and oxide D 0.1-1 part.

3. The fluorescent ceramic ink of claim 1, wherein, The oxide A includes at least one of zirconium oxide and aluminum oxide, the oxide B includes lanthanum oxide, the oxide C includes praseodymium oxide, and the oxide D includes at least one of manganese oxide and bismuth oxide.

4. The fluorescent ceramic ink of claim 1, wherein, The oily solvent includes at least one of butanol, ethylene glycol, n-hexanol, isopropyl alcohol, ethyl acetate, butyl acetate and octyl polyoxyethylene ether.

5. The fluorescent ceramic ink according to claim 4, wherein the ceramic ink is a ceramic ink for a ceramic tile. The oily solvent includes ethylene glycol and / or n-hexanol.

6. The fluorescent ceramic ink of claim 1, wherein, The inorganic luminescent powder is prepared by the following preparation method: The oxide A, the oxide B, the oxide C and the oxide D are respectively dissolved with an acid solution, then the obtained dissolution solution is uniformly mixed, then a precipitant is added dropwise and a precipitation reaction is carried out, solid-liquid separation is carried out, and the obtained powder is washed, dried and calcined, so that the inorganic luminescent powder is obtained.

7. The fluorescent ceramic ink of claim 1, wherein, The melting temperature of the inorganic luminescent powder is ≥1400℃, and / or the average particle size of the inorganic luminescent powder is ≤1μm.

8. The application of the fluorescent ceramic ink in claim 1-7 in the preparation of ceramic tiles.

9. A deep gray decorative pattern ceramic tile, characterized by, The ceramic tile includes the following layers in sequence: a body layer, a base glaze layer, a security code layer, a decorative pattern layer and a topmost glaze layer; the topmost glaze layer includes polishing glaze or antique glaze; The security code layer is set by the fluorescent ceramic ink in claim 1-7.

10. The method for manufacturing a deep gray decorative pattern ceramic tile according to any one of claims 1 to 9, wherein The method includes the following steps: The body layer is pressed and dried to a water content of ≤0.3%; The base glaze layer is set on the body layer; The security code layer is set by inkjet printing the fluorescent ceramic ink on the base glaze layer; The decorative pattern layer is set by inkjet printing the decorative pattern on the security code layer and baking at 150-250℃; The topmost polishing glaze or antique glaze is set on the decorative pattern layer to obtain a to-be-fired blank; The to-be-fired blank is fired, and then polished and edged to obtain the deep-gray decorative pattern ceramic tile.

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