A method for preparing a ceramic inkjet printing colorant

Abstract

This invention discloses a method for preparing pigments for ceramic inkjet printing, relating to the field of ceramic inkjet pigments, comprising the following steps: S1: preparing a mixture in the following proportions: 1.5–2 mol of tetraethyl orthosilicate, 1.4–1.8 mol of zirconium oxychloride, 0.04–0.2 mol of nano-iron oxide, 6–7 g of mineralizer, and water; S2: granulating the mixture by spray drying to obtain powder particles; S3: thoroughly mixing the powder particles and the mineralizer at a mass ratio of 6–10:1 and then calcining; S4: rinsing the calcined material clean, drying, and pulverizing to obtain a pigment with a D50 particle size of 0.5–0.8 μm. The preparation method of this invention has the advantages of improving the color development stability, antibacterial stability, and durability of the pigment.

Description

Technical Field

[0001] This invention relates to the technical field of ceramic inkjet pigments, and in particular to a method for preparing pigments for ceramic inkjet printing. Background Technology

[0002] Guided and chosen by the market, building ceramics enterprises will inevitably shift from simple cost competition to competition centered on product design, specifications, and technological innovation.

[0003] As a brand-new concept in ceramic decoration, color inkjet printing technology for ceramic decoration makes full use of abundant computer resources, introduces digital technology into traditional building ceramic enterprises, enables ceramic decoration to keep pace with the times, reflects fashionable features, meets people's personalized needs, and pushes ceramic decoration technology to a new stage.

[0004] Inkjet printing technology, developed in the late 1970s, is a non-contact digital printing technology that sprays ink onto various media surfaces through nozzles on a printhead, achieving non-contact, high-speed, and low-noise monochrome and color text and image printing. Building upon this, ceramic pigment powder is prepared into ink, which, under computer control, can be directly printed onto the surface of architectural ceramics using a specialized printer for decoration. Compared to existing decorative methods, inkjet printing has the following advantages: First, it saves energy and reduces emissions, eliminating the intermediate processes of sheet making, screen exposure, and engraving required in traditional mass production methods, shortening the production cycle and significantly improving the yield rate; second, the printing process is entirely computer-controlled, allowing for the decoration of complex patterns with high precision and repeatability, greatly improving the mechanization and production efficiency of the decoration process; finally, it is a non-contact decoration method, allowing for direct decoration on uneven surfaces.

[0005] However, the ceramic pigments used in inkjet printing technology still suffer from poor stability and color differences. Furthermore, research on functional ceramic pigments with antibacterial properties is limited, and they are commonly found in inks where antibacterial agents are directly added to pigments, resulting in poor antibacterial durability and stability. Summary of the Invention

[0006] To address the shortcomings of existing technologies, the present invention aims to provide a pigment for ceramic inkjet printing and its preparation method.

[0007] The above-mentioned objective of the present invention is achieved through the following technical solution:

[0008] A method for preparing a pigment for ceramic inkjet printing includes the following steps:

[0009] S1: Prepare the mixture in the following proportions: 1.5-2 mol of tetraethyl orthosilicate, 1.4-1.8 mol of zirconium oxychloride, 0.04-0.2 mol of nano iron oxide, 6-7 g of mineralizing agent and water.

[0010] S2: The mixture is spray-dried and granulated to obtain powder;

[0011] S3: Thoroughly mix the powder and foaming agent at a mass ratio of 6 to 10:1 and then calcine.

[0012] S4: Rinse the calcined material clean, dry it, and crush it to obtain the colorant.

[0013] Furthermore, the nano-iron oxide is α-iron oxide with a particle size of less than 100 nanometers.

[0014] Furthermore, mineralizing agents include lithium fluoride, sodium fluorosilicate, and sodium fluoride.

[0015] Furthermore, the preparation method of the foaming agent includes the following steps:

[0016] A1: Heat a saturated sucrose aqueous solution to 150-160°C and evaporate the water until it becomes a syrup.

[0017] A2: A mixture of oxygen and carbon dioxide is injected into the syrup under high pressure, wherein the volume percentage of oxygen is 40-70%.

[0018] A3: Cool the syrup to room temperature or below within 1-3 minutes to obtain the coarse material;

[0019] A4: The foaming agent can be obtained by crushing the coarse material to 100-1000μm.

[0020] This application selects a conventional zirconium iron red pigment formulation to prepare the mixture. Furthermore, by adding a specific foaming agent powder for co-calcination, the stability of the prepared pigment is greatly improved by simplifying the conventional granulation, calcination, and drying steps. This invention employs a method of mixing the foaming agent with the powder before calcination to improve the uniformity of calcination. During calcination, the foaming agent releases gas. This gas can adjust the powder during calcination, ensuring more uniform calcination of each particle through the impact of the released gas. Additionally, the gas in the foaming agent contains oxygen, which helps to increase the oxygen content in the powder during calcination, resulting in a more stable zirconium iron red pigment color. The main reason is that the color development of zirconium iron red primarily depends on the reaction of quartz and zirconium dioxide in an oxidizing atmosphere during high-temperature calcination, and the reaction of Fe... 3+The powder is coated with a material with a zirconium silicate crystal structure, and the foaming agent, through the impact of gas release and the release of oxygen, makes the oxygen content in various parts of the powder higher, which is more conducive to the calcination of the raw material in an oxidizing atmosphere, thus obtaining a more stable zirconium iron red color.

[0021] Furthermore, in step S3, after the powder and foaming agent are fully mixed, they are first moistened with 1% ammonium molybdate solution and then immediately calcined.

[0022] After the powder and foaming agent are thoroughly mixed, they are first moistened with water. This allows some of the foaming agent to dissolve and generate oxygen, which is then released into the gaps within the powder before calcination. Calcination then proceeds, ensuring a high oxygen content throughout the powder initially. At the high calcination temperature, the sucrose completely burns and decomposes into carbon dioxide and water vapor, releasing internal oxygen and replenishing the oxygen content in all parts of the powder, effectively improving the calcination effect. Secondly, pre-wetting, which releases some oxygen from the foaming agent, prevents excessive carbon dioxide from the sucrose decomposition during high-temperature calcination from diluting the oxygen content around the calcined powder. This ensures that oxygen dominates within the gaps of the powder, effectively enhancing the foaming agent's effect. Furthermore, the molybdate groups in ammonium molybdate are deposited into the powder through osmosis, and the oxygen generated from the partial decomposition of the foaming agent allows these molybdate groups to penetrate even deeper into the powder. The molybdate groups contribute to the Fe... 3+ The coating is used to make the red zirconium iron material more stable after calcination.

[0023] Furthermore, the sucrose aqueous solution in step A1 also contains silver ions, with a mass concentration of 0.1-4%.

[0024] The silver ion component added to the foaming agent in this invention has two advantages. First, silver ions have good antibacterial properties, which can effectively improve the antibacterial properties of the pigment. Second, during the calcination process with the powder, the silver ions can diffuse into the various gaps of the pigment through the impact of the gas generated in the foaming agent. Furthermore, as the calcination process continues, some silver ions will also combine with the pigment, thereby improving the uniformity of dispersion and adhesion stability of silver ions in the pigment.

[0025] Furthermore, the sucrose aqueous solution in step A1 also contains porous silica particles, accounting for 0.2% to 3% by mass.

[0026] This invention also incorporates porous silica particles into the foaming agent. These porous silica particles have a porous structure, which allows them to store more pores to accommodate more gas, thereby improving the gas release capacity and amount of the foaming agent. Furthermore, the porous structure of the silica particles can adsorb some silver ions, and the silver ions within the porous structure of the silica are more stable, further enhancing the antibacterial stability of the pigment.

[0027] Furthermore, the calcination time in step S3 is 1 to 3 hours.

[0028] Furthermore, the calcination process in step S3 includes a first high-temperature section, a low-temperature section, and a second high-temperature section. The temperature of the first high-temperature section is 900–1100°C, and the calcination time accounts for 1 / 4 of the total time. The temperature of the low-temperature section is 300–500°C, and the calcination time accounts for 1 / 4 of the total time. The temperature of the second high-temperature section is 1200°C, and the calcination time accounts for 1 / 2 of the total time.

[0029] By controlling the calcination process in stages and at different high and low temperatures, the calcination effect of the foaming agent and pigment is improved, and their mutual promoting effect is more obvious.

[0030] Furthermore, the D50 particle size of the calcined powder in step S4 is 0.5–0.8 μm.

[0031] Compared with the prior art, the beneficial effects of the present invention are:

[0032] The key to this invention lies in the use of a foaming agent. During calcination, the foaming agent releases gases, which, on the one hand, promote uniform calcination of the powder particles through impact, and on the other hand, provide oxygen, helping to increase the oxygen content in the powder during calcination, thus resulting in a more stable zirconium iron red pigment color. Secondly, by adding silver ions to the sucrose aqueous solution, the antibacterial properties of the pigment and the uniformity of silver ion dispersion are improved; the addition of porous silica particles enhances gas release capacity and antibacterial stability. Before calcination, the mixture of powder particles and foaming agent is moistened, ensuring that the oxygen content in the calcined powder is initially high throughout, increasing oxygen release and preventing color differences. The calcination time is 1–3 hours, divided into a first high-temperature stage of 900–1100℃, a low-temperature stage of 300–500℃, and a second high-temperature stage of 1200℃. This segmentation and temperature control improve the calcination effect. The final powder has a D50 particle size of 0.5–0.8 μm. This method improves the uniformity of pigment calcination and the performance of the final product. Detailed Implementation

[0033] The present invention will now be described in detail with reference to the embodiments.

[0034] Example 1

[0035] This embodiment discloses a method for preparing pigments for ceramic inkjet printing, including the following steps:

[0036] S1: Prepare the mixture according to the following ratio: mix 1.5 mol of tetraethyl orthosilicate, 1.4 mol of zirconium oxychloride, 0.04 mol of nano iron oxide, 6 g of mineralizing agent and 10 L of water; the nano iron oxide is α iron oxide with a particle size of less than 100 nanometers; the mineralizing agent includes lithium fluoride, sodium fluorosilicate and sodium fluoride, and the mass ratio of the three is 1:1:1.

[0037] S2: The mixture is spray-dried and granulated to obtain powder.

[0038] S3: Mix the powder and foaming agent thoroughly at a mass ratio of 6:1 and then calcine. The calcination temperature is controlled at 1100℃ and the calcination time is controlled at 2 hours.

[0039] The preparation method of the foaming agent includes the following steps:

[0040] A1: Heat a saturated sucrose aqueous solution to 160°C and then evaporate the water to a syrup-like consistency;

[0041] A2: A mixture of oxygen and carbon dioxide is injected into the syrup under high pressure, with oxygen accounting for 40% of the volume.

[0042] A3: Cool the syrup to room temperature or below within 1 minute to obtain the coarse material;

[0043] A4: The foaming agent can be obtained by crushing the coarse material to 100μm.

[0044] S4: Rinse the calcined material clean, dry it, and pulverize it to obtain a colorant with a D50 particle size of 0.5μm.

[0045] Example 2

[0046] This embodiment discloses a method for preparing pigments for ceramic inkjet printing, including the following steps:

[0047] S1: Prepare the mixture according to the following ratio: mix 2 mol of tetraethyl orthosilicate, 1.8 mol of zirconium oxychloride, 0.2 mol of nano iron oxide, 7 g of mineralizing agent and 10 L of water; the nano iron oxide is α iron oxide with a particle size of less than 100 nanometers; the mineralizing agent includes lithium fluoride, sodium fluorosilicate and sodium fluoride, and the mass ratio of the three is 1:1:1.

[0048] S2: The mixture is spray-dried and granulated to obtain powder.

[0049] S3: Mix the powder and foaming agent thoroughly at a mass ratio of 8:1 and then calcine. The calcination temperature is controlled at 1100℃ and the calcination time is controlled at 2 hours.

[0050] The preparation method of the foaming agent includes the following steps:

[0051] A1: Heat a saturated sucrose aqueous solution to 150°C and evaporate the water until it becomes a syrup.

[0052] A2: A mixture of oxygen and carbon dioxide is injected into the syrup under high pressure, with oxygen accounting for 60% of the volume.

[0053] A3: Cool the syrup to room temperature or below within 1 minute to obtain the coarse material;

[0054] A4: The foaming agent can be obtained by crushing the coarse material to 100μm.

[0055] S4: Rinse the calcined material clean, dry it, and pulverize it to obtain a colorant with a D50 particle size of 0.8μm.

[0056] Example 3

[0057] This embodiment discloses a method for preparing pigments for ceramic inkjet printing, including the following steps:

[0058] S1: Prepare the mixture according to the following ratio: mix 1.7 mol of tetraethyl orthosilicate, 1.6 mol of zirconium oxychloride, 0.1 mol of nano iron oxide, 6 g of mineralizing agent and 10 L of water; the nano iron oxide is α iron oxide with a particle size of less than 100 nanometers; the mineralizing agent includes lithium fluoride, sodium fluorosilicate and sodium fluoride, and the mass ratio of the three is 1:1:1.

[0059] S2: The mixture is spray-dried and granulated to obtain powder.

[0060] S3: Mix the powder and foaming agent thoroughly at a mass ratio of 8:1 and then calcine. The calcination temperature is controlled at 1100℃ and the calcination time is controlled at 2 hours.

[0061] The preparation method of the foaming agent includes the following steps:

[0062] A1: Heat a saturated sucrose aqueous solution to 150°C and evaporate the water until it becomes a syrup.

[0063] A2: A mixture of oxygen and carbon dioxide is injected into the syrup under high pressure, with oxygen accounting for 60% of the volume.

[0064] A3: Cool the syrup to room temperature or below within 1 minute to obtain the coarse material;

[0065] A4: The foaming agent can be obtained by crushing the coarse material to 100μm.

[0066] S4: Rinse the calcined material clean, dry it, and pulverize it to obtain a colorant with a D50 particle size of 0.7μm.

[0067] Example 4

[0068] This embodiment discloses a method for preparing pigments for ceramic inkjet printing, including the following steps:

[0069] S1: Prepare the mixture according to the following ratio: mix 1.5 mol of tetraethyl orthosilicate, 1.4 mol of zirconium oxychloride, 0.2 mol of nano iron oxide, 6 g of mineralizing agent and 10 L of water; the nano iron oxide is α iron oxide with a particle size of less than 100 nanometers; the mineralizing agent includes lithium fluoride, sodium fluorosilicate and sodium fluoride, and the mass ratio of the three is 1:1:1.

[0070] S2: The mixture is spray-dried and granulated to obtain powder.

[0071] S3: Mix the powder and foaming agent thoroughly at a mass ratio of 6:1 and then calcine. The calcination temperature is controlled at 1100℃ and the calcination time is controlled at 2 hours.

[0072] The preparation method of the foaming agent includes the following steps:

[0073] A1: Heat a saturated sucrose aqueous solution to 150°C and evaporate the water until it becomes a syrup.

[0074] A2: A mixture of oxygen and carbon dioxide is injected into the syrup under high pressure, with oxygen accounting for 60% of the volume.

[0075] A3: Cool the syrup to room temperature or below within 1 minute to obtain the coarse material;

[0076] A4: The foaming agent can be obtained by crushing the coarse material to 100μm.

[0077] S4: Rinse the calcined material clean, dry it, and pulverize it to obtain a colorant with a D50 particle size of 0.6μm.

[0078] Example 5

[0079] This embodiment discloses a method for preparing pigments for ceramic inkjet printing, including the following steps:

[0080] S1: Prepare the mixture according to the following ratio: mix 2 mol of tetraethyl orthosilicate, 1.8 mol of zirconium oxychloride, 0.2 mol of nano iron oxide, 7 g of mineralizing agent and 10 L of water; the nano iron oxide is α iron oxide with a particle size of less than 100 nanometers; the mineralizing agent includes lithium fluoride, sodium fluorosilicate and sodium fluoride, and the mass ratio of the three is 1:1:1.

[0081] S2: The mixture is spray-dried and granulated to obtain powder.

[0082] S3: Mix the powder and foaming agent thoroughly at a mass ratio of 10:1 and then calcine. The calcination temperature is controlled at 1100℃ and the calcination time is controlled at 2 hours.

[0083] The preparation method of the foaming agent includes the following steps:

[0084] A1: Heat a saturated sucrose aqueous solution to 160°C and then evaporate the water to a syrup-like consistency;

[0085] A2: A mixture of oxygen and carbon dioxide is injected into the syrup under high pressure, with oxygen accounting for 70% of the volume.

[0086] A3: Cool the syrup to room temperature or below within 3 minutes to obtain the coarse material;

[0087] A4: The foaming agent can be obtained by crushing the coarse material to 100μm.

[0088] S4: Rinse the calcined material clean, dry it, and pulverize it to obtain a colorant with a D50 particle size of 0.5μm.

[0089] Example 6

[0090] This embodiment discloses a method for preparing pigments for ceramic inkjet printing, including the following steps:

[0091] S1: Prepare the mixture according to the following ratio: mix 2 mol of tetraethyl orthosilicate, 1.8 mol of zirconium oxychloride, 0.2 mol of nano iron oxide, 7 g of mineralizing agent and 10 L of water; the nano iron oxide is α iron oxide with a particle size of less than 100 nanometers; the mineralizing agent includes lithium fluoride, sodium fluorosilicate and sodium fluoride, and the mass ratio of the three is 1:1:1.

[0092] S2: The mixture is spray-dried and granulated to obtain powder.

[0093] S3: After thoroughly mixing the powder and foaming agent at a mass ratio of 10:1, wet the mixture with 1% ammonium molybdate solution and then calcine it. The calcine temperature is controlled at 1100℃ and the calcine time is controlled at 2 hours.

[0094] The preparation method of the foaming agent includes the following steps:

[0095] A1: Heat a saturated sucrose aqueous solution to 160°C and then evaporate the water to a syrup-like consistency;

[0096] A2: A mixture of oxygen and carbon dioxide is injected into the syrup under high pressure, with oxygen accounting for 70% of the volume.

[0097] A3: Cool the syrup to room temperature or below within 3 minutes to obtain the coarse material;

[0098] A4: The foaming agent can be obtained by crushing the coarse material to 100μm.

[0099] S4: Rinse the calcined material clean, dry it, and pulverize it to obtain a colorant with a D50 particle size of 0.5μm.

[0100] Example 7

[0101] This embodiment discloses a method for preparing pigments for ceramic inkjet printing, including the following steps:

[0102] S1: Prepare the mixture according to the following ratio: mix 2 mol of tetraethyl orthosilicate, 1.8 mol of zirconium oxychloride, 0.2 mol of nano iron oxide, 7 g of mineralizing agent and 10 L of water; the nano iron oxide is α iron oxide with a particle size of less than 100 nanometers; the mineralizing agent includes lithium fluoride, sodium fluorosilicate and sodium fluoride, and the mass ratio of the three is 1:1:1.

[0103] S2: The mixture is spray-dried and granulated to obtain powder.

[0104] S3: After thoroughly mixing the powder and foaming agent at a mass ratio of 10:1, wet the mixture with 1% ammonium molybdate solution and then calcine it. The calcine temperature is controlled at 1100℃ and the calcine time is controlled at 2 hours.

[0105] The preparation method of the foaming agent includes the following steps:

[0106] A1: A mixed aqueous solution of sucrose and silver nitrate is heated to 160°C and the water is evaporated to a syrup-like state; wherein the sucrose reaches a saturation concentration, and the mass concentration of silver ions in the mixed aqueous solution is 0.1%;

[0107] A2: A mixture of oxygen and carbon dioxide is injected into the syrup under high pressure, with oxygen accounting for 70% of the volume.

[0108] A3: Cool the syrup to room temperature or below within 3 minutes to obtain the coarse material;

[0109] A4: The foaming agent can be obtained by crushing the coarse material to 100μm.

[0110] S4: Rinse the calcined material clean, dry it, and pulverize it to obtain a colorant with a D50 particle size of 0.5μm.

[0111] Example 8

[0112] This embodiment discloses a method for preparing pigments for ceramic inkjet printing, including the following steps:

[0113] S1: Prepare the mixture according to the following ratio: mix 2 mol of tetraethyl orthosilicate, 1.8 mol of zirconium oxychloride, 0.2 mol of nano iron oxide, 7 g of mineralizing agent and 10 L of water; the nano iron oxide is α iron oxide with a particle size of less than 100 nanometers; the mineralizing agent includes lithium fluoride, sodium fluorosilicate and sodium fluoride, and the mass ratio of the three is 1:1:1.

[0114] S2: The mixture is spray-dried and granulated to obtain powder.

[0115] S3: After thoroughly mixing the powder and foaming agent at a mass ratio of 10:1, wet the mixture with 1% ammonium molybdate solution and then calcine it. The calcine temperature is controlled at 1100℃ and the calcine time is controlled at 2 hours.

[0116] The preparation method of the foaming agent includes the following steps:

[0117] A1: A mixed aqueous solution of sucrose and silver nitrate is heated to 160°C and the water is evaporated to a syrup-like state; wherein, the sucrose reaches a saturation concentration, and the mass concentration of silver ions in the mixed aqueous solution is 4%;

[0118] A2: A mixture of oxygen and carbon dioxide is injected into the syrup under high pressure, with oxygen accounting for 70% of the volume.

[0119] A3: Cool the syrup to room temperature or below within 3 minutes to obtain the coarse material;

[0120] A4: The foaming agent can be obtained by crushing the coarse material to 100μm.

[0121] S4: Rinse the calcined material clean, dry it, and pulverize it to obtain a colorant with a D50 particle size of 0.5μm.

[0122] Example 9

[0123] This embodiment discloses a method for preparing pigments for ceramic inkjet printing, including the following steps:

[0124] S1: Prepare the mixture according to the following ratio: mix 2 mol of tetraethyl orthosilicate, 1.8 mol of zirconium oxychloride, 0.2 mol of nano iron oxide, 7 g of mineralizing agent and 10 L of water; the nano iron oxide is α iron oxide with a particle size of less than 100 nanometers; the mineralizing agent includes lithium fluoride, sodium fluorosilicate and sodium fluoride, and the mass ratio of the three is 1:1:1.

[0125] S2: The mixture is spray-dried and granulated to obtain powder.

[0126] S3: After thoroughly mixing the powder and foaming agent at a mass ratio of 10:1, wet the mixture with 1% ammonium molybdate solution and then calcine it. The calcine temperature is controlled at 1100℃ and the calcine time is controlled at 2 hours.

[0127] The preparation method of the foaming agent includes the following steps:

[0128] A1: A mixed aqueous solution of sucrose and silver nitrate is heated to 160°C and the water is evaporated to a syrup-like state; wherein the sucrose reaches a saturation concentration, and the mass concentration of silver ions in the mixed aqueous solution is 1%;

[0129] A2: A mixture of oxygen and carbon dioxide is injected into the syrup under high pressure, with oxygen accounting for 70% of the volume.

[0130] A3: Cool the syrup to room temperature or below within 3 minutes to obtain the coarse material;

[0131] A4: The foaming agent can be obtained by crushing the coarse material to 100μm.

[0132] S4: Rinse the calcined material clean, dry it, and pulverize it to obtain a colorant with a D50 particle size of 0.5μm.

[0133] Example 10

[0134] This embodiment discloses a method for preparing pigments for ceramic inkjet printing, including the following steps:

[0135] S1: Prepare the mixture according to the following ratio: mix 2 mol of tetraethyl orthosilicate, 1.8 mol of zirconium oxychloride, 0.2 mol of nano iron oxide, 7 g of mineralizing agent and 10 L of water; the nano iron oxide is α iron oxide with a particle size of less than 100 nanometers; the mineralizing agent includes lithium fluoride, sodium fluorosilicate and sodium fluoride, and the mass ratio of the three is 1:1:1.

[0136] S2: The mixture is spray-dried and granulated to obtain powder.

[0137] S3: After thoroughly mixing the powder and foaming agent at a mass ratio of 10:1, wet the mixture with 1% ammonium molybdate solution and then calcine it. The calcine temperature is controlled at 1100℃ and the calcine time is controlled at 2 hours.

[0138] The preparation method of the foaming agent includes the following steps:

[0139] A1: A mixed aqueous solution of sucrose, silver nitrate and porous silica is heated to 160°C and the water is evaporated to a syrup-like state; wherein, the sucrose reaches a saturated concentration, the mass concentration of silver ions in the mixed aqueous solution is 1%, the mass proportion of porous silica particles is 2%, and the D50 particle size of the porous silica particles is 500nm.

[0140] A2: A mixture of oxygen and carbon dioxide is injected into the syrup under high pressure, with oxygen accounting for 70% of the volume.

[0141] A3: Cool the syrup to room temperature or below within 3 minutes to obtain the coarse material;

[0142] A4: The foaming agent can be obtained by crushing the coarse material to 100μm.

[0143] S4: Rinse the calcined material clean, dry it, and pulverize it to obtain a colorant with a D50 particle size of 0.5μm.

[0144] Example 11

[0145] This embodiment discloses a method for preparing pigments for ceramic inkjet printing, including the following steps:

[0146] S1: Prepare the mixture according to the following ratio: mix 2 mol of tetraethyl orthosilicate, 1.8 mol of zirconium oxychloride, 0.2 mol of nano iron oxide, 7 g of mineralizing agent and 10 L of water; the nano iron oxide is α iron oxide with a particle size of less than 100 nanometers; the mineralizing agent includes lithium fluoride, sodium fluorosilicate and sodium fluoride, and the mass ratio of the three is 1:1:1.

[0147] S2: The mixture is spray-dried and granulated to obtain powder.

[0148] S3: After thoroughly mixing the powder and foaming agent at a mass ratio of 10:1, wet the mixture with 1% ammonium molybdate solution and then calcine it. The calcine temperature is controlled at 1100℃ and the calcine time is controlled at 3 hours.

[0149] The preparation method of the foaming agent includes the following steps:

[0150] A1: A mixed aqueous solution of sucrose, silver nitrate and porous silica is heated to 160°C and the water is evaporated to a syrup-like state; wherein, the sucrose reaches a saturated concentration, the mass concentration of silver ions in the mixed aqueous solution is 1%, the mass proportion of porous silica particles is 3%, and the D50 particle size of the porous silica particles is 500nm.

[0151] A2: A mixture of oxygen and carbon dioxide is injected into the syrup under high pressure, with oxygen accounting for 70% of the volume.

[0152] A3: Cool the syrup to room temperature or below within 3 minutes to obtain the coarse material;

[0153] A4: The foaming agent can be obtained by crushing the coarse material to 100μm.

[0154] S4: Rinse the calcined material clean, dry it, and pulverize it to obtain a colorant with a D50 particle size of 0.5μm.

[0155] Example 12

[0156] This embodiment discloses a method for preparing pigments for ceramic inkjet printing, including the following steps:

[0157] S1: Prepare the mixture according to the following ratio: mix 2 mol of tetraethyl orthosilicate, 1.8 mol of zirconium oxychloride, 0.2 mol of nano iron oxide, 7 g of mineralizing agent and 10 L of water; the nano iron oxide is α iron oxide with a particle size of less than 100 nanometers; the mineralizing agent includes lithium fluoride, sodium fluorosilicate and sodium fluoride, and the mass ratio of the three is 1:1:1.

[0158] S2: The mixture is spray-dried and granulated to obtain powder.

[0159] S3: After thoroughly mixing the powder and foaming agent at a mass ratio of 10:1, wet the mixture with 1% ammonium molybdate solution and then calcine it. The calcine temperature is controlled at 1100℃ and the calcine time is controlled at 3 hours.

[0160] The preparation method of the foaming agent includes the following steps:

[0161] A1: A mixed aqueous solution of sucrose, silver nitrate and porous silica is heated to 160°C and the water is evaporated to a syrup-like state; wherein, the sucrose reaches a saturated concentration, the mass concentration of silver ions in the mixed aqueous solution is 1%, the mass percentage of porous silica particles is 0.2%, and the D50 particle size of the porous silica particles is 500nm.

[0162] A2: A mixture of oxygen and carbon dioxide is injected into the syrup under high pressure, with oxygen accounting for 70% of the volume.

[0163] A3: Cool the syrup to room temperature or below within 3 minutes to obtain the coarse material;

[0164] A4: The foaming agent can be obtained by crushing the coarse material to 100μm.

[0165] S4: Rinse the calcined material clean, dry it, and pulverize it to obtain a colorant with a D50 particle size of 0.5μm.

[0166] Example 13

[0167] This embodiment discloses a method for preparing pigments for ceramic inkjet printing, including the following steps:

[0168] S1: Prepare the mixture according to the following ratio: mix 2 mol of tetraethyl orthosilicate, 1.8 mol of zirconium oxychloride, 0.2 mol of nano iron oxide, 7 g of mineralizing agent and 10 L of water; the nano iron oxide is α iron oxide with a particle size of less than 100 nanometers; the mineralizing agent includes lithium fluoride, sodium fluorosilicate and sodium fluoride, and the mass ratio of the three is 1:1:1.

[0169] S2: The mixture is spray-dried and granulated to obtain powder.

[0170] S3: After thoroughly mixing the powder and foaming agent at a mass ratio of 10:1, wet the mixture with 1% ammonium molybdate solution and then calcine it. The calcine process includes a first high-temperature stage, a low-temperature stage, and a second high-temperature stage. The temperature of the first high-temperature stage is 1000℃ and the calcine time accounts for 1 / 4 of the total time. The temperature of the low-temperature stage is 500℃ and the calcine time accounts for 1 / 4 of the total time. The temperature of the second high-temperature stage is 1200℃ and the calcine time accounts for 1 / 2 of the total time.

[0171] The preparation method of the foaming agent includes the following steps:

[0172] A1: A mixed aqueous solution of sucrose, silver nitrate and porous silica is heated to 160°C and the water is evaporated to a syrup-like state; wherein, the sucrose reaches a saturated concentration, the mass concentration of silver ions in the mixed aqueous solution is 1%, the mass proportion of porous silica particles is 3%, and the D50 particle size of the porous silica particles is 500nm.

[0173] A2: A mixture of oxygen and carbon dioxide is injected into the syrup under high pressure, with oxygen accounting for 70% of the volume.

[0174] A3: Cool the syrup to room temperature or below within 3 minutes to obtain the coarse material;

[0175] A4: The foaming agent can be obtained by crushing the coarse material to 100μm.

[0176] S4: Rinse the calcined material clean, dry it, and pulverize it to obtain a colorant with a D50 particle size of 0.5μm.

[0177] Example 14

[0178] This embodiment discloses a method for preparing pigments for ceramic inkjet printing, including the following steps:

[0179] S1: Prepare the mixture according to the following ratio: mix 2 mol of tetraethyl orthosilicate, 1.8 mol of zirconium oxychloride, 0.2 mol of nano iron oxide, 7 g of mineralizing agent and 10 L of water; the nano iron oxide is α iron oxide with a particle size of less than 100 nanometers; the mineralizing agent includes lithium fluoride, sodium fluorosilicate and sodium fluoride, and the mass ratio of the three is 1:1:1.

[0180] S2: The mixture is spray-dried and granulated to obtain powder.

[0181] S3: After thoroughly mixing the powder and foaming agent at a mass ratio of 10:1, wet the mixture with 1% ammonium molybdate solution and then calcine it. The calcine process includes a first high-temperature stage, a low-temperature stage, and a second high-temperature stage. The temperature of the first high-temperature stage is 1100℃ and the calcine time accounts for 1 / 4 of the total time. The temperature of the low-temperature stage is 300℃ and the calcine time accounts for 1 / 4 of the total time. The temperature of the second high-temperature stage is 1200℃ and the calcine time accounts for 1 / 2 of the total time.

[0182] The preparation method of the foaming agent includes the following steps:

[0183] A1: A mixed aqueous solution of sucrose, silver nitrate and porous silica is heated to 160°C and the water is evaporated to a syrup-like state; wherein, the sucrose reaches a saturated concentration, the mass concentration of silver ions in the mixed aqueous solution is 1%, the mass proportion of porous silica particles is 3%, and the D50 particle size of the porous silica particles is 500nm.

[0184] A2: A mixture of oxygen and carbon dioxide is injected into the syrup under high pressure, with oxygen accounting for 70% of the volume.

[0185] A3: Cool the syrup to room temperature or below within 3 minutes to obtain the coarse material;

[0186] A4: The foaming agent can be obtained by crushing the coarse material to 100μm.

[0187] S4: Rinse the calcined material clean, dry it, and pulverize it to obtain a colorant with a D50 particle size of 0.5μm.

[0188] Example 15

[0189] This embodiment discloses a method for preparing pigments for ceramic inkjet printing, including the following steps:

[0190] S1: Prepare the mixture according to the following ratio: mix 2 mol of tetraethyl orthosilicate, 1.8 mol of zirconium oxychloride, 0.2 mol of nano iron oxide, 7 g of mineralizing agent and 10 L of water; the nano iron oxide is α iron oxide with a particle size of less than 100 nanometers; the mineralizing agent includes lithium fluoride, sodium fluorosilicate and sodium fluoride, and the mass ratio of the three is 1:1:1.

[0191] S2: The mixture is spray-dried and granulated to obtain powder.

[0192] S3: After thoroughly mixing the powder and foaming agent at a mass ratio of 10:1, wet the mixture with 1% ammonium molybdate solution and then calcine it. The calcine process includes a first high-temperature stage, a low-temperature stage, and a second high-temperature stage. The temperature of the first high-temperature stage is 900℃ and the calcine time accounts for 1 / 4 of the total time. The temperature of the low-temperature stage is 400℃ and the calcine time accounts for 1 / 4 of the total time. The temperature of the second high-temperature stage is 1200℃ and the calcine time accounts for 1 / 2 of the total time.

[0193] The preparation method of the foaming agent includes the following steps:

[0194] A1: A mixed aqueous solution of sucrose, silver nitrate and porous silica is heated to 160°C and the water is evaporated to a syrup-like state; wherein, the sucrose reaches a saturated concentration, the mass concentration of silver ions in the mixed aqueous solution is 1%, the mass proportion of porous silica particles is 3%, and the D50 particle size of the porous silica particles is 500nm.

[0195] A2: A mixture of oxygen and carbon dioxide is injected into the syrup under high pressure, with oxygen accounting for 70% of the volume.

[0196] A3: Cool the syrup to room temperature or below within 3 minutes to obtain the coarse material;

[0197] A4: The foaming agent can be obtained by crushing the coarse material to 100μm.

[0198] S4: Rinse the calcined material clean, dry it, and pulverize it to obtain a colorant with a D50 particle size of 0.5μm.

[0199] Example 16

[0200] This embodiment discloses a method for preparing pigments for ceramic inkjet printing, including the following steps:

[0201] S1: Prepare the mixture according to the following ratio: mix 2 mol of tetraethyl orthosilicate, 1.8 mol of zirconium oxychloride, 0.2 mol of nano iron oxide, 7 g of mineralizing agent and 10 L of water; the nano iron oxide is α iron oxide with a particle size of less than 100 nanometers; the mineralizing agent includes lithium fluoride, sodium fluorosilicate and sodium fluoride, and the mass ratio of the three is 1:1:1.

[0202] S2: The mixture is spray-dried and granulated to obtain powder.

[0203] S3: After thoroughly mixing the powder and foaming agent at a mass ratio of 10:1, wet the mixture with water and then calcine it. The calcine temperature is controlled at 1100℃ and the calcine time is controlled at 2 hours.

[0204] The preparation method of the foaming agent includes the following steps:

[0205] A1: A mixed aqueous solution of sucrose and silver nitrate is heated to 160°C and the water is evaporated to a syrup-like state; wherein the sucrose reaches a saturation concentration, and the mass concentration of silver ions in the mixed aqueous solution is 1%;

[0206] A2: A mixture of oxygen and carbon dioxide is injected into the syrup under high pressure, with oxygen accounting for 70% of the volume.

[0207] A3: Cool the syrup to room temperature or below within 3 minutes to obtain the coarse material;

[0208] A4: The foaming agent can be obtained by crushing the coarse material to 100μm.

[0209] S4: Rinse the calcined material clean, dry it, and pulverize it to obtain a colorant with a D50 particle size of 0.5μm.

[0210] Example 17

[0211] This embodiment discloses a method for preparing pigments for ceramic inkjet printing, including the following steps:

[0212] S1: Prepare the mixture according to the following ratio: mix 2 mol of tetraethyl orthosilicate, 1.8 mol of zirconium oxychloride, 0.2 mol of nano iron oxide, 7 g of mineralizing agent and 10 L of water; the nano iron oxide is α iron oxide with a particle size of less than 100 nanometers; the mineralizing agent includes lithium fluoride, sodium fluorosilicate and sodium fluoride, and the mass ratio of the three is 1:1:1.

[0213] S2: The mixture is spray-dried and granulated to obtain powder.

[0214] S3: After thoroughly mixing the powder and non-gas-containing foaming agent at a mass ratio of 10:1, wetting them with water, and then calcining them at a temperature of 1100℃ for 2 hours.

[0215] The preparation method of the foaming agent includes the following steps:

[0216] A1: A mixed aqueous solution of sucrose and silver nitrate is heated to 160°C and the water is evaporated to a syrup-like state; wherein the sucrose reaches a saturation concentration, and the mass concentration of silver ions in the mixed aqueous solution is 1%;

[0217] A3: Cool the syrup to room temperature or below within 3 minutes to obtain the coarse material;

[0218] A4: A non-gas-containing foaming agent can be obtained by crushing the coarse material to 100μm.

[0219] S4: Rinse the calcined material clean, dry it, and pulverize it to obtain a colorant with a D50 particle size of 0.5μm.

[0220] Comparative Example

[0221] The difference between Comparative Example 1 and Example 1 is that step S3 involves calcining the powder particles at a temperature of 1100°C for 2 hours.

[0222] Detection methods

[0223] Hair color test

[0224] 1) Accurately weigh 100g of glaze material A (formula: 49 parts by weight of albite, 6.5 parts by weight of limestone, 10.7 parts by weight of wollastonite, 5.5 parts by weight of dolomite, 6.4 parts by weight of zinc oxide, 3.8 parts by weight of alumina, 7 parts by weight of white corundum, 4.5 parts by weight of quartz powder, 4.6 parts by weight of kaolin, and 2 parts by weight of frit), 0.1g of CMC, 0.2g of STPP, 100g of water, and 300g of ball milling stones. Place the ball milling jar in a high-speed ball mill and mill for three minutes to obtain slurry A.

[0225] 2) Take 2.3g of slurry A and spray it evenly onto a 50×50mm green body, then dry it to obtain a glaze.

[0226] 3) Apply 1 ml of a 20% solids content pigment suspension evenly to a 5 cm wide area. 2 The glaze is dried again to obtain the color layer;

[0227] 4) Accurately weigh 100g of glaze material b (formula: 48 parts by weight of potassium feldspar, 32 parts by weight of limestone, 4 parts by weight of alumina, 4 parts by weight of white corundum, 12 parts by weight of kaolin), 0.1g of CMC, 0.2g of STPP, 100g of water, and 300g of pebbles and put them into a clean ball mill jar. Place the ball mill jar into a high-speed ball mill and mill for three minutes to obtain slurry B.

[0228] 5) Take 2.3g of slurry B and spray it evenly on the glaze surface, completely covering the color layer, and then dry it;

[0229] 6) Place the billet at 1210℃ for 10 minutes, remove it and let it cool naturally. Then use a colorimeter to test its color difference. The test results are shown in Table 1 below.

[0230] Table 1

[0231] Example L a b Example 1 53.17 33.32 22.54 Example 2 53.39 33.2 21.56 Example 3 54.62 32.16 22.9 Example 4 53.83 33.97 22.37 Example 5 54.1 33.49 22.65 Example 6 58.48 29.64 24.79 Example 7 56.25 29.06 25.39 Example 8 57.84 29.96 24.83 Example 9 56.23 29.73 25.19 Example 10 57.62 29.25 25.05 Example 11 56.94 29.5 25.32 Example 12 58.92 29.95 24.31 Example 13 57.36 30.61 25.45 Example 14 58.29 29.09 25.71 Example 15 57.38 29.82 25.31 Example 16 55.12 31.45 23.21 Example 17 53.16 33.21 21.41 Comparative Example 1 50.23 34.99 20.14

[0232] Antibacterial stability test

[0233] After color difference testing, a portion of the pigment was scraped from the surface of the samples from Examples 5, 9, 10, and 17, and the antibacterial effect was determined using the inhibition zone method. The bacterial strains used were Staphylococcus aureus and Escherichia coli. The culture medium was nutrient agar, the incubation temperature was 37℃, and the incubation time was 24 hours. The concentration of the prepared bacterial suspension was 2.0 × 10⁻⁶.6 / ml~2.0×10 7 / ml. The diameter of the inhibition zone formed was 18mm~22mm. The sterilization rate test results are shown in Table 2:

[0234] Table 2

[0235] Example Sterilization rate (%) after 6 hours 24-hour sterilization rate (%) 48-hour sterilization rate (%) Example 5 6 7 6 Example 9 99 99 97 Example 10 99 99 98 Example 17 98 97 96

[0236] After color difference testing, a portion of the pigment was scraped from the surface of the samples from Examples 5, 9, 10, and 17 and placed in a location exposed to sunlight for 6 hours daily. After one year, the antibacterial effect was further determined using the inhibition zone method. The bacterial strains used were Staphylococcus aureus and Escherichia coli. The culture medium was nutrient agar, the incubation temperature was 37°C, and the incubation time was 24 hours. The concentration of the prepared bacterial suspension was 2.0 × 10⁻⁶. 6 / ml~2.0×10 7 / ml. The diameter of the formed inhibition zone is 18mm-20mm. The sterilization rate test results for Example 9 are: 94% sterilization rate after 6 hours, 99% after 24 hours, and 99% after 48 hours. The sterilization rate test results for Example 10 are: 96% sterilization rate after 6 hours, 99% after 24 hours, and 99% after 48 hours.

[0237] The sterilization rate test results of Example 16 are shown in Table 3:

[0238] Table 3

[0239] Example Sterilization rate (%) after 6 hours 24-hour sterilization rate (%) 48-hour sterilization rate (%) Example 5 3 4 3 Example 9 96 94 92 Example 10 96 95 93 Example 17 92 91 89

[0240] The above tests show that the colorant prepared by the present invention has better color difference stability and antibacterial stability, and its antibacterial durability is significantly improved.

[0241] The above description is merely a preferred embodiment of the present invention, and the scope of protection of the present invention is not limited to the above embodiments. All technical solutions falling within the scope of the present invention's concept are within the scope of protection of the present invention. It should be noted that for those skilled in the art, any improvements and modifications made without departing from the principle of the present invention should also be considered within the scope of protection of the present invention.

Claims

1. A method for producing a ceramic inkjet printing colorant, characterized by, The method comprises the following steps: S1: preparing a mixed solution in the following proportions: 1.5-2 mol of tetraethyl orthosilicate, 1.4-1.8 mol of zirconium oxychloride, 0.04-0.2 mol of nano iron oxide, 6-7 grams of a mineralizer, and water; S2: spray drying the mixed solution to obtain powder particles; S3: mixing the powder particles obtained in step S2 with a foaming agent in a mass ratio of 6-10:1, and then wetting the mixture with an aqueous ammonium molybdate solution, followed by calcination; The calcination process comprises a first high-temperature stage, a low-temperature stage, and a second high-temperature stage, wherein the temperature of the first high-temperature stage is 900-1100℃, the calcination time accounts for 1 / 4, the temperature of the low-temperature stage is 300-500℃, the calcination time accounts for 1 / 4, and the temperature of the second high-temperature stage is 1200℃, the calcination time accounts for 1 / 2; S4: rinsing the calcined material, drying, and crushing to obtain a colorant with a D50 particle size of 0.5-0.8 μm; The preparation method of the foaming agent comprises the following steps: A1: heating a saturated sucrose aqueous solution to 150-160℃, and then evaporating water to obtain a syrup; A2: high-pressure charging a mixed gas of oxygen and carbon dioxide into the syrup, wherein the volume ratio of oxygen is 40-70%; A3: cooling the syrup to room temperature or below within 1-3 min to obtain a crude material; A4: crushing the crude material to 100-1000 μm to obtain the foaming agent.

2. The method of preparing a ceramic inkjet ink according to claim 1, characterized in that: The nano iron oxide is α-iron oxide with a particle size of less than 100 nm.

3. The method for preparing a ceramic inkjet printing pigment according to claim 1, characterized in that: The mineralizer comprises lithium fluoride, sodium fluorosilicate, and sodium fluoride.

4. The method for preparing a ceramic inkjet printing pigment according to claim 1, characterized in that: The sucrose aqueous solution in step A1 further contains silver ions, and the mass concentration of the silver ions is 0.1-4%.

5. The method for preparing a ceramic inkjet printing pigment according to claim 1, characterized in that: The sucrose aqueous solution in step A1 further contains porous silica particles, and the mass ratio is 0.2-3%.

6. The method for preparing a ceramic inkjet printing pigment according to claim 1, characterized in that: The calcination time in step S3 is 1-3 hours.