Preparation method of pigment for ceramic ink-jet printing

Abstract

The invention discloses a preparation method of a pigment for ceramic ink-jet printing, and relates to the field of ceramic ink-jet pigments, and the preparation method comprises the following steps: S1, preparing a mixed solution according to the following proportion: preparing the mixed solution from 1.5-2 mol of tetraethoxysilane, 1.4-1.8 mol of zirconium oxychloride, 0.04-0.2 mol of nano iron oxide, 6-7 g of a mineralizer and water; s2, the mixed solution is subjected to spray drying granulation, and powder particles are obtained; s3, the powder particles and a foaming agent are fully mixed according to the mass ratio of (6-10): 1 and then calcined; and S4, rinsing the calcined material, drying, and crushing to obtain the pigment with the D50 particle size of 0.5-0.8 [mu] m. The preparation method disclosed by the invention has the advantages of improving the color development stability, antibacterial stability and durability of the pigment.

Description

Technical Field

[0001] The invention relates to the technical field of ceramic inkjet colorants, and in particular to a method for preparing a colorant for ceramic inkjet printing. Background Art

[0002] Under the guidance and selection of the market, building ceramic companies will inevitably shift from single cost competition to competition centered on product patterns, specifications, and technological innovation.

[0003] As a new concept of ceramic decoration, color inkjet printing technology for ceramic decoration makes full use of abundant computer resources and introduces digital technology into traditional architectural ceramic enterprises, so that ceramic decoration can keep pace with the times, reflect fashion characteristics, meet people's personalized needs, and push ceramic decoration technology to a new stage.

[0004] Inkjet printing technology is a non-contact digital printing technology successfully developed in the late 1970s. It sprays ink onto the surface of various media through the nozzle on the print head to achieve non-contact, high-speed, low-noise monochrome and color text and image printing. On this basis, the ceramic pigment powder is prepared into ink, and through computer control, a special printer can be used to print the configured ink directly onto the surface of architectural ceramics for decoration. Compared with existing decoration methods, inkjet printing has the following advantages: First, it saves energy and reduces emissions. The product gets rid of the intermediate processes such as film making, screen drying, and plate engraving required by traditional decoration methods in large-scale production, shortens the production cycle, and greatly improves the yield rate; second, the printing process is completely controlled by a computer, and complex patterns can be decorated. The pattern has high accuracy and repeatability, which greatly improves the mechanization degree and production efficiency of the decoration process; finally, non-contact decoration can be directly decorated on concave and convex surfaces.

[0005] However, the ceramic pigments used in current inkjet printing technology still have problems such as poor stability and color difference. In addition, there is little research on functional ceramic pigments with antibacterial ability, and it is common to directly add antibacterial agents to the ink components after compounding with pigments, and the antibacterial durability and stability are also poor. Summary of the invention

[0006] In view of the shortcomings of the prior art, the object of the present invention is to provide a colorant for ceramic inkjet printing and a preparation method thereof.

[0007] The above object of the present invention is achieved through the following technical solutions:

[0008] A method for preparing a colorant for ceramic inkjet printing comprises the following steps:

[0009] S1: Prepare a mixed solution in the following proportions: 1.5-2 mol of ethyl 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;

[0010] S2: granulating the mixed solution by spray drying to obtain powder particles;

[0011] S3: fully mixing the powder particles and the foaming agent in a mass ratio of 6 to 10:1 and calcining;

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

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

[0014] Furthermore, the mineralizer includes lithium fluoride, sodium fluorosilicate, and sodium fluoride.

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

[0016] A1: Heat the saturated sucrose aqueous solution to 150-160°C and evaporate the water to a syrupy state;

[0017] A2: A mixed gas of oxygen and carbon dioxide is injected into the syrup under high pressure, wherein the volume proportion of oxygen is 40-70%;

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

[0019] A4: The coarse material can be crushed into 100-1000 μm to obtain the foaming agent.

[0020] The present application selects a conventional formula of zirconium iron red material to prepare a mixed liquid, and on the basis of conventional granulation, calcination, drying and other steps, a simple step of adding a specific foaming agent powder and calcining together greatly improves the stability of the prepared colorant. The present invention adopts a method of first mixing the foaming agent and the powder and then calcining to improve the calcination uniformity of the powder during the calcination process. The foaming agent will release the gas in the foaming agent during the calcination process. On the one hand, this part of the gas can adjust the powder during the calcination process. Through the impact of the gas release, each particle of the powder can be calcined more uniformly under the impact of the gas; on the other hand, the gas in the foaming agent in the present invention contains oxygen components, which can help the powder to have a higher oxygen content at the powder during the calcination process, thereby making the color of the obtained zirconium iron red pigment more stable. The main reason is that the color development of zirconium iron red mainly depends on the reaction of quartz and zirconium dioxide in an oxidizing atmosphere during the high-temperature calcination process to convert Fe 3+It is coated therein to form a material with a zirconium silicate crystal structure, and the foaming agent releases gas impact and oxygen to make 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, thereby obtaining a more stable ferrozirconium red color.

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

[0022] After the powder particles and the foaming agent are fully mixed, they are first moistened with water, which can allow part of the foaming agent to dissolve first and produce oxygen, and part of the oxygen is released into the gaps inside the powder before calcination. Then calcination is carried out so that the oxygen content in various parts of the calcined powder is at a high level at the beginning. Then, under the high temperature of calcination, the sucrose is completely burned and decomposed into carbon dioxide and water vapor, and the internal oxygen is released, so that the oxygen content in each part of the powder is replenished, effectively improving the calcination effect. Secondly, pre-wetting allows part of the foaming agent to release some oxygen, which can avoid excessive carbon dioxide produced by the decomposition of sucrose during high-temperature calcination, which dilutes the oxygen content around the calcined powder, so that oxygen always dominates the gaps in the powder, thereby effectively improving the effect of the foaming agent. Secondly, the molybdate components in ammonium molybdate will be deposited in the powder with the penetration effect, and the oxygen produced by the partial decomposition of the foaming agent allows the molybdate components to penetrate deeper into the powder. The molybdate groups help Fe 3+ of packaging to make the color of the calcined ferrozirconium red material more stable.

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

[0024] The silver ion component added to the foaming agent of the present invention has good antibacterial effect on the one hand, and can effectively improve the antibacterial property of the colorant; on the other hand, the silver ions can diffuse into various gaps of the colorant through the impact of the gas generated in the foaming agent during the calcination process with the powder, and as the calcination process continues, part of the silver ions will also combine with the colorant, thereby improving the dispersion uniformity and adhesion stability of the silver ions in the colorant.

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

[0026] The present invention further adds porous silica particles to the foaming agent, and the porous silica particles have a porous structure. The porous silica can store more pores through the porous structure to accommodate more gas, thereby improving the gas release capacity and release amount of the foaming agent. On the other hand, the porous structure of the porous silica particles can also adsorb part of the silver ions, and the stability of the silver ions in the porous structure of the porous silica is higher, thereby further improving the antibacterial stability of the colorant.

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

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

[0029] By means of staged calcination and control of different high and low temperatures, the calcination effects of the foaming agent and the colorant are improved during the calcination process, and the mutual promotion effect is more obvious.

[0030] Furthermore, the D50 particle size of the powder after calcination in step S4 is 0.5 to 0.8 μm.

[0031] Compared with the prior art, the present invention has the following beneficial effects:

[0032] The key to the present invention lies in the use of a foaming agent. The foaming agent releases gas during the calcination process. On the one hand, these gases cause the powder particles to be calcined uniformly through impact, and on the other hand, they provide oxygen, which helps to increase the oxygen content at the powder during the calcination process, thereby making the color of the obtained ferrozirconium red pigment more stable. Secondly, by adding silver ions to the sucrose aqueous solution, the antibacterial property and uniformity of silver ion dispersion of the colorant are improved; porous silica particles are added to improve the gas release capacity and antibacterial stability. Before calcination, the powder particles and the foaming agent mixture are first moistened so that the oxygen content at each location in the calcined powder is at a high state at the beginning, thereby increasing the oxygen release amount and preventing color difference. The calcination time is 1 to 3 hours, and the process is divided into a first high temperature section of 900 to 1100°C, a low temperature section of 300 to 500°C, and a second high temperature section of 1200°C. The calcination effect is improved by segmentation and temperature control. The final powder D50 particle size is 0.5 to 0.8 μm. The method improves the uniformity of colorant calcination and the performance of the final product. DETAILED DESCRIPTION

[0033] The present invention is described in detail below in conjunction with embodiments.

[0034] Example 1

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

[0036] S1: A mixed solution is prepared in the following proportions: 1.5 mol of tetraethyl orthosilicate, 1.4 mol of zirconium oxychloride, 0.04 mol of nano-iron oxide, 6 g of a mineralizer and 10 L of water; the nano-iron oxide is α-iron oxide with a particle size of less than 100 nanometers; the mineralizer includes lithium fluoride, sodium fluorosilicate and sodium fluoride, and the mass ratio of the three is 1:1:1.

[0037] S2: The mixed solution is granulated by spray drying to obtain powder particles.

[0038] S3: The powder particles and the foaming agent are fully mixed in a mass ratio of 6:1 and then calcined. The calcination temperature is controlled to be 1100° C. and the calcination time is controlled to be 2 hours.

[0039] Wherein, the preparation method of the foaming agent comprises the following steps:

[0040] A1: Heat the saturated sucrose aqueous solution to 160°C and evaporate the water to a syrupy state;

[0041] A2: A mixed gas of oxygen and carbon dioxide is injected into the syrup under high pressure, wherein the volume proportion of oxygen is 40%;

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

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

[0044] S4: The calcined material is rinsed, dried and crushed to obtain a colorant with a D50 particle size of 0.5 μm.

[0045] Example 2

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

[0047] S1: A mixed solution is prepared in the following proportions: 2 mol of tetraethyl orthosilicate, 1.8 mol of zirconium oxychloride, 0.2 mol of nano-iron oxide, 7 g of a mineralizer and 10 L of water; the nano-iron oxide is α-iron oxide with a particle size of less than 100 nanometers; the mineralizer includes lithium fluoride, sodium fluorosilicate and sodium fluoride, and the mass ratio of the three is 1:1:1.

[0048] S2: The mixed solution is granulated by spray drying to obtain powder particles.

[0049] S3: The powder particles and the foaming agent are fully mixed in a mass ratio of 8:1 and then calcined. The calcination temperature is controlled to be 1100° C. and the calcination time is controlled to be 2 hours.

[0050] Wherein, the preparation method of the foaming agent comprises the following steps:

[0051] A1: Heat the saturated sucrose aqueous solution to 150°C and evaporate the water to a syrupy state;

[0052] A2: A mixed gas of oxygen and carbon dioxide is injected into the syrup under high pressure, wherein the volume proportion of oxygen is 60%;

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

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

[0055] S4: The calcined material is rinsed, dried and crushed to obtain a colorant with a D50 particle size of 0.8 μm.

[0056] Example 3

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

[0058] S1: A mixed solution is prepared in the following proportions: 1.7 mol of tetraethyl orthosilicate, 1.6 mol of zirconium oxychloride, 0.1 mol of nano-iron oxide, 6 g of a mineralizer and 10 L of water; the nano-iron oxide is α-iron oxide with a particle size of less than 100 nanometers; the mineralizer includes lithium fluoride, sodium fluorosilicate and sodium fluoride, and the mass ratio of the three is 1:1:1.

[0059] S2: The mixed solution is granulated by spray drying to obtain powder particles.

[0060] S3: The powder particles and the foaming agent are fully mixed in a mass ratio of 8:1 and then calcined. The calcination temperature is controlled to be 1100° C. and the calcination time is controlled to be 2 hours.

[0061] Wherein, the preparation method of the foaming agent comprises the following steps:

[0062] A1: Heat the saturated sucrose aqueous solution to 150°C and evaporate the water to a syrupy state;

[0063] A2: A mixed gas of oxygen and carbon dioxide is injected into the syrup under high pressure, wherein the volume proportion of oxygen is 60%;

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

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

[0066] S4: The calcined material is rinsed, dried and crushed to obtain a colorant with a D50 particle size of 0.7 μm.

[0067] Example 4

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

[0069] S1: A mixed solution is prepared in the following proportions: 1.5 mol of tetraethyl orthosilicate, 1.4 mol of zirconium oxychloride, 0.2 mol of nano-iron oxide, 6 g of a mineralizer and 10 L of water; the nano-iron oxide is α-iron oxide with a particle size of less than 100 nanometers; the mineralizer includes lithium fluoride, sodium fluorosilicate and sodium fluoride, and the mass ratio of the three is 1:1:1.

[0070] S2: The mixed solution is granulated by spray drying to obtain powder particles.

[0071] S3: The powder particles and the foaming agent are fully mixed in a mass ratio of 6:1 and then calcined. The calcination temperature is controlled to be 1100° C. and the calcination time is controlled to be 2 hours.

[0072] Wherein, the preparation method of the foaming agent comprises the following steps:

[0073] A1: Heat the saturated sucrose aqueous solution to 150°C and evaporate the water to a syrupy state;

[0074] A2: A mixed gas of oxygen and carbon dioxide is injected into the syrup under high pressure, wherein the volume proportion of oxygen is 60%;

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

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

[0077] S4: The calcined material is rinsed, dried and crushed to obtain a colorant with a D50 particle size of 0.6 μm.

[0078] Example 5

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

[0080] S1: A mixed solution is prepared in the following proportions: 2 mol of tetraethyl orthosilicate, 1.8 mol of zirconium oxychloride, 0.2 mol of nano-iron oxide, 7 g of a mineralizer and 10 L of water; the nano-iron oxide is α-iron oxide with a particle size of less than 100 nanometers; the mineralizer includes lithium fluoride, sodium fluorosilicate and sodium fluoride, and the mass ratio of the three is 1:1:1.

[0081] S2: The mixed solution is granulated by spray drying to obtain powder particles.

[0082] S3: The powder particles and the foaming agent are fully mixed in a mass ratio of 10:1 and then calcined. The calcination temperature is controlled to be 1100° C. and the calcination time is controlled to be 2 hours.

[0083] Wherein, the preparation method of the foaming agent comprises the following steps:

[0084] A1: Heat the saturated sucrose aqueous solution to 160°C and evaporate the water to a syrupy state;

[0085] A2: A mixed gas of oxygen and carbon dioxide is injected into the syrup under high pressure, wherein the volume proportion of oxygen is 70%;

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

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

[0088] S4: The calcined material is rinsed, dried and crushed to obtain a colorant with a D50 particle size of 0.5 μm.

[0089] Example 6

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

[0091] S1: A mixed solution is prepared in the following proportions: 2 mol of tetraethyl orthosilicate, 1.8 mol of zirconium oxychloride, 0.2 mol of nano-iron oxide, 7 g of a mineralizer and 10 L of water; the nano-iron oxide is α-iron oxide with a particle size of less than 100 nanometers; the mineralizer includes lithium fluoride, sodium fluorosilicate and sodium fluoride, and the mass ratio of the three is 1:1:1.

[0092] S2: The mixed solution is granulated by spray drying to obtain powder particles.

[0093] S3: The powder particles and the foaming agent are fully mixed in a mass ratio of 10:1, and then moistened with 1% mass concentration of ammonium molybdate water and calcined. The calcination temperature is controlled at 1100° C. and the calcination time is controlled at 2 hours.

[0094] Wherein, the preparation method of the foaming agent comprises the following steps:

[0095] A1: Heat the saturated sucrose aqueous solution to 160°C and evaporate the water to a syrupy state;

[0096] A2: A mixed gas of oxygen and carbon dioxide is injected into the syrup under high pressure, wherein the volume proportion of oxygen is 70%;

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

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

[0099] S4: The calcined material is rinsed, dried and crushed to obtain a colorant with a D50 particle size of 0.5 μm.

[0100] Example 7

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

[0102] S1: A mixed solution is prepared in the following proportions: 2 mol of tetraethyl orthosilicate, 1.8 mol of zirconium oxychloride, 0.2 mol of nano-iron oxide, 7 g of a mineralizer and 10 L of water; the nano-iron oxide is α-iron oxide with a particle size of less than 100 nanometers; the mineralizer includes lithium fluoride, sodium fluorosilicate and sodium fluoride, and the mass ratio of the three is 1:1:1.

[0103] S2: The mixed solution is granulated by spray drying to obtain powder particles.

[0104] S3: The powder particles and the foaming agent are fully mixed in a mass ratio of 10:1, and then moistened with 1% mass concentration of ammonium molybdate water and calcined. The calcination temperature is controlled at 1100° C. and the calcination time is controlled at 2 hours.

[0105] Wherein, the preparation method of the foaming agent comprises the following steps:

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

[0107] A2: A mixed gas of oxygen and carbon dioxide is injected into the syrup under high pressure, wherein the volume proportion of oxygen is 70%;

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

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

[0110] S4: The calcined material is rinsed, dried and crushed to obtain a colorant with a D50 particle size of 0.5 μm.

[0111] Example 8

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

[0113] S1: A mixed solution is prepared in the following proportions: 2 mol of tetraethyl orthosilicate, 1.8 mol of zirconium oxychloride, 0.2 mol of nano-iron oxide, 7 g of a mineralizer and 10 L of water; the nano-iron oxide is α-iron oxide with a particle size of less than 100 nanometers; the mineralizer includes lithium fluoride, sodium fluorosilicate and sodium fluoride, and the mass ratio of the three is 1:1:1.

[0114] S2: The mixed solution is granulated by spray drying to obtain powder particles.

[0115] S3: The powder particles and the foaming agent are fully mixed in a mass ratio of 10:1, and then moistened with 1% mass concentration of ammonium molybdate water and calcined. The calcination temperature is controlled at 1100° C. and the calcination time is controlled at 2 hours.

[0116] Wherein, the preparation method of the foaming agent comprises the following steps:

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

[0118] A2: A mixed gas of oxygen and carbon dioxide is injected into the syrup under high pressure, wherein the volume proportion of oxygen is 70%;

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

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

[0121] S4: The calcined material is rinsed, dried and crushed to obtain a colorant with a D50 particle size of 0.5 μm.

[0122] Example 9

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

[0124] S1: A mixed solution is prepared in the following proportions: 2 mol of tetraethyl orthosilicate, 1.8 mol of zirconium oxychloride, 0.2 mol of nano-iron oxide, 7 g of a mineralizer and 10 L of water; the nano-iron oxide is α-iron oxide with a particle size of less than 100 nanometers; the mineralizer includes lithium fluoride, sodium fluorosilicate and sodium fluoride, and the mass ratio of the three is 1:1:1.

[0125] S2: The mixed solution is granulated by spray drying to obtain powder particles.

[0126] S3: The powder particles and the foaming agent are fully mixed in a mass ratio of 10:1, and then moistened with 1% mass concentration of ammonium molybdate water and calcined. The calcination temperature is controlled at 1100° C. and the calcination time is controlled at 2 hours.

[0127] Wherein, the preparation method of the foaming agent comprises the following steps:

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

[0129] A2: A mixed gas of oxygen and carbon dioxide is injected into the syrup under high pressure, wherein the volume proportion of oxygen is 70%;

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

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

[0132] S4: The calcined material is rinsed, dried and crushed to obtain a colorant with a D50 particle size of 0.5 μm.

[0133] Example 10

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

[0135] S1: A mixed solution is prepared in the following proportions: 2 mol of tetraethyl orthosilicate, 1.8 mol of zirconium oxychloride, 0.2 mol of nano-iron oxide, 7 g of a mineralizer and 10 L of water; the nano-iron oxide is α-iron oxide with a particle size of less than 100 nanometers; the mineralizer includes lithium fluoride, sodium fluorosilicate and sodium fluoride, and the mass ratio of the three is 1:1:1.

[0136] S2: The mixed solution is granulated by spray drying to obtain powder particles.

[0137] S3: The powder particles and the foaming agent are fully mixed in a mass ratio of 10:1, and then moistened with 1% mass concentration of ammonium molybdate water and calcined. The calcination temperature is controlled at 1100° C. and the calcination time is controlled at 2 hours.

[0138] Wherein, the preparation method of the foaming agent comprises the following steps:

[0139] A1: A mixed aqueous solution of sucrose, silver nitrate and porous silica is heated to 160°C and then the water is evaporated to a syrupy 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 mixed gas of oxygen and carbon dioxide is injected into the syrup under high pressure, wherein the volume proportion of oxygen is 70%;

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

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

[0143] S4: The calcined material is rinsed, dried and crushed to obtain a colorant with a D50 particle size of 0.5 μm.

[0144] Embodiment 11

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

[0146] S1: A mixed solution is prepared in the following proportions: 2 mol of tetraethyl orthosilicate, 1.8 mol of zirconium oxychloride, 0.2 mol of nano-iron oxide, 7 g of a mineralizer and 10 L of water; the nano-iron oxide is α-iron oxide with a particle size of less than 100 nanometers; the mineralizer includes lithium fluoride, sodium fluorosilicate and sodium fluoride, and the mass ratio of the three is 1:1:1.

[0147] S2: The mixed solution is granulated by spray drying to obtain powder particles.

[0148] S3: The powder particles and the foaming agent are fully mixed in a mass ratio of 10:1, and then moistened with 1% mass concentration of ammonium molybdate water and calcined. The calcination temperature is controlled at 1100° C. and the calcination time is controlled at 3 hours.

[0149] Wherein, the preparation method of the foaming agent comprises the following steps:

[0150] A1: A mixed aqueous solution of sucrose, silver nitrate and porous silica is heated to 160°C and then the water is evaporated to a syrupy 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 mixed gas of oxygen and carbon dioxide is injected into the syrup under high pressure, wherein the volume proportion of oxygen is 70%;

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

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

[0154] S4: The calcined material is rinsed, dried and crushed to obtain a colorant with a D50 particle size of 0.5 μm.

[0155] Example 12

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

[0157] S1: A mixed solution is prepared in the following proportions: 2 mol of tetraethyl orthosilicate, 1.8 mol of zirconium oxychloride, 0.2 mol of nano-iron oxide, 7 g of a mineralizer and 10 L of water; the nano-iron oxide is α-iron oxide with a particle size of less than 100 nanometers; the mineralizer includes lithium fluoride, sodium fluorosilicate and sodium fluoride, and the mass ratio of the three is 1:1:1.

[0158] S2: The mixed solution is granulated by spray drying to obtain powder particles.

[0159] S3: The powder particles and the foaming agent are fully mixed in a mass ratio of 10:1, and then moistened with 1% mass concentration of ammonium molybdate water and calcined. The calcination temperature is controlled at 1100° C. and the calcination time is controlled at 3 hours.

[0160] Wherein, the preparation method of the foaming agent comprises the following steps:

[0161] A1: Heat a mixed aqueous solution of sucrose, silver nitrate and porous silica to 160°C and evaporate the water to a syrupy 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 0.2%, and the D50 particle size of the porous silica particles is 500nm.

[0162] A2: A mixed gas of oxygen and carbon dioxide is injected into the syrup under high pressure, wherein the volume proportion of oxygen is 70%;

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

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

[0165] S4: The calcined material is rinsed, dried and crushed to obtain a colorant with a D50 particle size of 0.5 μm.

[0166] Embodiment 13

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

[0168] S1: A mixed solution is prepared in the following proportions: 2 mol of tetraethyl orthosilicate, 1.8 mol of zirconium oxychloride, 0.2 mol of nano-iron oxide, 7 g of a mineralizer and 10 L of water; the nano-iron oxide is α-iron oxide with a particle size of less than 100 nanometers; the mineralizer includes lithium fluoride, sodium fluorosilicate and sodium fluoride, and the mass ratio of the three is 1:1:1.

[0169] S2: The mixed solution is granulated by spray drying to obtain powder particles.

[0170] S3: The powder particles and the foaming agent are fully mixed in a mass ratio of 10:1, and then moistened with 1% mass concentration of ammonium molybdate water and calcined. The calcination process 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 1000°C and the calcination time accounts for 1 / 4, the temperature of the low temperature section is 500°C and the calcination time accounts for 1 / 4, and the temperature of the second high temperature section is 1200°C and the calcination time accounts for 1 / 2.

[0171] Wherein, the preparation method of the foaming agent comprises the following steps:

[0172] A1: A mixed aqueous solution of sucrose, silver nitrate and porous silica is heated to 160°C and then the water is evaporated to a syrupy 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 mixed gas of oxygen and carbon dioxide is injected into the syrup under high pressure, wherein the volume proportion of oxygen is 70%;

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

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

[0176] S4: The calcined material is rinsed, dried and crushed to obtain a colorant with a D50 particle size of 0.5 μm.

[0177] Embodiment 14

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

[0179] S1: A mixed solution is prepared in the following proportions: 2 mol of tetraethyl orthosilicate, 1.8 mol of zirconium oxychloride, 0.2 mol of nano-iron oxide, 7 g of a mineralizer and 10 L of water; the nano-iron oxide is α-iron oxide with a particle size of less than 100 nanometers; the mineralizer includes lithium fluoride, sodium fluorosilicate and sodium fluoride, and the mass ratio of the three is 1:1:1.

[0180] S2: The mixed solution is granulated by spray drying to obtain powder particles.

[0181] S3: The powder particles and the foaming agent are fully mixed in a mass ratio of 10:1, and then moistened with 1% mass concentration of ammonium molybdate water and calcined. The calcination process 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 1100°C, and the calcination time accounts for 1 / 4. The temperature of the low temperature section is 300°C, and the calcination time accounts for 1 / 4. The temperature of the second high temperature section is 1200°C, and the calcination time accounts for 1 / 2.

[0182] Wherein, the preparation method of the foaming agent comprises the following steps:

[0183] A1: A mixed aqueous solution of sucrose, silver nitrate and porous silica is heated to 160°C and then the water is evaporated to a syrupy 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 mixed gas of oxygen and carbon dioxide is injected into the syrup under high pressure, wherein the volume proportion of oxygen is 70%;

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

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

[0187] S4: The calcined material is rinsed, dried and crushed to obtain a colorant with a D50 particle size of 0.5 μm.

[0188] Embodiment 15

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

[0190] S1: A mixed solution is prepared in the following proportions: 2 mol of tetraethyl orthosilicate, 1.8 mol of zirconium oxychloride, 0.2 mol of nano-iron oxide, 7 g of a mineralizer and 10 L of water; the nano-iron oxide is α-iron oxide with a particle size of less than 100 nanometers; the mineralizer includes lithium fluoride, sodium fluorosilicate and sodium fluoride, and the mass ratio of the three is 1:1:1.

[0191] S2: The mixed solution is granulated by spray drying to obtain powder particles.

[0192] S3: The powder particles and the foaming agent are fully mixed in a mass ratio of 10:1, and then moistened with 1% mass concentration of ammonium molybdate water and calcined. The calcination process 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°C and the calcination time accounts for 1 / 4, the temperature of the low temperature section is 400°C and the calcination time accounts for 1 / 4, and the temperature of the second high temperature section is 1200°C and the calcination time accounts for 1 / 2.

[0193] Wherein, the preparation method of the foaming agent comprises the following steps:

[0194] A1: A mixed aqueous solution of sucrose, silver nitrate and porous silica is heated to 160°C and then the water is evaporated to a syrupy 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 mixed gas of oxygen and carbon dioxide is injected into the syrup under high pressure, wherein the volume proportion of oxygen is 70%;

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

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

[0198] S4: The calcined material is rinsed, dried and crushed to obtain a colorant with a D50 particle size of 0.5 μm.

[0199] Example 16

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

[0201] S1: A mixed solution is prepared in the following proportions: 2 mol of tetraethyl orthosilicate, 1.8 mol of zirconium oxychloride, 0.2 mol of nano-iron oxide, 7 g of a mineralizer and 10 L of water; the nano-iron oxide is α-iron oxide with a particle size of less than 100 nanometers; the mineralizer includes lithium fluoride, sodium fluorosilicate and sodium fluoride, and the mass ratio of the three is 1:1:1.

[0202] S2: The mixed solution is granulated by spray drying to obtain powder particles.

[0203] S3: The powder particles and the foaming agent are fully mixed in a mass ratio of 10:1, moistened with water, and then calcined. The calcination temperature is controlled at 1100° C. and the calcination time is controlled at 2 hours.

[0204] Wherein, the preparation method of the foaming agent comprises the following steps:

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

[0206] A2: A mixed gas of oxygen and carbon dioxide is injected into the syrup under high pressure, wherein the volume proportion of oxygen is 70%;

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

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

[0209] S4: The calcined material is rinsed, dried and crushed to obtain a colorant with a D50 particle size of 0.5 μm.

[0210] Embodiment 17

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

[0212] S1: A mixed solution is prepared in the following proportions: 2 mol of tetraethyl orthosilicate, 1.8 mol of zirconium oxychloride, 0.2 mol of nano-iron oxide, 7 g of a mineralizer and 10 L of water; the nano-iron oxide is α-iron oxide with a particle size of less than 100 nanometers; the mineralizer includes lithium fluoride, sodium fluorosilicate and sodium fluoride, and the mass ratio of the three is 1:1:1.

[0213] S2: The mixed solution is granulated by spray drying to obtain powder particles.

[0214] S3: The powder particles and the foaming agent without gas are fully mixed in a mass ratio of 10:1, moistened with water, and then calcined. The calcination temperature is controlled at 1100° C. and the calcination time is controlled at 2 hours.

[0215] Wherein, the preparation method of the foaming agent comprises the following steps:

[0216] A1: A mixed aqueous solution of sucrose and silver nitrate is heated to 160°C and then the water is evaporated to a syrupy state; wherein the sucrose reaches a saturated 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 a crude material;

[0218] A4: Grind the coarse material to 100 μm to obtain a gas-free foaming agent.

[0219] S4: The calcined material is rinsed, dried and crushed to obtain a colorant with a D50 particle size of 0.5 μm.

[0220] Comparative Example

[0221] The difference between Comparative Example 1 and Example 1 is that step S3 is to calcine the powder particles, the calcination temperature is controlled to be 1100° C., and the calcination time is controlled to be 2 hours.

[0222] Detection Methods

[0223] Hair color test

[0224] 1) Accurately weigh 100 g of glaze 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 aluminum oxide, 7 parts by weight of white corundum, 4.5 parts by weight of quartz powder, 4.6 parts by weight of kaolin, 2 parts by weight of frit), 0.1 g of CMC, 0.2 g of STPP, 100 g of water, and 300 g of ball stone, and put them into a clean ball mill, and then put the ball mill into a fast ball mill for three minutes to obtain slurry A;

[0225] 2) Take 2.3g of slurry A and spray it evenly on a 50×50mm green body, dry it, and obtain a glaze surface;

[0226] 3) Apply 1 ml of a 20% solid content pigment water suspension evenly on a 5 cm 2 On the glaze, dry again to obtain the color-producing layer;

[0227] 4) Accurately weigh 100 g of glaze 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), 0.1 g of CMC, 0.2 g of STPP, 100 g of water, and 300 g of ball stone, and put them into a clean ball mill, and then put the ball mill into a fast ball mill for three minutes to obtain slurry B;

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

[0229] 6) The green body was placed at 1210°C and kept at a constant temperature for 10 minutes. After being taken out and naturally cooled, the color difference was detected using a colorimeter. The detection 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 Embodiment 11 56.94 29.5 25.32 Example 12 58.92 29.95 24.31 Embodiment 13 57.36 30.61 25.45 Embodiment 14 58.29 29.09 25.71 Embodiment 15 57.38 29.82 25.31 Example 16 55.12 31.45 23.21 Embodiment 17 53.16 33.21 21.41 Comparative Example 1 50.23 34.99 20.14

[0232] Antimicrobial stability test

[0233] Part of the pigment was scraped from the sample surface after the color difference test of Examples 5, 9, 10, and 17, and the antibacterial effect was determined by the inhibition zone method. The bacterial species used were Staphylococcus aureus and Escherichia coli, the culture medium was nutrient agar, the culture temperature was 37°C, the culture time was 24h, and the concentration of the prepared bacterial suspension was 2.0×106 / ml~2.0×10 7 / ml. The diameter of the inhibition zone formed is 18mm~22mm. The sterilization rate test results are shown in Table 2:

[0234] Table 2

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

[0236] Part of the pigment was scraped from the surface of the samples after the color difference test in Examples 5, 9, 10, and 17 and placed in a location where the sun was shining for 6 hours every day. After 1 year of storage, the antibacterial effect was determined by the inhibition zone method. The bacterial species used were Staphylococcus aureus and Escherichia coli, the culture medium was nutrient agar, the culture temperature was 37°C, the culture time was 24h, and the concentration of the prepared bacterial suspension was 2.0×10 6 / ml~2.0×10 7 / ml. The diameter of the inhibition zone formed is 18mm-20mm. The sterilization rate test results of Example 9 are: 94% in 6 hours, 99% in 24 hours, and 99% in 48 hours. The sterilization rate test results of Example 10 are: 96% in 6 hours, 99% in 24 hours, and 99% in 48 hours.

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

[0238] Table 3

[0239] Example 6-hour sterilization rate (%) 24-hour sterilization rate (%) 48-hour sterilization rate (%) Example 5 3 4 3 Example 9 96 94 92 Example 10 96 95 93 Embodiment 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 is only a preferred embodiment of the present invention, and the protection scope of the present invention is not limited to the above embodiments. All technical solutions under the concept of the present invention belong to the protection scope of the present invention. It should be pointed out that for ordinary technicians in this technical field, some improvements and modifications without departing from the principle of the present invention should also be regarded as the protection scope of the present invention.

Claims

1. A method for preparing a colorant for ceramic inkjet printing, characterized in that: The following steps are involved: S1: Prepare a mixed solution in the following proportions: 1.5-2 mol of ethyl 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 mixed solution by spray drying to obtain powder particles; S3: fully mixing the powder particles and the foaming agent in a mass ratio of 6 to 10:1 and calcining; S4: The calcined material is rinsed, dried and crushed to obtain a colorant with a D50 particle size of 0.5 to 0.8 μm.

2. The method for preparing a ceramic inkjet printing colorant according to claim 1, characterized in that: Nano-iron oxide is alpha-iron oxide with a particle size less than 100 nanometers.

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

4. The method for preparing a ceramic inkjet printing colorant according to claim 1, characterized in that: The preparation method of the foaming agent comprises the following steps: A1: Heat the saturated sucrose aqueous solution to 150-160°C and evaporate the water to a syrupy state; A2: A mixed gas of oxygen and carbon dioxide is injected into the syrup under high pressure, wherein the volume proportion of oxygen is 40-70%; A3: Cool the syrup to room temperature or below within 1 to 3 minutes to obtain a crude material; A4: The coarse material can be crushed into 100-1000 μm to obtain the foaming agent.

5. The method for preparing a ceramic inkjet printing colorant according to claim 4, characterized in that: In the step S3, after the powder particles and the foaming agent are fully mixed, they are first moistened with 1% by mass concentration of ammonium molybdate water and then calcined.

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

7. The method for preparing a ceramic inkjet printing colorant according to claim 4, characterized in that: In the step A1, the sucrose aqueous solution also contains porous silica particles, accounting for 0.2-3% by weight.

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

9. The method for preparing a ceramic inkjet printing colorant according to claim 8, characterized in that: The calcination process in the S3 step includes a first high temperature section, a low temperature section and a second high temperature section, wherein the temperature of the first high temperature section is 900-1100°C, and the calcination time accounts for 1 / 4, the temperature of the low temperature section is 300-500°C, and the calcination time accounts for 1 / 4, and the temperature of the second high temperature section is 1200°C, and the calcination time accounts for 1 / 2.