A water-based ceramic glaze ink, its preparation method and application

Abstract

This invention discloses an aqueous ceramic glaze ink, its preparation method, and its application, relating to the field of ceramic printing technology. The invention uses lithium magnesium silicate as an inorganic rheology modifier; its three-dimensional network structure effectively blocks and supports solid particles and regulates the ink's shear-thinning properties. Compared to natural layered silicates, lithium magnesium silicate has higher purity, more stable performance, stronger resistance to high-valence ions, and controllable thixotropy. Sodium tripolyphosphate is added to the base glaze to chelate calcium ions, reducing damage to the lithium magnesium silicate structure. Sodium hexametaphosphate is added to enhance dispersion and chelation, water glass provides an alkaline environment to stabilize the structure, and sodium carboxymethyl cellulose is used for thickening and stabilization. By first preparing a lithium magnesium silicate solution and then compounding it with the base glaze, electrolyte shock is reduced, and system stability is improved.

Description

Technical Field

[0001] This invention relates to the field of ceramic printing technology, and more specifically, to a water-based ceramic glaze ink, its preparation method, and its application. Background Technology

[0002] Glaze is an important carrier for the functional use and decorative expression of ceramic tiles. Applying glaze in the form of ink and printing three-dimensional textures on the body or water-based glaze surface through inkjet printing can better meet the personalized market demand and flexible and efficient production needs compared to the traditional glaze application methods of spraying.

[0003] Oil-based ceramic inks are relatively mature, primarily using pigments with less glaze. They suffer from low solids content, low ink volume, difficulty in creating three-dimensional textures, high manufacturing costs due to their high organic solvent content, poor environmental performance, and difficulty in quickly evaporating and reducing moisture content before firing, leading to quality problems such as glaze curling and brick cracking, thus reducing the yield of high-quality products and limiting the application range of glaze inkjet printing. Water-based glaze inks, on the other hand, use water as a solvent, allowing for natural bonding after printing on the ceramic body or water-based glaze surface. They produce a dust-free printing environment, have low glaze loss, precise ink volume control, and offer diverse three-dimensional texture effects. With the development of ceramic inkjet equipment, high-volume water-based glaze ink printing technology represents a better direction for inkjet printing combined with glazes.

[0004] In recent years, there has been considerable research on water-based glaze inks, primarily focusing on ink dispersion stability. However, research on the impact of ink viscosity and flow rate on printed textures is scarce. In printing, excessively low viscosity coupled with excessively high flow rates and slow curing leads to disordered ink flow on the substrate surface under high ink volume, making it difficult to form clear, three-dimensional textures. Conversely, excessively high ink viscosity causes jetting difficulties, printhead clogging, shortened lifespan, insufficient ink supply, and inaccurate positioning. Therefore, inks need to have low viscosity upon ejection and weak flowability on the substrate surface. Achieving a balance between dispersion stability, high solids content, high ink volume, and a three-dimensional printing effect is a technical problem worthy of in-depth research.

[0005] In view of this, the present invention is proposed. Summary of the Invention

[0006] The purpose of this invention is to provide a water-based ceramic glaze ink, its preparation method, and its applications. By using lithium magnesium silicate as an inorganic rheology modifier and combining it with a specific compound base glaze, good dispersion stability and suitable viscosity and flow rate are achieved at high solids content, making it suitable for high ink volume printing and ensuring a three-dimensional shaping effect after water penetration. Simultaneously, this ink exhibits excellent dispersibility, and the precipitated portion is not hardened, contains no organic solvents, is environmentally friendly, simple to operate, and low in cost.

[0007] This invention is implemented as follows: In a first aspect, the present invention provides an aqueous ceramic glaze ink comprising the following raw materials by weight percentage: 88-95% base glaze slurry, 0.5-1.1% inorganic rheology modifier and 4-12% water.

[0008] In an optional embodiment, the base glaze slurry comprises the following raw materials in parts by weight: 16-25 parts of sodium feldspar, 36-50 parts of potassium feldspar, 4-6.5 parts of nepheline, 8-11 parts of kaolin, 5.5-8 parts of calcined clay, 4-5.5 parts of quartz, 2-5.5 parts of α-alumina, 5.5-8 parts of calcite, 12-18 parts of zirconium silicate, and 0.5-0.88 parts of grinding aid.

[0009] In an optional embodiment, the grinding aid comprises: 0.05-0.1 parts sodium carboxymethyl cellulose, 0.15-0.3 parts sodium tripolyphosphate, 0.2-0.3 parts sodium hexametaphosphate, and 0.1-0.18 parts water glass.

[0010] In an optional embodiment, the chemical composition of the base glaze slurry, by mass percentage, is: SiO2 54%-58%, Al2O3 18.25%-20.78%, CaO 2.61%-3.91%, MgO 0.05%-0.18%, K2O 3.75%-4.53%, Na2O 2.58%-3.64%, Fe2O3 0.15%-0.35%, TiO2 0.05%-0.13%, ZrO2 6.65%-10.06%, and LOI 3.27%-4.61%.

[0011] In an optional embodiment, the inorganic rheology modifier is lithium magnesium silicate.

[0012] In an optional embodiment, the solid content of the water-based ceramic glaze ink is 60-65%.

[0013] Secondly, the present invention provides a method for preparing water-based ceramic glaze ink, comprising the following steps: mixing basic glaze slurry raw materials according to a specified ratio, adding water and grinding aid for wet ball milling, sieving and cooling to obtain basic glaze slurry; adding lithium magnesium silicate dry powder to water for wet ball milling, sieving and cooling to obtain inorganic rheology modifier; stirring and mixing the basic glaze slurry and the inorganic rheology modifier to obtain water-based ceramic glaze ink.

[0014] In an optional embodiment, the weight ratio of the base glaze raw material to water is 100:(40-45), and in the preparation step of the base glaze slurry, the ball milling time is 15-20 minutes, and the sieve residue is 0.2%-0.8% after passing through a 500-mesh sieve.

[0015] In an optional embodiment, the weight ratio of the lithium magnesium silicate powder to water is 100:(4.5-5.5), and the ball milling time in the preparation step of the inorganic rheology modifier is 20-30 minutes.

[0016] Thirdly, the present invention provides an application of water-based ceramic glaze ink in inkjet printing of three-dimensional textures on the surface of ceramic products.

[0017] The present invention has the following beneficial effects: This invention significantly improves the overall performance of glaze slurry by optimizing its formulation. The addition of an inorganic rheology modifier effectively improves the glaze slurry's fluidity, resulting in more uniform glazing, fewer bubbles, and thus increased yield. Simultaneously, the bonding force between the glaze slurry and the body is enhanced, achieving complete coverage even on complex or rough surfaces and preventing peeling. The adjusted glaze slurry also improves surface hardness, abrasion resistance, and corrosion resistance, extending product lifespan. Compared to traditional methods, this formulation design is more rational and efficient, reducing energy consumption and environmental impact while ensuring quality, thus meeting sustainable development requirements. Furthermore, the low cost of raw materials and ease of operation facilitate low-cost, large-scale production. Attached Figure Description

[0018] To more clearly illustrate the technical solutions of the embodiments of the present invention, the accompanying drawings used in the embodiments will be briefly introduced below. It should be understood that the following drawings only show some embodiments of the present invention and should not be regarded as a limitation on the scope. For those skilled in the art, other related drawings can be obtained based on these drawings without creative effort.

[0019] Figure 1 This is an image showing the ink printing effect of an embodiment of the present invention; Figure 2 This is a comparative example of the ink printing effect of the present invention. Detailed Implementation

[0020] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. Where specific conditions are not specified in the embodiments, conventional conditions or conditions recommended by the manufacturer shall apply. Reagents or instruments whose manufacturers are not specified are all conventional products that can be purchased commercially.

[0021] The following is a detailed description of the water-based ceramic glaze ink proposed in this invention, its preparation method, and its application.

[0022] In a first aspect, the present invention provides an aqueous ceramic glaze ink comprising the following raw materials by weight percentage: 88-95% base glaze slurry, 0.5-1.1% inorganic rheology modifier and 4-12% water.

[0023] The base glaze slurry comprises the following raw materials in parts by weight: 16-25 parts of sodium feldspar, 36-50 parts of potassium feldspar, 4-6.5 parts of nepheline, 8-11 parts of kaolin, 5.5-8 parts of calcined clay, 4-5.5 parts of quartz, 2-5.5 parts of α-alumina, 5.5-8 parts of calcite, 12-18 parts of zirconium silicate, and 0.5-0.88 parts of grinding aid; the inorganic rheology modifier is lithium magnesium silicate.

[0024] Preferably, the water-based ceramic glaze ink provided by the present invention has a viscosity of 80-200 mPa•s, a flow rate of 18-28 m³ / s, and a specific gravity of 1.60-1.70.

[0025] This invention uses lithium magnesium silicate as an inorganic rheology modifier. Its three-dimensional network structure can block and support solid particles and adjust the shear thinning properties of glaze inks. Unlike natural layered silicates (such as montmorillonite and magnesium aluminum silicate), lithium magnesium silicate can be artificially synthesized, has high purity and stable quality, more controllable thixotropy, better resistance to high-valence ions (such as calcium ions), and is less sensitive to electrolytes than magnesium aluminum silicate. It maintains relatively stable viscosity and structure in electrolyte-containing systems.

[0026] In an optional embodiment, the grinding aid comprises: 0.05-0.1 parts sodium carboxymethyl cellulose, 0.15-0.3 parts sodium tripolyphosphate, 0.2-0.3 parts sodium hexametaphosphate, and 0.1-0.18 parts water glass.

[0027] Sodium tripolyphosphate is used in the base glaze, which has a strong ability to chelate calcium ions, reducing the damage of calcium ions to the structure of the subsequently added lithium magnesium silicate. Sodium hexametaphosphate assists in chelating calcium ions and enhances the dispersion effect. Water glass provides an alkaline environment for the stability of the lithium magnesium silicate structure, and sodium carboxymethyl cellulose provides thickening and stabilizing conditions for the water-based glaze ink base.

[0028] In an optional embodiment, the chemical composition of the base glaze slurry, by mass percentage, is: SiO2 54%-58%, Al2O3 18.25%-20.78%, CaO 2.61%-3.91%, MgO 0.05%-0.18%, K2O 3.75%-4.53%, Na2O 2.58%-3.64%, Fe2O3 0.15%-0.35%, TiO2 0.05%-0.13%, ZrO2 6.65%-10.06%, and LOI 3.27%-4.61%.

[0029] In an optional embodiment, the solid content of the water-based ceramic glaze ink is 60-65%, taking into account viscosity and flow rate to form suitable ink properties to adapt to high ink volume printing and the three-dimensional shaping effect after ink moisture seeps in.

[0030] Secondly, the present invention provides a method for preparing water-based ceramic glaze ink, comprising the following steps: S1. Preparation of basic glaze: Mix the basic glaze slurry raw materials according to the formula, add water and grinding aid, perform wet ball milling, sieve and cool to obtain basic glaze slurry.

[0031] In an optional embodiment, the weight ratio of the base glaze raw material to water is 100:(40-45), and in the preparation step of the base glaze slurry, the ball milling time is 15-20 minutes, and the sieve residue is 0.2%-0.8% after passing through a 500-mesh sieve.

[0032] S2. Preparation of inorganic rheology modifier: Add lithium magnesium silicate dry powder to water and perform wet ball milling, sieve and cool to obtain inorganic rheology modifier.

[0033] In an optional embodiment, the weight ratio of the lithium magnesium silicate powder to water is 100:(4.5-5.5), and the ball milling time in the preparation step of the inorganic rheology modifier is 20-30 minutes.

[0034] It should be noted that steps S1 and S2 do not have a specific order and can be performed simultaneously.

[0035] S3. The base glaze slurry and the inorganic rheology modifier are stirred and mixed at a speed of 60-100 rpm. The inorganic rheology modifier and water are added while stirring the base glaze, and the properties of the glaze ink are adjusted according to the values ​​of viscosity, flow rate and specific gravity to obtain water-based ceramic glaze ink.

[0036] By first preparing an aqueous solution of lithium magnesium silicate and then adding it to the compounded base glaze, the calcium ions and strong electrolyte sodium ions in the base glaze can reduce the impact on the lithium magnesium silicate network.

[0037] Thirdly, the present invention provides an application of water-based ceramic glaze ink in inkjet printing of three-dimensional textures on the surface of ceramic products.

[0038] The features and performance of the present invention will be further described in detail below with reference to embodiments.

[0039] Example 1 This embodiment provides a water-based ceramic glaze ink, comprising the following raw materials by weight percentage: 88.68% base glaze paste, 0.94% inorganic rheology modifier, and 10.38% water.

[0040] The base glaze slurry comprises the following raw materials in parts by weight: 18 parts sodium feldspar, 37 parts potassium feldspar, 4 parts nepheline, 8 parts kaolin, 6 parts calcined clay, 4 parts quartz, 4 parts α-alumina, 6 parts calcite, 12 parts zirconium silicate, and 0.77 parts grinding aid.

[0041] The grinding aids include: 0.08 parts sodium carboxymethyl cellulose, 0.25 parts sodium tripolyphosphate, 0.28 parts sodium hexametaphosphate, and 0.16 parts water glass.

[0042] The chemical composition of the base glaze slurry, by mass percentage, is: SiO2 56.81%, Al2O3 19.90%, CaO 3.31%, MgO 0.05%, K2O 4.18%, Na2O 3.07%, Fe2O3 0.23%, TiO2 0.1%, ZrO 2 8.43%, and LOI 3.89%.

[0043] Its preparation method includes the following steps: S1. Prepare the basic glaze slurry by wet ball milling. Weigh the ingredients according to the formula composition by mass, add 41 parts of water, ball mill for 18 minutes, pass through a 500-mesh sieve, the residue is 0.26%, and cool to room temperature to obtain the basic glaze slurry.

[0044] S2. Inorganic rheology modifiers are prepared by wet ball milling. The raw materials of each component are weighed according to the formula. 4.7 parts of magnesium lithium silicate dry powder are added to 100 parts of water, ball milled for 25 minutes, sieved, cooled and set aside to obtain inorganic rheology modifiers.

[0045] S3. The base glaze slurry is stirred and mixed with the inorganic rheology modifier. Water-based ceramic glaze ink is obtained by stirring the base glaze while adding the inorganic rheology modifier and water.

[0046] Example 2 This embodiment provides a water-based ceramic glaze ink and its preparation method. The steps are the same as those in Embodiment 1, except that the raw materials include the following weight percentages: 92.95% base glaze slurry, 0.68% inorganic rheology modifier and 6.36% water.

[0047] Example 3 This embodiment provides a water-based ceramic glaze ink, the steps of which are the same as those in Embodiment 1, the only difference being that it includes the following raw materials by weight percentage: 90.20% base glaze slurry, 0.98% inorganic rheology modifier and 8.82% water.

[0048] The base glaze slurry comprises the following raw materials in parts by weight: 18.3 parts sodium feldspar, 37.5 parts potassium feldspar, 4.1 parts nepheline, 8.3 parts kaolin, 5.8 parts calcined clay, 4.1 parts quartz, 2.5 parts α-alumina, 5.8 parts calcite, 12.5 parts zirconium silicate, and 0.77 parts grinding aid.

[0049] The grinding aids include: 0.08 parts sodium carboxymethyl cellulose, 0.25 parts sodium tripolyphosphate, 0.28 parts sodium hexametaphosphate, and 0.16 parts water glass.

[0050] The chemical composition of the base glaze slurry, by mass percentage, is as follows: SiO2 57.78%, Al2O3 18.56%, CaO 3.37%, MgO 0.05%, K2O 4.25%, Na2O 3.12%, Fe2O3 0.23%, TiO2 0.1%, ZrO2 8.57%, and LOI 3.96%.

[0051] Comparative Example 1 This comparative example provides a water-based ceramic glaze ink and its preparation method. The steps are the same as those in Example 1, except that the raw materials include the following weight percentages: 93.33% base glaze slurry, 1.91% inorganic rheology modifier and 4.76% water.

[0052] Comparative Example 2 This comparative example provides a water-based ceramic glaze ink and its preparation method, the steps of which are the same as those in Example 1, the only difference being that it includes the following raw materials by weight percentage: 92.09% base glaze slurry and 7.91% water.

[0053] Comparative Example 3 This comparative example provides a water-based ceramic glaze ink and its preparation method. The steps are the same as those in Example 1, except that the raw materials include the following weight percentages: 97.03% base glaze slurry, 0.99% inorganic rheology modifier and 1.98% water.

[0054] Comparative Example 4 This comparative example provides a water-based ceramic glaze ink and its preparation method. The steps are the same as those in Example 1, except that the raw materials include the following weight percentages: 83.49% base glaze slurry, 0.93% inorganic rheology modifier and 15.58% water.

[0055] Comparative Example 5 This comparative example provides a water-based ceramic glaze ink and its preparation method, the steps of which are the same as those in Example 1, the only difference being that no grinding aid is added.

[0056] Test case The performance of the water-based ceramic glaze ink samples prepared in Examples 1-2 and Comparative Examples 1-4 was tested, and the results are shown in Table 1.

[0057]

[0058] Table 1. Performance Comparison Table Figure 1 The ink printing effect of Example 1 shows that a certain three-dimensional effect is achieved after printing without obvious streaks or ink shortages. Figure 2 As shown in Example 1, the ink printing effect is too high, resulting in ink streaking defects.

[0059] As shown in Table 1, no hard precipitates were observed in Examples 1-3 and Comparative Examples 1-4 after standing for 7 days, and the precipitates easily dissolved after stirring, indicating that the base glaze slurry possesses a certain degree of dispersion stability. The 7-day sedimentation rate of Comparative Examples 1 and 3 was significantly lower than that of Example 2, indicating that the increase in the base glaze slurry and inorganic rheology modifier improved the dispersion stability of the ink.

[0060] Comparing Example 2 with Comparative Examples 1 and 2, it is shown that when the proportion of the base glaze is similar, increasing the amount of inorganic rheology modifier increases the ink viscosity. Comparative Examples 1 and 3, compared to Example 2, show that increased amounts of base glaze and inorganic rheology modifier lead to higher viscosity; higher viscosity results in spraying difficulties, nozzle clogging, and shortened lifespan, failing to meet printing requirements. When printed on brick blanks, Comparative Examples 1 and 3 exhibit more ink gaps and thinner textures compared to Examples 1-3.

[0061] The ink flow rates in Comparative Examples 2 and 4 were faster than those in Examples 1-3, indicating that the ink flow rate increased when there was a lack of inorganic rheology modifier and a reduced proportion of base glaze. Printing with a large ink volume caused the ink to flow around before it dried, preventing the formation of a three-dimensional texture effect. When printed on brick blanks, Comparative Examples 2 and 3 showed adhesion between textures compared to Examples 1-3, and the textures were less clear and less blurred.

[0062] The viscosity and flow rate changes in Comparative Examples 1-4 show that, under normal circumstances, the flow rate changes along with the viscosity. In conjunction with the comparison of Examples 1-3, it shows that when the content of the base glaze is reduced, the inorganic rheology modifier has the ability to maintain the flow rate while increasing the viscosity to a certain extent. After printing, it can better balance the problems of ink shortage and ink flow than Comparative Examples 1-4.

[0063] In Comparative Example 5, the base glaze slurry, after ball milling without grinding aids, exhibits severe thixotropy, significantly reducing its fluidity and making it difficult to form balls. The formula contains calcite, primarily composed of calcium carbonate. This calcite undergoes slight dissolution or reaction on the particle surface, releasing calcium ions. During wet ball milling, the calcite particles become finer and more numerous, resulting in a dramatic increase in surface area and easier release of calcium ions. As divalent cations, these high charge density compresses or even neutralizes the negatively charged double layer of negatively charged colloidal particles such as kaolin in the glaze slurry, weakening the electrostatic repulsion between particles and adsorbing particles at both ends, forming flocculation. This causes the base glaze slurry to become thick, losing its fluidity and basic dispersibility. Grinding aids play a synergistic role when mixed with inorganic rheology modifiers and also play an important role in reducing viscosity and dispersing in the base glaze slurry.

[0064] The above description is merely a preferred embodiment of the present invention and is not intended to limit the invention. Various modifications and variations can be made to the present invention by those skilled in the art. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. An aqueous ceramic glaze ink, characterized by, The raw materials include the following weight percentages: 88-95% base glaze, 0.5-1.1% inorganic rheological modifier and 4-12% water.

2. The aqueous ceramic glaze ink according to claim 1, characterized in that, The base glaze includes the following mass fractions of raw materials: 16-25 parts of sodium feldspar, 36-50 parts of potassium feldspar, 4-6.5 parts of nepheline, 8-11 parts of kaolin, 5.5-8 parts of calcined soil, 4-5.5 parts of quartz, 2-5.5 parts of α-type aluminum oxide, 5.5-8 parts of calcite, 12-18 parts of zirconium silicate and 0.5-0.88 parts of grinding aid.

3. The aqueous ceramic enamel ink according to claim 2, characterized in that, The grinding aid includes: 0.05-0.1 parts of sodium carboxymethyl cellulose, 0.15-0.3 parts of sodium tripolyphosphate, 0.2-0.3 parts of sodium hexametaphosphate and 0.1-0.18 parts of water glass.

4. The aqueous ceramic enamel ink according to claim 2, characterized in that, The chemical composition of the base glaze is, by mass percentage: SiO2 54%-58%, Al2O3 18.25%-20.78%, CaO 2.61%-3.91%, MgO 0.05%-0.18%, K2O 3.75%-4.53%, Na2O 2.58%-3.64%, Fe2O3 0.15%-0.35%, TiO2 0.05%-0.13%, ZrO2 6.65%-10.06% and LOI 3.27%-4.61%.

5. The aqueous ceramic enamel ink according to claim 1, wherein, The inorganic rheological modifier is magnesium lithium silicate.

6. The aqueous ceramic enamel ink according to claim 1, wherein, The solid content of the water-based ceramic glaze ink is 60-65%.

7. A method for preparing an aqueous ceramic enamel ink according to any one of claims 1 to 6, characterized in that, The method includes the following steps: mixing base glaze raw materials according to the ratio, adding water and grinding aid for wet ball milling, sieving and cooling to obtain the base glaze; adding magnesium lithium silicate dry powder into water for wet ball milling, sieving and cooling to obtain the inorganic rheological modifier; stirring and mixing the base glaze and the inorganic rheological modifier to obtain the water-based ceramic glaze ink.

8. The method for preparing a water-based ceramic glaze ink according to claim 7, characterized in that, The weight ratio of the base glaze raw materials and water is 100: (40-45), and in the preparation step of the base glaze, the ball milling time is 15-20 minutes, the sieve residue is 0.2%-0.8% after sieving through a 500-mesh sieve.

9. The method of claim 7, wherein the water-based ceramic enamel ink is prepared by mixing the water-based ceramic enamel ink with a pigment, a dispersant, a thickener, a defoamer, a preservative, and a pH adjuster. The weight ratio of the magnesium lithium silicate dry powder and water is 100: (4.5-5.5), and in the preparation step of the inorganic rheological modifier, the ball milling time is 20-30 minutes.

10. Use of the water-based ceramic glaze ink according to any one of claims 1-6 in inkjet printing of a three-dimensional texture on the surface of a ceramic product.

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