A surface protective glaze for 3D printing rock slabs and preparation method thereof

Abstract

The present invention relates to the field of ceramic glazes, and in particular to a surface protective glaze for 3D printed rock slabs and a preparation method thereof. By introducing methacryloyloxyethyl phosphate and γ-methacryloyloxypropyltrimethoxysilane, and copolymerizing with acrylic compounds, the improved glaze has significantly improved thermal stability, mechanical stability, antioxidant properties and color fixation properties. These improvements enable the glaze to better maintain color stability and adhesion during high-temperature firing, thereby improving overall performance and service life. Through experimental verification, the effects of these improvements can be further confirmed to ensure their reliability and superiority in practical applications. Although this method has a complex process, the performance improvement and long-term stability it brings give it greater advantages and prospects in the application of high-performance 3D printed rock slab protective glazes.

Description

Technical Field

[0001] The present invention relates to the field of ceramic glazes, and in particular to a surface protective glaze for 3D printing rock slabs and a preparation method thereof. Background Art

[0002] With the development and increasing demand for building decoration materials, 3D-printed rock slabs, as a high-performance, environmentally friendly, and aesthetically pleasing building decoration material, have attracted widespread attention and application. 3D-printed rock slabs boast excellent properties such as high hardness, high wear resistance, high temperature resistance, and corrosion resistance, making them widely used in interior and exterior decoration, furniture countertops, and floor coverings. However, in practice, the surface of 3D-printed rock slabs is susceptible to wear, contamination, and environmental impacts, resulting in a reduction in their service life and aesthetics. Therefore, effective surface protection is crucial.

[0003] Traditional methods of protecting 3D printed slabs rely primarily on applying protective glazes. These glazes not only impart a glossy and aesthetically pleasing surface to 3D printed slabs, but also effectively enhance their wear resistance, stain resistance, and weather resistance. However, existing protective glazes suffer from technical drawbacks, such as insufficient adhesion, poor color fixation, and low high-temperature stability. These limitations limit their performance and effectiveness.

[0004] The main components of traditional glazes include base glaze, organic solvents, defoamers, and leveling agents. While these ingredients can improve the glaze's performance to a certain extent, during high-temperature firing, the adhesion between the glaze and the substrate is often insufficient, leading to flaking and cracking, resulting in poor protective effects. Furthermore, traditional glazes exhibit poor color retention at high temperatures, causing color particles to easily bleed and diffuse, affecting the aesthetics of the slab.

[0005] To improve the adhesion and color-fixing properties of glazes, researchers have introduced new materials and processes. For example, the addition of nanomaterials (such as nano-alumina and nano-titanium dioxide) can significantly increase the hardness and wear resistance of glazes, enhancing their dispersibility and stability. However, while these improvements have improved the performance of glazes to a certain extent, they are still insufficient to address the problem of insufficient adhesion between glazes and substrates at high temperatures.

[0006] In recent years, with the continuous advancement of chemistry and materials science, some chemical substances with special functions have been introduced into glaze formulations to further enhance their performance. For example, the introduction of high-temperature binders and interfacial modifiers can chemically react with the substrate surface during high-temperature firing, forming strong chemical bonds and significantly enhancing the glaze's adhesion and color fixation properties.

[0007] High-temperature binders such as methacryloxyethyl phosphate (MPEP) and interfacial modifiers such as γ-methacryloxypropyltrimethoxysilane (MPTA) are two chemical substances with bifunctional groups. MPEP and MPTA not only copolymerize with acrylic monomers to form high-molecular-weight polymers, enhancing the mechanical strength and durability of the glaze, but also react chemically with the substrate surface at high temperatures to form strong chemical bonds, strengthening the adhesion between the glaze and the substrate. Furthermore, the introduction of these substances can enhance the glaze's antioxidant properties and thermal stability, further improving its overall performance.

[0008] However, while directly adding high-temperature binders and interfacial modifiers can improve adhesion to a certain extent, the effect is limited and easily affected by process control. Furthermore, directly adding high-temperature binders and interfacial modifiers can easily lead to uneven dispersion, affecting the mechanical properties of the slab. MPEP and MPTA may also decompose or migrate at high temperatures, affecting the stability of the glaze. Summary of the Invention

[0009] In response to the deficiencies in the prior art, the present invention provides a surface protective glaze for 3D printed rock slabs and a preparation method thereof.

[0010] The present invention provides a surface protective glaze for 3D printing rock slabs, which comprises the following raw materials in parts by mass:

[0011] Basic glaze: 35-55 parts;

[0012] Nano-alumina: 2-5 parts;

[0013] Organic solvent: 45-55 parts;

[0014] Defoaming agent: 0.04-0.8 parts;

[0015] Leveling agent: 0.04-0.08 parts;

[0016] Polyurethane: 2-5 parts;

[0017] Glaze dispersant: 4-8 parts.

[0018] The basic glaze is a common basic glaze formula in this field, including transparent glaze and opaque glaze.

[0019] Preferably, the organic solvent is at least one of dimethyl sulfoxide, dimethylformamide, dimethylacetamide, ethyl acetate, acetone, and methyl ethyl ketone; more preferably, the organic solvent is dimethyl sulfoxide.

[0020] Preferably, the defoamer is BYK-052 defoamer, Airex902W defoaming agent, At least one of 111 defoamer, BYK-065 defoamer, and DeeFo2150 defoamer.

[0021] Preferably, the leveling agent is BYK-306 leveling agent, Glide450 leveling agent, EFKA-3770 leveling agent, BYK-358N leveling agent, At least one of Flow375 leveling agents.

[0022] Preferably, the polyurethane is 5703 polyurethane, 9370A polyurethane, HT-2000 polyurethane, 985A polyurethane, 2363-80AE polyurethane, 1180A polyurethane; preferably, the polyurethane is 9370A Polyurethane.

[0023] The preparation method of the glaze dispersant comprises the following steps:

[0024] (1) adding an acrylic acid compound and an acrylic acid ester compound to dimethyl sulfoxide;

[0025] (2) adding vinyl triethoxysilane and N-vinyl pyrrolidone;

[0026] (3) adding azobisisobutyronitrile and an adhesion enhancer, stirring, and obtaining the glaze dispersant.

[0027] Preferably, the preparation method of the glaze dispersant comprises the following steps:

[0028] (1) adding 50-60 g of an acrylic acid compound and 20-30 g of an acrylic acid ester compound to 30-50 g of dimethyl sulfoxide at 70-80° C. and nitrogen atmosphere, and stirring at 150-200 rpm to obtain an acrylic acid prepolymer solution;

[0029] (2) maintaining stirring at 150-200 r / min, adding 5-15 g of vinyltriethoxysilane as a crosslinking agent to the acrylic polymer solution obtained in step (1) at a rate of 3-5 g / min to enhance the network structure and durability of the material, and then adding 1-3 g of N-vinylpyrrolidone, stirring at 100-300 r / min for 5-15 min, by capturing the polymerization active center, controlling the molecular weight and molecular weight distribution of the polymer, and obtaining a cross-linked acrylic polymer solution;

[0030] (3) adding 1-3 g of azobisisobutyronitrile as an initiator for a free radical polymerization reaction to the cross-linked acrylic polymer solution obtained in step (2), adding 6-12 g of an adhesion enhancer while stirring at 150-200 r / min, and restarting the polymerization reaction. These substances have bifunctional groups and can copolymerize with acrylic compounds to form a polymer, and react with the surface of the substrate at high temperature to enhance the bonding force; stirring at 70-80° C. and 100-300 r / min for 60-180 min to ensure that the polymerization reaction is fully carried out to form the desired high molecular weight polymer, and cooling to room temperature to obtain the glaze dispersant.

[0031] Preferably, the acrylic compound is at least one of acrylic acid and methacrylic acid.

[0032] Preferably, the acrylic acid ester compound is at least one of methyl methacrylate and butyl acrylate.

[0033] Preferably, the adhesion enhancer is at least one of methacryloxyethyl phosphate and γ-methacryloxypropyltrimethoxysilane; preferably, the adhesion enhancer is a mixture of methacryloxyethyl phosphate and γ-methacryloxypropyltrimethoxysilane in a mass ratio of (5-10): (1-2).

[0034] The present invention also provides a method for preparing a surface protective glaze for 3D printed rock slabs, comprising the following steps: adding 35-55 parts of a basic glaze, 2-5 parts of nano-alumina, 45-55 parts of an organic solvent, 0.04-0.8 parts of a defoaming agent, 0.04-0.08 parts of a leveling agent, 2-5 parts of a polyurethane, and 4-8 parts of a glaze dispersant, by mass, into a sand mill and grinding them evenly to obtain the surface protective glaze for 3D printed rock slabs.

[0035] Preferably, zirconia balls with a diameter of 0.5-1.5 mm are used as grinding media, the sanding time is 3-6 h, and the grinding speed is 500-1500 r / min.

[0036] The organic glaze prepared by the present invention can effectively prevent water penetration and protect the substrate compared to traditional water-soluble glazes, and can better penetrate into the surface of the substrate and improve adhesion.

[0037] In addition, traditional glazes have weak bonding with the substrate at high temperatures, which makes the glaze prone to falling off and color loss during high-temperature firing. Although directly adding methacryloxyethyl phosphate and γ-methacryloxypropyltrimethoxysilane can improve adhesion to a certain extent, the effect is limited and is easily affected by process control. It may decompose or migrate at high temperatures, affecting the stability of the glaze. Uneven dispersion of additives may also lead to inconsistent mechanical properties.

[0038] To improve this defect, the present invention introduces methacryloxyethyl phosphate and γ-methacryloxypropyltrimethoxysilane, and copolymerizes them with acrylic compounds. Methacryloxyethyl phosphate and γ-methacryloxypropyltrimethoxysilane form chemical bonds with the substrate at high temperatures. Such chemical bonds improve the thermal stability of the glaze, making it more stable during high-temperature sintering and less prone to decomposition or deterioration. The polymer chains formed by copolymerization form stronger chemical bonds with the surface of the substrate, significantly improving adhesion and bonding strength, giving the glaze higher mechanical strength and wear resistance, thereby improving the overall stability of the glaze.

[0039] Since methacryloyloxyethyl phosphate and γ-methacryloyloxypropyltrimethoxysilane can form strong chemical bonds with the surface of the substrate at high temperatures, this chemical bond not only enhances the adhesion of the glaze, but also effectively locks the color particles, preventing the loss and diffusion of color during high-temperature firing.

[0040] However, the unimproved glaze lacks the chemical bonding effect at high temperature and the protection of nanomaterials. During the high-temperature firing process, the color particles are easily lost and diffused, resulting in poor color fixing performance.

[0041] Beneficial effects of the present invention:

[0042] By introducing methacryloxyethyl phosphate and γ-methacryloxypropyltrimethoxysilane, and copolymerizing them with acrylic compounds, the improved glaze has significantly improved its thermal stability, mechanical stability, antioxidant properties, and color fixation properties. These improvements enable the glaze to better maintain color stability and adhesion during high-temperature firing, thereby improving overall performance and service life. Experimental verification can further confirm the effectiveness of these improvements and ensure their reliability and superiority in practical applications. Although this method is complex, the performance improvements and long-term stability it brings give it greater advantages and prospects in the application of high-performance 3D printed rock slab protective glazes. DETAILED DESCRIPTION

[0043] Nano-alumina, model: TAP-A26, Nanjing Tianxing New Materials Co., Ltd.

[0044] Methacryloyloxyethyl phosphate, CAS number: 32435-46-4.

[0045] γ-Methacryloxypropyltrimethoxysilane, CAS number: 2530-85-0.

[0046] N-vinylpyrrolidone, CAS number: 88-12-0.

[0047] The basic glaze used in the following examples and comparative examples is composed of the following raw materials in the following weight percentages: potassium feldspar: 30%, quartz: 20%, zinc borate: 10%, titanium oxide: 10%, barium carbonate: 15%, and kaolin: 15%.

[0048] A method for preparing a surface protective glaze for 3D printed rock slabs comprises the following steps: adding, by mass, 50 parts of a basic glaze, 3 parts of nano-alumina, 50 parts of an organic solvent, 0.2 parts of a defoaming agent, 0.06 parts of a leveling agent, 3 parts of polyurethane, and 6 parts of a glaze dispersant into a sand mill and grinding them uniformly to obtain the surface protective glaze for 3D printed rock slabs.

[0049] Zirconia balls with a diameter of 1 mm were used as the grinding medium, the sanding time was 4 h, and the grinding speed was 1200 r / min.

[0050] Example 1

[0051] A surface protective glaze for 3D printing rock slabs, comprising the following raw materials in parts by mass:

[0052] Basic glaze: 50 parts;

[0053] Nano-alumina: 3 parts;

[0054] Organic solvent: 50 parts;

[0055] Defoaming agent: 0.2 parts;

[0056] Leveling agent: 0.06 parts;

[0057] Polyurethane: 3 parts;

[0058] Glaze dispersant: 6 parts.

[0059] The organic solvent is dimethyl sulfoxide.

[0060] The defoamer is BYK-052 defoamer.

[0061] The leveling agent is BYK-306 leveling agent.

[0062] The polyurethane is 9370A Polyurethane.

[0063] The preparation method of the glaze dispersant comprises the following steps:

[0064] (1) Add 55 g of an acrylic acid compound and 25 g of an acrylic acid ester compound to 40 g of dimethyl sulfoxide at 75° C. under nitrogen atmosphere, and stir at 200 rpm to obtain an acrylic acid prepolymer solution;

[0065] (2) maintaining stirring at 200 r / min, adding 10 g of vinyltriethoxysilane dropwise to the acrylic polymer solution obtained in step (1) at a rate of 5 g / min, then adding 2 g of N-vinylpyrrolidone, and stirring at 300 r / min for 10 min to obtain a cross-linked acrylic polymer solution;

[0066] (3) adding 2 g of azobisisobutyronitrile to the cross-linked acrylic polymer solution obtained in step (2), adding 10 g of an adhesion enhancer while stirring at 200 r / min, stirring at 75° C. and 300 r / min for 120 min, and cooling to room temperature to obtain the glaze dispersant.

[0067] The acrylic compound is prepared by mixing acrylic acid and methacrylic acid in a mass ratio of 1:2.

[0068] The acrylic acid ester compound is prepared by mixing methyl methacrylate and butyl acrylate in a mass ratio of 2:3.

[0069] The adhesion enhancer is prepared by mixing methacryloyloxyethyl phosphate and gamma-methacryloyloxypropyltrimethoxysilane in a mass ratio of 5:1.

[0070] Example 2

[0071] A surface protective glaze for 3D printing rock slabs, comprising the following raw materials in parts by mass:

[0072] Basic glaze: 50 parts;

[0073] Nano-alumina: 3 parts;

[0074] Organic solvent: 50 parts;

[0075] Defoaming agent: 0.2 parts;

[0076] Leveling agent: 0.06 parts;

[0077] Polyurethane: 3 parts;

[0078] Glaze dispersant: 6 parts.

[0079] The organic solvent is dimethyl sulfoxide.

[0080] The defoamer is BYK-052 defoamer.

[0081] The leveling agent is BYK-306 leveling agent.

[0082] The polyurethane is 9370A Polyurethane.

[0083] The preparation method of the glaze dispersant comprises the following steps:

[0084] (1) Add 55 g of an acrylic acid compound and 25 g of an acrylic acid ester compound to 40 g of dimethyl sulfoxide at 75° C. under nitrogen atmosphere, and stir at 200 rpm to obtain an acrylic acid prepolymer solution;

[0085] (2) maintaining stirring at 200 r / min, adding 10 g of vinyltriethoxysilane dropwise to the acrylic polymer solution obtained in step (1) at a rate of 5 g / min, and stirring for 10 min to obtain a cross-linked acrylic polymer solution;

[0086] (3) adding 2 g of azobisisobutyronitrile to the cross-linked acrylic polymer solution obtained in step (2), adding 10 g of an adhesion enhancer while stirring at 200 r / min, stirring at 75° C. and 300 r / min for 120 min, and cooling to room temperature to obtain the glaze dispersant.

[0087] The acrylic compound is prepared by mixing acrylic acid and methacrylic acid in a mass ratio of 1:2.

[0088] The acrylic acid ester compound is prepared by mixing methyl methacrylate and butyl acrylate in a mass ratio of 2:3.

[0089] The adhesion enhancer is prepared by mixing methacryloyloxyethyl phosphate and gamma-methacryloyloxypropyltrimethoxysilane in a mass ratio of 5:1.

[0090] Example 3

[0091] A surface protective glaze for 3D printing rock slabs, comprising the following raw materials in parts by mass:

[0092] Basic glaze: 50 parts;

[0093] Nano-alumina: 3 parts;

[0094] Organic solvent: 50 parts;

[0095] Defoaming agent: 0.2 parts;

[0096] Leveling agent: 0.06 parts;

[0097] Polyurethane: 3 parts;

[0098] Glaze dispersant: 6 parts.

[0099] The organic solvent is dimethyl sulfoxide.

[0100] The defoamer is BYK-052 defoamer.

[0101] The leveling agent is BYK-306 leveling agent.

[0102] The polyurethane is 9370A Polyurethane.

[0103] The preparation method of the glaze dispersant comprises the following steps:

[0104] (1) Add 55 g of an acrylic acid compound and 25 g of an acrylic acid ester compound to 40 g of dimethyl sulfoxide at 75° C. under nitrogen atmosphere, and stir at 200 rpm to obtain an acrylic acid prepolymer solution;

[0105] (2) maintaining stirring at 200 r / min, adding 10 g of vinyltriethoxysilane dropwise to the acrylic polymer solution obtained in step (1) at a rate of 5 g / min, then adding 2 g of N-vinylpyrrolidone, stirring at 300 r / min for 10 min, and cooling to room temperature to obtain the glaze dispersant.

[0106] The acrylic compound is prepared by mixing acrylic acid and methacrylic acid in a mass ratio of 1:2.

[0107] The acrylic acid ester compound is prepared by mixing methyl methacrylate and butyl acrylate in a mass ratio of 2:3.

[0108] Example 4

[0109] A surface protective glaze for 3D printing rock slabs, comprising the following raw materials in parts by mass:

[0110] Basic glaze: 50 parts;

[0111] Nano-alumina: 3 parts;

[0112] Organic solvent: 50 parts;

[0113] Defoaming agent: 0.2 parts;

[0114] Leveling agent: 0.06 parts;

[0115] Polyurethane: 3 parts;

[0116] Glaze dispersant: 6 parts.

[0117] The organic solvent is dimethyl sulfoxide.

[0118] The defoamer is BYK-052 defoamer.

[0119] The leveling agent is BYK-306 leveling agent.

[0120] The polyurethane is 9370A Polyurethane.

[0121] The preparation method of the glaze dispersant comprises the following steps:

[0122] (1) Add 55 g of an acrylic acid compound and 25 g of an acrylic acid ester compound to 40 g of dimethyl sulfoxide at 75° C. under nitrogen atmosphere, and stir at 200 rpm to obtain an acrylic acid prepolymer solution;

[0123] (2) Maintaining stirring at 200 r / min, 10 g of vinyltriethoxysilane was added dropwise to the acrylic polymer solution obtained in step (1) at a rate of 5 g / min, stirred at 300 r / min for 10 min, and cooled to room temperature to obtain the glaze dispersant.

[0124] The acrylic compound is prepared by mixing acrylic acid and methacrylic acid in a mass ratio of 1:2.

[0125] The acrylic acid ester compound is prepared by mixing methyl methacrylate and butyl acrylate in a mass ratio of 2:3.

[0126] Example 5

[0127] A surface protective glaze for 3D printing rock slabs, comprising the following raw materials in parts by mass:

[0128] Basic glaze: 50 parts;

[0129] Nano-alumina: 3 parts;

[0130] Organic solvent: 50 parts;

[0131] Defoaming agent: 0.2 parts;

[0132] Leveling agent: 0.06 parts;

[0133] Polyurethane: 3 parts;

[0134] Glaze dispersant: 6 parts.

[0135] The organic solvent is dimethyl sulfoxide.

[0136] The defoamer is BYK-052 defoamer.

[0137] The leveling agent is BYK-306 leveling agent.

[0138] The polyurethane is 9370A Polyurethane.

[0139] The preparation method of the glaze dispersant comprises the following steps:

[0140] (1) Add 55 g of an acrylic acid compound and 25 g of an acrylic acid ester compound to 40 g of dimethyl sulfoxide at 75° C. under nitrogen atmosphere, and stir at 200 rpm to obtain an acrylic acid prepolymer solution;

[0141] (2) maintaining stirring at 200 r / min, adding 10 g of vinyltriethoxysilane dropwise to the acrylic polymer solution obtained in step (1) at a rate of 5 g / min, then adding 2 g of N-vinylpyrrolidone, and stirring at 300 r / min for 10 min to obtain a cross-linked acrylic polymer solution;

[0142] (3) adding 2 g of azobisisobutyronitrile to the cross-linked acrylic polymer solution obtained in step (2), adding 10 g of an adhesion enhancer while stirring at 200 r / min, stirring at 75° C. and 300 r / min for 120 min, and cooling to room temperature to obtain the glaze dispersant.

[0143] The acrylic compound is prepared by mixing acrylic acid and methacrylic acid in a mass ratio of 1:2.

[0144] The acrylic acid ester compound is prepared by mixing methyl methacrylate and butyl acrylate in a mass ratio of 2:3.

[0145] The adhesion enhancer is methacryloyloxyethyl phosphate.

[0146] Example 6

[0147] A surface protective glaze for 3D printing rock slabs, comprising the following raw materials in parts by mass:

[0148] Basic glaze: 50 parts;

[0149] Nano-alumina: 3 parts;

[0150] Organic solvent: 50 parts;

[0151] Defoaming agent: 0.2 parts;

[0152] Leveling agent: 0.06 parts;

[0153] Polyurethane: 3 parts;

[0154] Glaze dispersant: 6 parts.

[0155] The organic solvent is dimethyl sulfoxide.

[0156] The defoamer is BYK-052 defoamer.

[0157] The leveling agent is BYK-306 leveling agent.

[0158] The polyurethane is 9370A Polyurethane.

[0159] The preparation method of the glaze dispersant comprises the following steps:

[0160] (1) Add 55 g of an acrylic acid compound and 25 g of an acrylic acid ester compound to 40 g of dimethyl sulfoxide at 75° C. under nitrogen atmosphere, and stir at 200 rpm to obtain an acrylic acid prepolymer solution;

[0161] (2) maintaining stirring at 200 r / min, adding 10 g of vinyltriethoxysilane dropwise to the acrylic polymer solution obtained in step (1) at a rate of 5 g / min, then adding 2 g of N-vinylpyrrolidone, and stirring at 300 r / min for 10 min to obtain a cross-linked acrylic polymer solution;

[0162] (3) adding 2 g of azobisisobutyronitrile to the cross-linked acrylic polymer solution obtained in step (2), adding 10 g of an adhesion enhancer while stirring at 200 r / min, stirring at 75° C. and 300 r / min for 120 min, and cooling to room temperature to obtain the glaze dispersant.

[0163] The acrylic compound is prepared by mixing acrylic acid and methacrylic acid in a mass ratio of 1:2.

[0164] The acrylic acid ester compound is prepared by mixing methyl methacrylate and butyl acrylate in a mass ratio of 2:3.

[0165] The adhesion enhancer is γ-methacryloxypropyltrimethoxysilane.

[0166] Comparative Example 1

[0167] A surface protective glaze for 3D printing rock slabs, comprising the following raw materials in parts by mass:

[0168] Basic glaze: 50 parts;

[0169] Nano-alumina: 3 parts;

[0170] Organic solvent: 50 parts;

[0171] Defoaming agent: 0.2 parts;

[0172] Leveling agent: 0.06 parts;

[0173] Glaze dispersant: 6 parts.

[0174] The organic solvent is dimethyl sulfoxide.

[0175] The defoamer is BYK-052 defoamer.

[0176] The leveling agent is BYK-306 leveling agent.

[0177] The preparation method of the glaze dispersant comprises the following steps:

[0178] (1) Add 55 g of an acrylic acid compound and 25 g of an acrylic acid ester compound to 40 g of dimethyl sulfoxide at 75° C. under nitrogen atmosphere, and stir at 200 rpm to obtain an acrylic acid prepolymer solution;

[0179] (2) maintaining stirring at 200 r / min, adding 10 g of vinyltriethoxysilane dropwise to the acrylic polymer solution obtained in step (1) at a rate of 5 g / min, then adding 2 g of N-vinylpyrrolidone, and stirring at 300 r / min for 10 min to obtain a cross-linked acrylic polymer solution;

[0180] (3) adding 2 g of azobisisobutyronitrile to the cross-linked acrylic polymer solution obtained in step (2), adding 10 g of an adhesion enhancer while stirring at 200 r / min, stirring at 75° C. and 300 r / min for 120 min, and cooling to room temperature to obtain the glaze dispersant.

[0181] The acrylic compound is prepared by mixing acrylic acid and methacrylic acid in a mass ratio of 1:2.

[0182] The acrylic acid ester compound is prepared by mixing methyl methacrylate and butyl acrylate in a mass ratio of 2:3.

[0183] The adhesion enhancer is prepared by mixing methacryloyloxyethyl phosphate and gamma-methacryloyloxypropyltrimethoxysilane in a mass ratio of 5:1.

[0184] Comparative Example 2

[0185] A surface protective glaze for 3D printing rock slabs, comprising the following raw materials in parts by mass:

[0186] Basic glaze: 50 parts;

[0187] Nano-alumina: 3 parts;

[0188] Organic solvent: 50 parts;

[0189] Defoaming agent: 0.2 parts;

[0190] Leveling agent: 0.06 parts;

[0191] Polyurethane: 3 parts;

[0192] The organic solvent is dimethyl sulfoxide.

[0193] The defoamer is BYK-052 defoamer.

[0194] The leveling agent is BYK-306 leveling agent.

[0195] The polyurethane is 9370A Polyurethane.

[0196] Test Example 1:

[0197] A method for preparing a printed rock plate comprises the following steps: performing inkjet printing decoration on the surface of the 3D printed rock plate to obtain a printed 3D printed rock plate;

[0198] Use inkjet machine to spray the surface protective glaze of 3D printed rock plate on the surface of printed 3D printed rock plate, and control the spraying amount to 50g / m 2 , sintered at 1120℃ for 60min, cooled to room temperature, and obtained the printed rock plate.

[0199] The ink used is cobalt blue ink with a grayscale value of 100%.

[0200] The above preparation method was used to prepare the printed slabs for attaching the surface protective glaze for 3D printed slabs obtained in Examples 1-6 and Comparative Examples 1-2. The Lab values ​​of the printed slabs were measured using a standard colorimeter to obtain the color range of the ink. In Lab, the L value represents brightness; the a value represents red-green values; and the b value represents yellow-blue values.

[0201] During the test, the printed 3D printed rock slabs obtained in Examples 1-6 and Comparative Examples 1-2 without applying surface protective glaze and without sintering were used as standard color cards for each and their corresponding comparative examples.

[0202] The Lab data of each embodiment and comparative example were compared with the Lab data of their respective standard color cards, and the color difference value was calculated using a formula to determine the effect of the glaze on the inkjet color.

[0203] Color difference formula: ΔEab*=[(ΔL*) 2 +(Δa*) 2 +(Δb*) 2 ] 1 / 2

[0204] Table 1: Color difference

[0205] ΔEab Example 1 1.2 Example 2 1.6 Example 3 2.7 Example 4 3.3 Example 5 1.5 Example 6 1.6 Comparative Example 1 4.2 Comparative Example 2 5.3

[0206] Test Example 2

[0207] A pull-out test was performed with reference to the GB / T5210-2006 standard. A printed rock plate was prepared with reference to the preparation method of the printed rock plate in Test Example 1. A disc with a diameter of 30 mm was cut from the printed rock plate and placed on a pull-out testing machine for a pull-out test. The adhesion force is the tensile force required for the glaze to fall off.

[0208] Table 2: Adhesion

[0209] Adhesion / MPa Example 1 8.4 Example 2 7.2 Example 3 6.1 Example 4 5.3 Example 5 7.2 Example 6 7.1 Comparative Example 1 4.1 Comparative Example 2 3.7

[0210] Tables 1 and 2 show that the surface protective glaze for the 3D printed rock slab prepared in Example 1 of the present invention has the best color fixation effect and the strongest adhesion. Example 2 is slightly inferior to Example 1 because N-vinyl pyrrolidone is not added during the preparation of the glaze dispersant. N-vinyl pyrrolidone can control the molecular weight of the acrylic polymer within a certain range, preventing the polymer from being too large and difficult to dissolve and disperse, which is more conducive to the subsequent polymerization of the adhesion enhancer. Example 3, which did not add an adhesion enhancer, exhibited significantly lower color fixation and adhesion than Example 1. This demonstrates that the introduction of methacryloxyethyl phosphate and γ-methacryloxypropyltrimethoxysilane, copolymerized with an acrylic compound, allows them to form chemical bonds with the substrate at high temperatures. These bonds enhance the thermal stability of the glaze, making it more stable during high-temperature sintering and less susceptible to decomposition or deterioration. The polymer chains formed through copolymerization form stronger chemical bonds with the substrate surface, significantly improving adhesion and bonding, imparting greater mechanical strength and wear resistance to the glaze, and thus enhancing its overall stability. Because methacryloxyethyl phosphate and γ-methacryloxypropyltrimethoxysilane can form strong chemical bonds with the substrate surface at high temperatures, these bonds not only enhance the glaze's adhesion but also effectively lock in the color particles, preventing color loss and diffusion during high-temperature firing. Example 4, which employed a simple acrylic copolymer as a glaze dispersant, achieved significantly lower results than Example 1. In Examples 5 and 6, methacryloxyethyl phosphate or γ-methacryloxypropyltrimethoxysilane was used alone, and the effects were slightly lower than those in Example 1, which proved that the combination of methacryloxyethyl phosphate and γ-methacryloxypropyltrimethoxysilane had the best effect.

[0211] In summary: By introducing methacryloyloxyethyl phosphate and γ-methacryloyloxypropyltrimethoxysilane and copolymerizing them with acrylic compounds, the improved glaze has significantly improved thermal stability, mechanical stability, antioxidant properties, and color fixation properties. These improvements enable the glaze to better maintain color stability and adhesion during high-temperature firing, thereby improving overall performance and service life. Through experimental verification, the effects of these improvements can be further confirmed, ensuring their reliability and superiority in practical applications. Although this method is complex, the performance improvements and long-term stability it brings give it greater advantages and prospects in the application of high-performance 3D printed rock slab protective glazes.

Claims

1. A surface protective glaze for 3D printed rock slabs, characterized in that: Calculated by mass, it includes the following raw materials: Basic glaze: 35-55 parts; Nano-alumina: 2-5 parts; Organic solvent: 45-55 parts; Defoaming agent: 0.04-0.8 parts; Leveling agent: 0.04-0.08 parts; Polyurethane: 2-5 parts; Glaze dispersant: 4-8 parts; The preparation method of the glaze dispersant comprises the following steps: (1) adding an acrylic acid compound and an acrylic acid ester compound to dimethyl sulfoxide; (2) Adding vinyltriethoxysilane and N-vinylpyrrolidone; (3) adding azobisisobutyronitrile and an adhesion enhancer, stirring, and obtaining the glaze dispersant; The adhesion enhancer is at least one of methacryloxyethyl phosphate and γ-methacryloxypropyltrimethoxysilane.

2. The surface protective glaze for 3D printing rock slabs according to claim 1, characterized in that: The preparation method of the glaze dispersant comprises the following steps: (1) Add 50-60 g of acrylic acid compound and 20-30 g of acrylic acid ester compound to 30-50 g of dimethyl sulfoxide at 70-80 ° C and nitrogen atmosphere, and stir at 150-200 r / min to obtain acrylic acid prepolymer solution; (2) maintaining stirring at 150-200 r / min, adding 5-15 g of vinyltriethoxysilane dropwise to the acrylic acid prepolymer solution obtained in step (1) at a rate of 3-5 g / min, then adding 1-3 g of N-vinylpyrrolidone, and stirring at 100-300 r / min for 5-15 min to obtain a cross-linked acrylic acid polymer solution; (3) Add 1-3 g of azobisisobutyronitrile to the cross-linked acrylic polymer solution obtained in step (2), add 6-12 g of an adhesion enhancer while stirring at 150-200 r / min, stir at 70-80° C. and 100-300 r / min for 60-180 min, and cool to room temperature to obtain the glaze dispersant.

3. The surface protective glaze for 3D printing rock slabs according to claim 2, characterized in that: The acrylic compound is at least one of acrylic acid and methacrylic acid.

4. The surface protective glaze for 3D printing rock slabs according to claim 2, characterized in that: The acrylic acid ester compound is at least one of methyl methacrylate and butyl acrylate.

5. The surface protective glaze for 3D printing rock slabs according to any one of claims 1 to 4, characterized in that: The organic solvent is at least one of dimethyl sulfoxide, dimethylformamide, dimethylacetamide, ethyl acetate, acetone, and methyl ethyl ketone.

6. The surface protective glaze for 3D printing rock slabs according to any one of claims 1 to 4, characterized in that: The defoamer is at least one of BYK-052 defoamer, TEGO® Airex902W defoamer, Foamaster® 111 defoamer, and BYK-065 defoamer.

7. The surface protective glaze for 3D printing rock slabs according to any one of claims 1 to 4, characterized in that: The leveling agent is at least one of BYK-306 leveling agent, TEGO®Glide450 leveling agent, EFKA-3770 leveling agent, BYK-358N leveling agent, and TEGO®Flow375 leveling agent.

8. The surface protective glaze for 3D printing rock slabs according to any one of claims 1 to 4, characterized in that: The polyurethane is at least one of Estane® 5703 polyurethane, Desmopan® 9370A polyurethane, Texin® 985A polyurethane, Pellethane® 2363-80AE polyurethane, and Elastollan® 1180A polyurethane.

9. A method for preparing a surface protective glaze for 3D printed rock slabs according to any one of claims 1 to 8, characterized in that: The following steps are involved: The basic glaze, nano-alumina, organic solvent, defoamer, leveling agent, polyurethane, and glaze dispersant are added to a sand mill and ground evenly to obtain the surface protective glaze for 3D printing rock slabs.