Water-washing-resistant glass toughening ink with organic-inorganic dual heat rheological relay characteristic and preparation method thereof

Abstract

The invention discloses water-washing-resistant glass toughening ink with organic and inorganic dual heat rheological relay characteristics and a preparation method of the water-washing-resistant glass toughening ink, and belongs to the field of glass surface decoration materials, the water-washing-resistant glass toughening ink is prepared from the following components by weight: 30-65% of a photosensitive resin carrier system, 25-60% of a gradient sintering inorganic aggregate system, and 3-15% of a photoinitiator and auxiliary agent system; according to the invention, by introducing a thermal hysteresis anchoring component and constructing a gradient sintering inorganic aggregate system, the organic and inorganic thermal rheological relay of the whole process from room temperature curing, medium temperature pyrolysis to high temperature sintering is realized, the bonding empty window period of traditional ink in a temperature zone of 300-560 DEG C is filled, and pulverization, cracking and falling of an ink layer in the tempering process are avoided.

Description

Technical Field

[0001] This invention relates to the field of glass surface decorative materials, specifically to a water-resistant tempered glass ink with organic and inorganic dual thermorheological relay properties and its preparation method. Background Technology

[0002] Digital inkjet printing technology, with its advantages of flexible patterns, high production efficiency, and environmental friendliness, has been widely used in the glass decoration industry. However, adapting this technology to the complete glass deep processing flow, including high-pressure water washing, edge grinding, and tempering, places stringent requirements on the comprehensive performance of UV-cured inks, which existing ink systems are currently unable to meet. Specifically, the current mainstream UV-cured glass decoration inks mainly face the following interrelated technical problems:

[0003] 1. The inherent contradiction between immediate mechanical strength and high-temperature thermal behavior. To resist high-pressure water washing, the cured ink layer needs to possess high initial adhesion, cohesive strength, and hydrophobicity. This is usually achieved by increasing the functionality of monomers or adding additives, but this leads to excessively high cross-linking density of the cured network. During the rapid heating process in the subsequent tempering furnace, this rigid network accumulates enormous internal stress due to the difference in thermal expansion coefficients with the glass substrate. More importantly, when the temperature rises to the range where organic matter begins to decompose violently, the highly cross-linked network cannot effectively release stress through chain segment relaxation, easily inducing large-area cracking or detachment of the ink layer from the substrate in the early stages of sintering, rendering the excellent initial water-wash resistance meaningless.

[0004] 2. The kinetic mismatch between the thermal decomposition of organic carriers and the melting and sintering of inorganic fillers. The typical temperature window for glass tempering is 680-750℃, and it must be completed within minutes. During this process, the organic resins, monomers, and other carrier components in the ink typically complete pyrolysis and vaporization before 450℃, losing their binding function. Meanwhile, the glass powder, which forms the main body of the final decorative layer, usually has a softening point temperature above 560℃. Therefore, within this critical temperature range of approximately 450-560℃, the ink layer simultaneously loses effective support from the organic binder phase and fails to obtain liquid-phase flux from the inorganic molten phase, resulting in its structural strength being minimized. This bonding gap makes the ink layer highly susceptible to pulverization, displacement, or detachment under the influence of furnace airflow, mechanical vibration, and its own gravity—a phenomenon commonly referred to in the industry as sintering delamination. Existing technologies often only mitigate this by delaying the heating process and adding transition insulation steps, which directly conflicts with the rapid cycle requirements of efficient tempering processes.

[0005] 3. The contradiction between the controllability of the pyrolysis process and the optical quality of the final sintered layer. To achieve simultaneous completion with the tempering process, the ink must achieve complete and clean sintering at the tempering temperature. However, traditional UV systems based on acrylate monomers tend to experience random C-C bond breakage during high-temperature pyrolysis, generating a large number of free radical intermediates and unsaturated fragments. These substances are highly susceptible to further condensation, forming stable carbonaceous residues. As a result, the sintered decorative layer often retains a significant amount of carbon black, leading to a hazy, dull, and low-gloss coating, and may be accompanied by defects such as bubbles and pinholes. While forced oxidation can be achieved by introducing large amounts of oxygen or extending the high-temperature dwell time, this not only increases process complexity and energy consumption but may also adversely affect the glass substrate or furnace equipment.

[0006] Therefore, we propose a water-resistant tempered glass ink with organic-inorganic dual thermorheological relay properties and its preparation method to alleviate or solve the above problems.

[0007] The information disclosed above in this background section is only for enhancing the understanding of the background section of this invention, and therefore may include prior art that is not known to those skilled in the art. Summary of the Invention

[0008] To address the aforementioned technical problems, this invention provides a water-resistant tempered glass ink with dual organic-inorganic thermorheological relay properties and its preparation method, thereby solving the problems of poor water resistance, easy adhesion and delamination during tempering and sintering, high residual carbon content after sintering, and low gloss in the prior art.

[0009] To achieve the above objectives, the present invention provides a water-resistant tempered glass ink, which is made of the following components by weight percentage:

[0010] Photosensitive resin carrier system: 30-65%, wherein the photosensitive resin carrier system comprises a thermal hysteresis anchoring component and methacrylate monomers, wherein the thermal hysteresis anchoring component maintains a molten viscous flow state and a thermal weight loss rate of less than 60% in the temperature range of 200-450℃, and the methacrylate monomers are pyrolyzed in the temperature range of 280-420℃ through an α-methyl side chain removal mechanism.

[0011] Gradient sintering inorganic aggregate system: 25-60%, wherein the gradient sintering inorganic aggregate system comprises structural phase inorganic powder and fluxing phase inorganic powder with different softening point temperatures, the temperature difference between the two softening points ΔT≥40℃, and the fluxing phase is low softening point glass powder containing network breaking agent;

[0012] Photoinitiator and auxiliaries system: 3-15%;

[0013] The ink layer formed by UV curing has an adhesion grade of ≥4B after being washed with 3 bar water pressure for 30 seconds, and a residual carbon rate of less than 3% after sintering at 680℃-750℃.

[0014] Preferably, the thermal hysteresis anchoring component is selected from thermoplastic polymers with a weight-average molecular weight Mw of 8,000-150,000 and a 50% thermal weight loss temperature Td50 of higher than 360°C. The thermoplastic polymer includes at least one of modified acrylic resins, modified polyester resins, modified polyurethane resins, modified polyamide resins, modified cellulose resins, and modified polycarbonate resins.

[0015] The thermal hysteresis anchoring component accounts for 5-40% of the mass of the photosensitive resin carrier system, preferably 8-25%.

[0016] The methacrylate monomers account for 10-60% by mass in the photosensitive resin carrier system, preferably 15-45%; the pyrolysis mechanism of the methacrylate monomers in the temperature range of 280-420℃ is an α-methyl side chain removal reaction, generating volatile small molecule olefins and methacrylic acid, with a pyrolysis residual carbon rate of less than 5%.

[0017] Preferably, the methacrylate monomers include at least one of methacrylates having rigid side chains, methacrylates having hydrophobic side chains, and multifunctional methacrylates; the rigid side chains include at least one of alicyclic structures, aromatic ring structures, and cage structures; and the hydrophobic side chains include at least one of long-chain alkyl groups, branched alkyl groups, fluorinated alkyl groups, and silanized alkyl groups.

[0018] Preferably, the methacrylate with rigid side chains includes at least one of isobornyl methacrylate, tricyclodecane methacrylate, adamantane methacrylate, phenoxyethyl methacrylate, benzyl methacrylate, and POSS-modified methacrylate; the methacrylate with hydrophobic side chains includes at least one of lauryl methacrylate, stearyl methacrylate, isooctyl methacrylate, and perfluorooctyl ethyl methacrylate.

[0019] Preferably, the photosensitive resin carrier system further comprises oxidizing functional group monomers, which release oxidizing substances during pyrolysis to promote the oxidative decomposition of organic residues; the oxidizing functional group monomers include at least one of nitro-containing monomers, peroxy-containing monomers, and monomers containing high-valence metal oxides.

[0020] The nitro-containing monomer includes at least one of nitroacrylate, nitromethacrylate, nitrostyrene, and nitrovinyl ether; the oxidizing functional group monomer accounts for 0.1-8% of the mass of the photosensitive resin carrier system, preferably 0.5-5%.

[0021] In the gradient sintering inorganic aggregate system, the softening point temperature range of the fluxing phase is 400-520℃, and the softening point temperature range of the structural phase is 550-680℃; the mass percentage of the fluxing phase in the inorganic aggregate system is 3-40%, preferably 8-28%.

[0022] Preferably, the network breaking agent includes at least one of alkali metal oxides, alkaline earth metal oxides, heavy metal oxides, halides, borates, and phosphates; the mass percentage of the network breaking agent in the flux phase is 15-65%.

[0023] Preferably, the alkali metal oxide includes at least one of lithium oxide, sodium oxide, and potassium oxide; the alkaline earth metal oxide includes at least one of magnesium oxide, calcium oxide, strontium oxide, and barium oxide; and the heavy metal oxide includes at least one of bismuth oxide, lead oxide, and zinc oxide.

[0024] Preferably, the preparation method of the flux phase is as follows: the network forming agent and the network breaking agent are mixed at a mass ratio of (35:65)-(85:15), melted and held at a temperature of 800-1200℃, quenched and then pulverized; the network forming agent includes at least one of silicon oxide, boron oxide, aluminum oxide, zirconium oxide, titanium oxide, tin oxide and phosphorus oxide.

[0025] Preferably, the structural phase comprises a high-temperature stable inorganic powder, which includes at least one of high-temperature glass powder, ceramic powder, and high-temperature resistant inorganic pigment; the high-temperature glass powder comprises a combination of two or more of silicon oxide, aluminum oxide, zirconium oxide, titanium oxide, and tin oxide.

[0026] Preferably, the gradient sintering inorganic aggregate system further includes high-temperature resistant inorganic pigments, wherein the inorganic pigments include at least one of spinel structure metal oxides, perovskite structure metal oxides, encapsulated composite pigments, and solid solution composite pigments, and the inorganic pigments account for 5-30% of the total composition of the ink by mass.

[0027] Preferably, the photoinitiator and auxiliary agent system includes at least one of a free radical photoinitiator, a dispersant, a leveling agent, an antifoaming agent, a coupling agent, and an antioxidant; the free radical photoinitiator accounts for 2-8% of the total mass.

[0028] The glass transition temperature (Tg) of the cured ink is 40-95℃, the tensile strength of the cured film is ≥15 MPa, and the elongation at break is 8-45%; the water contact angle of the cured film is ≥75°, preferably ≥85°.

[0029] After the ink is sintered at a temperature of 680-750℃, the residual carbon content of the ink layer is less than 3%, and the gloss of the sintered ink layer is ≥75 GU, preferably ≥82 GU.

[0030] A method for preparing water-resistant tempered glass ink includes the following steps:

[0031] S1. Mix the structural phase powder and the fluxing phase powder in a set ratio, add a dispersion medium accounting for 15-40% of the total amount of the mixed powder, and grind in a ball mill or sand mill at a speed of 400-1000 rpm for 10-30 hours to obtain an inorganic aggregate pre-dispersion, and control the D50 particle size after grinding to be 0.3-1.2 micrometers;

[0032] S2. Dissolve or disperse the thermal hysteresis anchoring component in a photocurable monomer mixture containing the methacrylate monomer, add a photoinitiator, and stir at 50-80°C until it is uniformly transparent or semi-transparent to obtain a photosensitive resin carrier mixture;

[0033] S3. Mix the inorganic aggregate pre-dispersion prepared in step S1 with the photosensitive resin carrier mixture prepared in step S2 in a certain proportion, add dispersant, leveling agent and other additives, and grind in a ball mill or sand mill at a speed of 200-600 rpm for 1-5 hours.

[0034] S4. The mixture obtained in step S3 is filtered through a filter membrane with a pore size of 0.5-2.0 micrometers and then degassed under vacuum to obtain the glass decorative ink.

[0035] Preferably, the dispersion medium in step S1 is selected from at least one of methacrylic acid monomer, acrylic acid monomer, photocurable diluent, and organic solvent.

[0036] Preferably, the dissolution temperature of the thermally hysteretic anchoring component in step S2 is controlled within the range of 20-60°C above its glass transition temperature.

[0037] Preferably, in step S2, the oxidizing functional group monomer is also added, and the oxidizing functional group monomer is premixed with the methacrylate monomer before the photoinitiator is added.

[0038] Compared with the prior art, the beneficial effects of the present invention are:

[0039] This invention introduces thermally delayed anchoring components and constructs a gradient sintering inorganic aggregate system, realizing organic-inorganic thermal rheological relay throughout the entire process from room temperature curing, medium temperature pyrolysis to high temperature sintering. This fills the bonding gap of traditional inks in the 300-560℃ temperature range and eliminates the powdering, cracking and peeling of the ink layer during the tempering process.

[0040] This invention employs a photosensitive resin system with methacrylate monomers as the core, utilizing its unique α-methyl side chain ordered pyrolysis mechanism and combining it with the self-oxidation effect of oxidizing functional group monomers to reduce the residual carbon rate of the ink layer after rapid tempering and sintering to below 3%, while simultaneously increasing the sintering gloss to above 82 GU, thus improving the decorative effect.

[0041] This invention utilizes the inherent high hydrophobicity of methacrylate monomers and a reasonable system design to achieve a water contact angle greater than 85° for the UV-cured ink layer. Even under 3-5 bar high-pressure water washing, it can still maintain excellent adhesion at the 4B-5B level, ensuring that the printed products can successfully pass through the forced water washing pretreatment process.

[0042] The ink system of this invention can complete the complete decomposition and oxidation of organic matter and the melting and densification of inorganic phase within a short time of tens of seconds to several minutes within the standard tempering temperature range of 680-750℃. It does not require independent pre-sintering or a special oxygen-rich atmosphere, which simplifies the process, improves production efficiency and reduces energy consumption.

[0043] The above overview is for illustrative purposes only and is not intended to be limiting in any way. In addition to the illustrative aspects, embodiments, and features described above, further aspects, embodiments, and features of the invention will become readily apparent from the accompanying drawings and the following detailed description. Attached Figure Description

[0044] Figure 1 This is a flowchart illustrating the preparation method of the water-resistant tempered glass ink of the present invention. Detailed Implementation

[0045] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. It should be noted that the drawings are schematic and not illustrated to scale. For clarity and convenience, the relative sizes and proportions of the parts shown in the drawings have been exaggerated or reduced in size. Any size is only illustrative and not limiting.

[0046] Example 1

[0047] Water-resistant tempered glass ink, by weight percentage, is composed of the following components:

[0048] Thermally hysteresis anchoring component modified acrylic resin Mw approx. 30000: 12%; isobornyl methacrylate: 20%; lauryl methacrylate: 8%; trimethylolpropane trimethacrylate: 10%; auxiliary monomer pentaerythritol triacrylate: 5%; nitro-containing monomer nitroacrylate: 2%; photoinitiator TPO: 4%; fluxing phase powder softening point 480℃: 10%; structural phase powder softening point 620℃: 20%; high-temperature resistant inorganic black pigment spinel structure: 8%; dispersant: 3%; leveling agent: 1.5%; coupling agent: 0.5%; other additives: make up to 100% as needed.

[0049] A method for preparing water-resistant tempered glass ink includes the following steps:

[0050] S1. Mix 10% fluxing phase powder, 20% structural phase powder, and 8% inorganic pigment, add 12% isobornyl methacrylate as a dispersion medium, and grind in a ball mill at 650 rpm for 18 hours to obtain an inorganic aggregate predispersant. The D50 particle size was measured to be 0.55 micrometers.

[0051] S2. Dissolve 12% modified acrylic resin in a mixture of 8% isoborneol methacrylate, 8% lauryl methacrylate, 10% trimethylolpropane trimethacrylate, and 5% pentaerythritol triacrylate. Add 2% nitro monomer and 4% photoinitiator TPO. Stir at 65°C for 2 hours until uniform and transparent to obtain a photosensitive resin carrier mixture.

[0052] S3. Mix the inorganic aggregate pre-dispersion obtained in step S1 with the photosensitive resin carrier mixture obtained in step S2, add 3% dispersant, 1.5% leveling agent, 0.5% coupling agent and other additives, and grind in a ball mill at 400 rpm for 3 hours.

[0053] S4. Filter the mixture obtained in step S3 through a 1.0-micron pore size filter membrane and degas it under vacuum for 30 minutes to obtain the finished ink.

[0054] Performance testing of the obtained finished ink:

[0055] The ink is printed onto the surface of a glass substrate using inkjet printing. The UV lamp power is 120 W / cm, the curing speed is 15m / min, and the ink layer thickness after curing is approximately 8 micrometers.

[0056] Water contact angle test: The water contact angle of the cured ink layer is 89°, which is significantly higher than the 68° of the acrylic system.

[0057] Water wash resistance test: After curing, the glass was rinsed with 3 bar water pressure for 30 seconds, and the adhesion was tested using the cross-cut adhesion test. The result was 5B grade, with no peeling. After rinsing with 5 bar water pressure for 60 seconds, the adhesion was still 5B grade.

[0058] Tempering and sintering test: The cured glass was treated in a tempering furnace at 700℃ with a heating rate of about 50℃ / min and a holding time of 60 seconds. After quenching, the ink layer was observed to be intact, without cracks or desorption, with a gloss of 92 GU, which is significantly higher than the 65 GU of the acrylic system, and an adhesion grade of 0.

[0059] Carbon residue test: The carbon residue of the ink layer after sintering was 1.8%, which is much lower than the 18% of the acrylate system, as determined by thermogravimetric analysis.

[0060] Example 2 differs from Example 1 in that the flux phase accounts for 18% of the inorganic aggregate system, and the structural phase accounts for 12%.

[0061] Performance test results: water contact angle 88°, water washability 5B grade, adhesion after tempering grade 0, gloss 90 GU, carbon residue rate 2.1%, excellent performance.

[0062] Example 3 differs from Example 1 in that the fluxing phase accounts for 5% and the structural phase accounts for 25%.

[0063] Performance test results: water contact angle 89°, water wash resistance 5B grade, but slight stress cracks were observed at the edge of the ink layer after tempering, gloss 85 GU, indicating that the gradient sintering effect is weakened when the flux ratio is too low.

[0064] Example 4 differs from Example 1 in that the proportion of the thermally hysteretic anchoring component is adjusted to 28%.

[0065] Performance test results: water contact angle 92°, water washability 5B grade, adhesion after tempering grade 0, gloss 91 GU, but the UV curing speed decreased slightly, and the UV lamp power needs to be increased to 150 W / cm to achieve the same curing effect.

[0066] Example 5 differs from Example 1 in that it does not add nitro monomers, but instead uses an equal amount of isobornyl methacrylate.

[0067] Performance test results: water contact angle 89°, washability rating 5B, adhesion rating 0 after tempering, gloss 86 GU, and carbon residue rate 4.5%. This indicates that nitro monomers have a significant effect on reducing carbon residue and improving gloss.

[0068] Example 6 differs from Example 1 in that no thermal hysteresis anchoring component is added; instead, an equal amount of isobornyl methacrylate is used instead.

[0069] Performance test results: Water contact angle 90°, water wash resistance 5B grade, but slight powdering of the ink layer was observed when the tempering furnace temperature reached 450℃, and partial peeling occurred at 550℃, with a gloss of 78 GU. This indicates that the thermal hysteresis anchoring component is still important for solving the bonding gap problem, but due to the controllable pyrolysis characteristics of methacrylate, the degree of peeling is significantly less than that of the acrylate system.

[0070] Comparative Example 1: Traditional Acrylic Ester System

[0071] It uses commercially available conventional UV glass ink, whose main components are isoborneol acrylate, trimethylolpropane triacrylate, conventional glass powder with a softening point of 580℃, inorganic pigments, etc. It does not contain thermal hysteresis anchoring components, does not use a gradient sintering system, and does not contain nitro monomers.

[0072] Performance test results: Water contact angle 68°; after UV curing, water wash resistance rating 2B; significant peeling occurred after 3 bar water pressure rinsing for 30 seconds. After tempering, the ink layer experienced large-area desorption and severe cracking, with a gloss level of only 55 GU and a carbon residue rate of 19%, rendering it unusable.

[0073] Comparative Example 2 uses isobornyl acrylate instead of isobornyl methacrylate, and the other components are the same as in Example 1.

[0074] Performance test results: Water contact angle 70°; after UV curing, water wash resistance grade 4B; slight peeling after 3 bar water pressure rinsing for 30 seconds. After tempering, adhesion grade 2, slight cracking, gloss 68 GU, and carbon residue 15%. This indicates that even with gradient sintering and thermally delayed components, the overall performance of the acrylate system is still significantly inferior to that of the methacrylate system.

[0075] Comparative Example 3 uses methacrylate monomers, but does not employ a gradient sintering system; it uses only a single glass powder with a softening point of 580°C.

[0076] Performance test results: water contact angle 88°, water wash resistance 5B grade, but after tempering, the ink layer showed significant powdering and desorption in the 400℃-550℃ range, with a gloss level of 75 GU. This indicates that the gradient sintering system remains important for solving the bonding gap problem. Experimental results are shown in Table 1.

[0077] Table 1

[0078] serial number System characteristics Water-resistant (3 bar, 30 seconds) Water contact angle Adhesion after sintering Sintering gloss (GU) Residual carbon rate Overall evaluation Example 1 Complete Invention Scheme 5B 89° Level 0 92 1.8% excellent Example 2 High fluxing phase ratio 5B 88° Level 0 90 2.1% excellent Example 3 Low fluxing phase ratio 5B 89° Grade 1 (micro-crack) 85 2.3% good Example 4 High thermal hysteresis components 5B 92° Level 0 91 1.9% Excellent (curing is slightly slower) Example 5 nitro monomers 5B 89° Level 0 86 4.5% good Comparative Example 1 Traditional acrylates 2B 68° Completely detached 55 19% Unqualified Comparative Example 2 acrylate architecture 4B 70° Level 2 (Cracked) 68 15% generally Comparative Example 3 Single glass powder 5B 88° Level 3 (Powdering) 75 3.5% generally

[0079] As can be seen from the above embodiments and comparative examples, the present invention achieves excellent water erosion resistance of ink immediately after printing through the multiple synergistic effects of thermal hysteresis anchoring components, controlled pyrolysis of methacrylate, gradient sintering of inorganic aggregates, and optional oxidizing functional group monomers. Furthermore, it achieves continuous and complete organic-inorganic thermal rheological relay during the rapid tempering sintering process, ultimately obtaining a high-quality sintered ink layer with excellent adhesion, high gloss, and extremely low carbon residue.

[0080] In the description of this specification, the references to terms such as "one embodiment," "some embodiments," "example," "specific example," or "some examples," etc., indicate that a specific feature, structure, material, or characteristic described in connection with that embodiment or example is included in at least one embodiment or example of the present invention. In this specification, the illustrative expressions of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in one or more embodiments or examples. Moreover, without contradiction, those skilled in the art can combine and integrate the different embodiments or examples described in this specification, as well as the features of different embodiments or examples.

[0081] Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art can still modify the technical solutions described in the foregoing embodiments or make equivalent substitutions for some of the technical features. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A water-resistant tempered glass ink, characterized in that, It is made from the following components by weight percentage: Photosensitive resin carrier system: 30-65%, wherein the photosensitive resin carrier system comprises a thermal hysteresis anchoring component and methacrylate monomers, wherein the thermal hysteresis anchoring component maintains a molten viscous flow state and a thermal weight loss rate of less than 60% in the temperature range of 200-450℃, and the methacrylate monomers are pyrolyzed in the temperature range of 280-420℃ through an α-methyl side chain removal mechanism. Gradient sintering inorganic aggregate system: 25-60%, wherein the gradient sintering inorganic aggregate system comprises structural phase inorganic powder and fluxing phase inorganic powder with different softening point temperatures, the temperature difference between the two softening points ΔT≥40℃, and the fluxing phase is low softening point glass powder containing network breaking agent; Photoinitiator and auxiliaries system: 3-15%; The ink layer formed by UV curing has an adhesion grade of ≥4B after being washed with 3 bar water pressure for 30 seconds, and a residual carbon rate of less than 3% after sintering at 680℃-750℃.

2. The water-resistant tempered glass ink according to claim 1, characterized in that, The thermal hysteresis anchoring component is a thermoplastic polymer with a weight-average molecular weight of 8,000-150,000, and its temperature Td50, which has a 50% thermal weight loss, is higher than 360°C; the thermal hysteresis anchoring component accounts for 5-40% of the mass of the photosensitive resin carrier system.

3. The water-resistant tempered glass ink according to claim 1, characterized in that, The methacrylate monomers account for 10-60% of the mass of the photosensitive resin carrier system; the methacrylate monomers are selected from at least one of methacrylates with rigid side chains, methacrylates with hydrophobic side chains, and polyfunctional methacrylates. The methacrylates with rigid side chains include at least one of isobornyl methacrylate, tricyclodecane methacrylate, adamantane methacrylate, phenoxyethyl methacrylate, benzyl methacrylate, and POSS-modified methacrylate. The methacrylates having hydrophobic side chains include at least one of lauryl methacrylate, stearyl methacrylate, isooctyl methacrylate, and perfluorooctyl ethyl methacrylate.

4. The water-resistant tempered glass ink according to claim 1, characterized in that, The photosensitive resin carrier system further comprises 0.1-8% by mass of oxidizing functional group monomers, wherein the oxidizing functional group monomers are selected from at least one of nitro monomers, peroxy monomers and monomers containing high-valence metal oxides; wherein the nitro monomers include at least one of nitroacrylates, nitromethacrylates, nitrostyrene and nitrovinyl ethers.

5. The water-resistant tempered glass ink according to claim 1, characterized in that, The softening point temperature of the fluxing phase inorganic powder is 400-520℃, and the softening point temperature of the structural phase inorganic powder is 550-680℃; the mass ratio of the fluxing phase inorganic powder in the gradient sintering inorganic aggregate system is 3-40%.

6. The water-resistant tempered glass ink according to claim 1, characterized in that, The network breaking agent is selected from at least one of alkali metal oxides, alkaline earth metal oxides, heavy metal oxides, halides, borates, and phosphates.

7. The water-resistant tempered glass ink according to claim 1, characterized in that, The gradient sintering inorganic aggregate system also includes high-temperature resistant inorganic pigments, which account for 5-30% of the total mass of the ink. The high-temperature resistant inorganic pigments include at least one of spinel structure metal oxides, perovskite structure metal oxides, encapsulated composite pigments, and solid solution composite pigments.

8. The water-resistant tempered glass ink according to claim 1, characterized in that, The photoinitiator and additive system includes at least one of free radical photoinitiator, dispersant, leveling agent, defoamer, coupling agent, and antioxidant; the free radical photoinitiator accounts for 2-8% of the total mass of the ink.

9. A method for preparing the water-resistant tempered glass ink according to any one of claims 1-8, characterized in that, Includes the following steps: S1. Mix the structural phase inorganic powder with the fluxing phase inorganic powder, add a dispersion medium and grind to obtain an inorganic aggregate predispersion; The dispersion medium is selected from at least one of methacrylate monomers, acrylate monomers, photocurable diluents, and organic solvents; S2. Dissolve or disperse the thermally hysteretic anchoring component in a mixture containing methacrylate monomers, with a D50 particle size of 0.3-1.2 micrometers, and add a photoinitiator to obtain a photosensitive resin carrier mixture; S3. Mix the inorganic aggregate predispersant with the photosensitive resin carrier mixture, add additives and grind; S4. Filter and degas the ground mixture to obtain the glass tempered ink.

10. The preparation method according to claim 9, characterized in that, When preparing the inorganic aggregate predispersant, the amount of the dispersion medium added is 15-40% of the total weight of the mixed powder, the grinding speed is 400-1000 rpm, and the grinding time is 10-30 hours; the preparation of the photosensitive resin carrier mixture is carried out at 50-80℃; the fine grinding speed after mixing is 200-600 rpm, and the grinding time is 1-5 hours; the filtration adopts a filter membrane with a pore size of 0.5-2.0 micrometers.

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