High borosilicate glass printing ink and sintering and curing process thereof

Abstract

The invention discloses high borosilicate glass printing ink and a sintering and curing process of the high borosilicate glass printing ink. Comprising the following solid components: 12 to 18 parts of bismuth silicate crystal, 8 to 12 parts of Bi2O3-B2O3-SiO2 series glass, 1 to 3 parts of zinc oxide, 5 to 7 parts of boric oxide, 20 to 25 parts of copper oxide, 1 to 3 parts of chromic oxide, 20 to 25 parts of rosin modified phenolic resin, 1 to 3 parts of fluxing agent calcium fluoride or 5 to 15 parts of lithium carbonate, 20 to 25 parts of zirconium oxide coated copper chromite black, 0.3 to 0.5 part of aluminum oxide and 1 to 2 parts of titanium dioxide. The invention has the advantages that the accurate regulation and control of CTE and the chemical durability are combined, and a stable and reliable ink solution with excellent performance is provided for the industries of building curtain walls, automobile glass and the like.

Description

Technical Field

[0001] The invention relates to the technical field of surface decoration and functional processing of high borosilicate glass, and in particular to a high borosilicate glass ink and a sintering and curing process thereof. Background Art

[0002] In the construction, automobile and other industries, high borosilicate glass has become a popular material due to its excellent thermal stability and weather resistance. However, the inks that match it have many problems that need to be solved:

[0003] CTE mismatch: The glass powder used in traditional borosilicate glass ink has a CTE of 4.1×10 -6 ~4.8×10 -6 / ℃, which is significantly higher than low expansion borosilicate glass (3.0±0.1×10 -6 / ℃). This significant difference makes the interface between ink and glass very prone to cracking after sintering. This problem is particularly prominent in scenes such as building curtain walls that are used for a long time and the ambient temperature fluctuates frequently. Interface cracking not only seriously affects the overall performance of the glass and reduces its aesthetics, but also greatly shortens the service life of the glass and increases the cost of replacement and maintenance.

[0004] Copper chrome black has poor acid and alkali resistance and changes color at high temperature: The copper chrome black pigment in traditional inks has poor color stability under high temperature conditions and is prone to color change. At the same time, according to the ASTM C274-18 standard, its acid resistance can only reach level 4, which is difficult to meet the corrosion resistance requirements of automotive glass exposed to complex external environments for a long time. When automotive glass is corroded by acidic substances, the change in ink color not only affects the appearance, but may also interfere with the driver's vision, posing certain safety hazards.

[0005] Process limitations: Most current processes rely on a single glass phase, which poses a huge challenge in balancing CTE matching and chemical durability. This process limitation severely restricts the expanded application of high-borosilicate glass inks in high-performance fields and has become a key bottleneck restricting the development of the industry. Summary of the invention

[0006] The purpose of the present invention is to provide a high borosilicate glass ink and a sintering and curing process thereof, firstly, to solve the problem of interface cracking caused by the mismatch between the CTE of the ink and the low expansion borosilicate glass; secondly, to enhance the stability of the copper chrome black pigment at high temperature and improve its acid and alkali resistance; thirdly, to break through the limitations of traditional processes, achieve both precise control of CTE and chemical durability, and provide an excellent, stable and reliable ink solution for industries such as building curtain walls and automotive glass.

[0007] The above technical objectives of the present invention are achieved through the following technical solutions:

[0008] A high borosilicate glass ink, characterized in that, by mass parts, it comprises the following solid components: 12-18 parts of bismuth silicate crystals, 8-12 parts of Bi2O3-B2O3-SiO2 system glass, 1-3 parts of zinc oxide, 5-7 parts of boron oxide, 20-25 parts of copper oxide, 1-3 parts of chromium oxide, 20-25 parts of rosin modified phenolic resin, 1-3 parts of flux calcium fluoride or 5-15 parts of lithium carbonate, 20-25 parts of zirconia-coated copper chromite black, 0.3-0.5 parts of alumina, and 1-2 parts of titanium dioxide.

[0009] Preferably, the spheroid fineness of the bismuth silicate crystals, Bi2O3-B2O3-SiO2 system glass and copper oxide is all 300 mesh.

[0010] Preferably, the preparation method of the zirconia-coated copper chromite black is as follows: First, prepare a zirconium oxychloride solution with a concentration of 0.1-0.3 mol / L, add the copper chromite black pigment to the zirconium oxychloride solution according to the solid-liquid volume-mass ratio of 1 g:10 mL - 1 g:15 mL, stir evenly at a temperature of 40-60 °C, then slowly dropwise add an ammonia water solution with a pH value of 8-10, control the dropping speed at 2-5 mL / min, and continuously stir at the same time. Keep the system temperature constant during the reaction, the reaction time is 2-4 hours. After the reaction is completed, filter and wash with deionized water for multiple times until no chloride ion impurities can be detected in the washing liquid. Finally, dry at 80-120 °C, and then add 2 wt% - 4 wt% of high-temperature pearlescent powder and calcine at 600 °C - 800 °C, and the calcination time is 1-3 h.

[0011] A sintering and curing process for a high borosilicate glass ink, characterized in that it comprises the following steps:

[0012] Accurately weigh each solid component according to mass parts and mix them, then add a dispersant and a bonding promoter and place them in a stirring container, and stir slowly at 30 r / min at room temperature for 30 min to form a slurry evenly;

[0013] After stirring is completed, add an ultrasonic-assisted liquid, and turn on the ultrasonic device to further mix and disperse;

[0014] After ultrasonic treatment, dry grinding and air flow grinding are carried out in sequence, control the final particle size and performance of the final slurry to meet the standards, and obtain the high borosilicate glass ink after filtration;

[0015] Pour the high borosilicate glass ink into a mold, put it into a sintering furnace, and complete sintering and curing in a gradient heating manner.

[0016] Preferably, the dispersant is fatty acid polyethylene glycol ester, and the addition amount is 0.5% - 1.5% of the total mass of the solid components.

[0017] Preferably, the adhesion promoter is a silane coupling agent, and the addition amount is 1% - 3% of the total mass of the solid components.

[0018] Preferably, the ultrasonic-assisted solution is a mixed solution of ethanol and water with a volume ratio of 1:1. The addition amount of the ultrasonic-assisted solution is 30% - 50% of the total volume of the slurry, the ultrasonic power is 500 W, and the ultrasonic time is 60 min.

[0019] Preferably, the dry grinding equipment is a planetary ball mill, the grinding medium is zirconia balls, the ball-to-material ratio is controlled at 5:1 - 8:1, the rotation speed is set at 200 - 300 r / min, and the grinding time is 3 - 5 hours to initially bring the slurry to a particle size range of 100 - 200 μm. The jet mill equipment is a flat jet mill, the compressed air pressure is controlled at 0.6 - 0.8 MPa, and the feeding speed is 5 - 10 kg / h.

[0020] Preferably, the final particle size of the final slurry is 3 - 15 μm, the viscosity is 1000 - 3000 mPa·s, the light transmittance is higher than 85%, the haze is lower than 5%, the adhesion of the slurry on the glass substrate is not less than 5B tested by the cross-cut method, and the filtration accuracy is 100 μm.

[0021] Preferably, the gradient temperature increase is specifically as follows: heating at a rate of 2 °C / min to 150 °C and holding for 30 min; then heating at a rate of 3 °C / min to 350 °C and holding for 30 min; finally heating at a rate of 5 °C / min to 500 °C and holding for 60 min, with nitrogen protection throughout the process.

[0022] In summary, the present invention has the following beneficial effects:

[0023] 1. By adding a specific proportion of calcium fluoride or lithium carbonate as a flux in the ink formulation, the present invention can accurately control the melting temperature of the ink within the range of 440 °C - 470 °C, effectively inhibiting the crystallization phenomenon of the glass powder. In practical applications, the ink with an appropriate amount of flux added has significantly better fluidity during the sintering process than the traditional ink without addition. The edges of the printed pattern are clearer and smoother, and the surface quality is significantly improved, greatly enhancing the stability and uniformity of the ink.

[0024] 2. The present invention uses an advanced zirconia coating technology to treat copper chromite black. The color difference ΔE of zirconia-coated copper chromite black is less than 1.5, while the color difference of untreated copper chromite black is as high as more than 3.0. This method can significantly reduce the color change phenomenon of copper chromite black at high temperatures, ensuring that the ink color remains stable under various harsh conditions. At the same time, tested according to the ASTM C274 - 18 standard, its acid resistance is improved to level 4 or above, effectively guaranteeing the durability of automotive glass under complex road conditions and changing climates.

[0025] 3. The present invention finely adjusts the composition ratio of the Bi2O3-B2O3-SiO2 system glass and introduces ZrO2 low-melting-point glass. Through the synergistic effect between multiple glass phases, the precise control of the CTE of the ink is realized. Finally, the CTE of the ink is successfully reduced to 3.0×10 -6 / °C, and the matching error with the substrate is less than 5%. Compared with traditional inks, the matching degree with glass is increased by more than 30%, greatly enhancing the bonding force between the two and effectively preventing interface problems caused by temperature changes.

[0026] 4. The present invention innovatively combines the airflow mill and dry grinding process. Compared with the traditional single grinding method, the composite grinding improves the fineness of the ink by about 40% and reduces the energy consumption by nearly 30%. The finer and more uniform particles help to improve the printing resolution, improve the contact state between the ink and the glass substrate at the micro level, lay a good foundation for subsequent sintering and curing, and the ink coating prepared by composite grinding is denser and more uniform, significantly improving the product quality.

[0027] 5. The present invention adopts a gradient heating method in the sintering stage to induce the formation of columnar crystals. Practical tests show that compared with the traditional process, the scratch resistance value of the ink is greater than 20 N, and the wear resistance is improved by about 50%. Specific Embodiments

[0028] The following further describes the specific embodiments of the present invention. This embodiment does not constitute a limitation to the present invention.

[0029] Example 1

[0030] The preparation method of zirconia-coated copper chromite black is as follows: First, prepare a zirconium oxychloride solution with a concentration of 0.1 mol / L. Add copper chromite black pigment to the zirconium oxychloride solution according to the solid-liquid volume-mass ratio of 1 g:10 mL, stir evenly at a temperature of 50 °C, then slowly add an ammonia water solution with a pH value of 9, control the dropping speed at 3 mL / min, and continuously stir while maintaining the system temperature constant during the reaction. The reaction time is 3 hours. After the reaction, filter and wash with deionized water multiple times until no chloride ion impurities are detected in the washing solution. Finally, dry at 80 °C, and then add 2 wt% of high-temperature pearlescent powder and calcine at 800 °C for 1 h.

[0031] Example 2

[0032] A high borosilicate glass ink, calculated according to mass parts, includes the following solid components: 12 parts of bismuth silicate crystals, 12 parts of Bi2O3-B2O3-SiO2 system glass, 3 parts of zinc oxide, 7 parts of boron oxide, 20 parts of copper oxide, 1 part of chromium oxide, 20 parts of rosin-modified phenolic resin, 1 part of flux calcium fluoride, 20 parts of zirconia-coated copper chromite black, 0.5 part of alumina, and 1 part of titanium dioxide. The spheroidal fineness of bismuth silicate crystals, Bi2O3-B2O3-SiO2 system glass and copper oxide is all 300 mesh.

[0033] A sintering and curing process for a high borosilicate glass ink includes the following steps:

[0034] Accurately weigh each solid component according to mass parts and mix them, then add a dispersant and a bonding promoter and place them in a stirring container, and stir slowly at 30 r / min at room temperature for 30 min to uniformly form a slurry;

[0035] After stirring, add an ultrasonic-assisted liquid and turn on the ultrasonic device to further mix and disperse;

[0036] After ultrasonic treatment, dry grinding and air jet grinding are carried out in sequence. Control the final particle size of the final slurry to be 3 - 15 μm, the viscosity to be 1000 - 3000 mPa·s, the light transmittance to be higher than 85%, the haze to be lower than 5%. Use the cross-cut method to test that the adhesion of the slurry on the glass substrate is not less than 5B. After passing through a 100 μm filter, a high borosilicate glass ink is obtained;

[0037] Pour the high borosilicate glass ink into a mold, put it into a sintering furnace, and complete sintering and curing in a gradient heating manner.

[0038] The dispersant is fatty acid polyethylene glycol ester, and the addition amount is 1.5% of the total mass of the solid components.

[0039] The bonding promoter is a silane coupling agent, and the addition amount is 1% of the total mass of the solid components.

[0040] The ultrasonic-assisted solution is a mixed solution of ethanol and water with a volume ratio of 1:1. The addition amount of the ultrasonic-assisted solution is 50% of the total volume of the slurry, the ultrasonic power is 500 W, and the ultrasonic time is 60 min.

[0041] The dry grinding equipment selects a planetary ball mill, the grinding medium is zirconia balls, the ball-to-material ratio is controlled at 5:1, the rotation speed is set at 300 r / min, and the grinding time is 3 hours to make the slurry initially reach a particle size range of 100 - 200 μm. The air jet grinding equipment selects a flat air jet mill, the compressed air pressure is controlled at 0.6 MPa, and the feeding speed is 10 kg / h.

[0042] The temperature increase in a gradient manner is specifically as follows: The temperature is increased to 150 °C at a rate of 2 °C / min and held for 30 min; then it is increased to 350 °C at a rate of 3 °C / min and held for 30 min; finally, it is increased to 500 °C at a rate of 5 °C / min and held for 60 min. Nitrogen is introduced throughout the process for protection.

[0043] Example 3

[0044] A high-borosilicate glass ink, by mass parts, includes the following solid components: 18 parts of bismuth silicate crystals, 10 parts of Bi2O3-B2O3-SiO2-based glass, 2 parts of zinc oxide, 5 parts of boron oxide, 22 parts of copper oxide, 2 parts of chromium oxide, 22 parts of rosin-modified phenolic resin, 2 parts of flux calcium fluoride, 25 parts of copper-chrome black coated with zirconia, 0.3 part of alumina, and 1 part of titanium dioxide. The spheroid fineness of bismuth silicate crystals, Bi2O3-B2O3-SiO2-based glass, and copper oxide is all 300 mesh.

[0045] A sintering and curing process for a high-borosilicate glass ink includes the following steps:

[0046] Accurately weigh each solid component according to mass parts and mix them, then add a dispersant and a bonding promoter and place them in a stirring container, and stir slowly at 30 r / min for 30 min at room temperature to uniformly form a slurry;

[0047] After stirring, add an ultrasonic-assisted liquid and turn on the ultrasonic device to further mix and disperse;

[0048] After ultrasonic treatment, dry grinding and air jet grinding are carried out in sequence. Control the final particle size of the final slurry to be 3 - 15 μm, the viscosity to be 1000 - 3000 mPa·s, the light transmittance to be higher than 85%, the haze to be lower than 5%. The adhesion of the slurry on the glass substrate is tested by the cross-cut method and is not lower than 5B. After passing through a 100 μm filter, a high-borosilicate glass ink is obtained;

[0049] Pour the high-borosilicate glass ink into a mold, place it in a sintering furnace, and complete sintering and curing in a gradient temperature increase manner.

[0050] The dispersant is fatty acid polyethylene glycol ester, and the addition amount is 0.5% of the total mass of the solid components.

[0051] The bonding promoter is a silane coupling agent, and the addition amount is 1% of the total mass of the solid components.

[0052] The ultrasonic-assisted solution is a mixed solution of ethanol and water with a volume ratio of 1:1. The addition amount of the ultrasonic-assisted solution is 50% of the total volume of the slurry, the ultrasonic power is 500 W, and the ultrasonic time is 60 min.

[0053] For the dry grinding equipment, a planetary ball mill is selected, with zirconia balls as the grinding medium. The ball-to-material ratio is controlled at 8:1, the rotation speed is set at 300 r / min, and the grinding time is 3 hours to initially bring the slurry to a particle size range of 100 - 200 μm. For the jet mill equipment, a flat jet mill is selected, with the compressed air pressure controlled at 0.6 MPa and the feeding speed at 5 kg / h.

[0054] The gradient temperature increase is specifically as follows: Heat up at a rate of 2 °C / min to 150 °C and hold for 30 min; then heat up at 3 °C / min to 350 °C and hold for 30 min; finally heat up at 5 °C / min to 500 °C and hold for 60 min, with nitrogen gas passed through for protection throughout the process.

[0055] Example 4

[0056] A high borosilicate glass ink, by mass parts, includes the following solid components: 18 parts of bismuth silicate crystal, 12 parts of Bi2O3 - B2O3 - SiO2 system glass, 2 parts of zinc oxide, 6 parts of boron oxide, 24 parts of copper oxide, 2 parts of chromium oxide, 24 parts of rosin-modified phenolic resin, 5 parts of flux lithium carbonate, 25 parts of zirconia-coated copper chromite black, 0.5 part of alumina, and 2 parts of titanium dioxide. The spheroidal fineness of bismuth silicate crystal, Bi2O3 - B2O3 - SiO2 system glass, and copper oxide is all 300 mesh.

[0057] A sintering and curing process for a high borosilicate glass ink includes the following steps:

[0058] Precisely weigh each solid component according to mass parts and mix them, then add a dispersant and a bonding promoter and place them in a stirring container. Stir slowly at 30 r / min at room temperature for 30 min to uniformly form a slurry;

[0059] After stirring, add an ultrasonic-assisted liquid and turn on the ultrasonic device to further mix and disperse;

[0060] After ultrasonic treatment, perform dry grinding and jet milling in sequence, controlling the final particle size of the final slurry to be 3 - 15 μm, the viscosity to be 1000 - 3000 mPa·s, the light transmittance to be higher than 85%, and the haze to be lower than 5%. Use the cross-cut method to test that the adhesion of the slurry on the glass substrate is not lower than 5B. After 100 μm filtration, a high borosilicate glass ink is obtained;

[0061] Pour the high borosilicate glass ink into a mold, place it in a sintering furnace, and complete sintering and curing in a gradient temperature increase manner.

[0062] The dispersant is fatty acid polyethylene glycol ester, and the addition amount is 1.5% of the total mass of the solid components.

[0063] The bonding promoter is silane coupling agent, and the addition amount is 2% of the total mass of the solid components.

[0064] The ultrasonic-assisted solution is a mixed solution of ethanol and water with a volume ratio of 1:1. The addition amount of the ultrasonic-assisted solution is 40% of the total volume of the slurry. The ultrasonic power is 500 W, and the ultrasonic time is 60 min.

[0065] The dry grinding equipment is a planetary ball mill. The grinding medium is zirconia balls. The ball-to-powder ratio is controlled at 6:1, the rotation speed is set at 250 r / min, and the grinding time is 4 hours to initially achieve a particle size range of 200 μm for the slurry. The jet mill equipment is a flat jet mill. The compressed air pressure is controlled at 0.7 MPa, and the feeding speed is 8 kg / h.

[0066] The gradient heating is specifically as follows: heating at a rate of 2 °C / min to 150 °C and holding for 30 min; then heating at a rate of 3 °C / min to 350 °C and holding for 30 min; finally heating at a rate of 5 °C / min to 500 °C and holding for 60 min. Nitrogen is introduced for protection throughout the process.

[0067] Example 5

[0068] A high borosilicate glass ink, according to mass parts, includes the following solid components: 17 parts of bismuth silicate crystal, 10 parts of Bi2O3 - B2O3 - SiO2 system glass, 2 parts of zinc oxide, 6 parts of boron oxide, 24 parts of copper oxide, 2 parts of chromium oxide, 24 parts of rosin-modified phenolic resin, 15 parts of flux, 24 parts of zirconia-coated copper chromite black, 0.4 parts of alumina, and 2 parts of titanium dioxide. The spheroid fineness of the bismuth silicate crystal, Bi2O3 - B2O3 - SiO2 system glass, and copper oxide is all 300 mesh.

[0069] A sintering and curing process for a high borosilicate glass ink includes the following steps:

[0070] Precisely weigh each solid component according to mass parts and mix them, then add a dispersant and a bonding promoter and place them in a stirring container. Stir slowly at 30 r / min at room temperature for 30 min to form a homogeneous slurry;

[0071] After stirring, add the ultrasonic-assisted liquid and turn on the ultrasonic device to further mix and disperse;

[0072] After ultrasonic treatment, dry grinding and jet milling are carried out in sequence. Control the final particle size of the final slurry to be 3 - 15 μm, the viscosity to be 1000 - 3000 mPa·s, the light transmittance to be higher than 85%, and the haze to be lower than 5%. Use the cross-cut method to test that the adhesion of the slurry on the glass substrate is not less than 5B. After passing through a 100 μm filter, a high borosilicate glass ink is obtained;

[0073] Pour the high borosilicate glass ink into a mold, place it in a sintering furnace, and complete sintering and curing in a gradient heating manner.

[0074] The dispersant is fatty acid polyethylene glycol ester, and the addition amount is 1% of the total mass of the solid components.

[0075] The adhesion promoter is a silane coupling agent, and the addition amount is 2% of the total mass of the solid components.

[0076] The ultrasonic-assisted solution is a mixed solution of ethanol and water with a volume ratio of 1:1. The addition amount of the ultrasonic-assisted solution is 40% of the total volume of the slurry. The ultrasonic power is 500 W, and the ultrasonic time is 60 min.

[0077] The dry grinding equipment is a planetary ball mill. The grinding medium is zirconia balls. The ball-to-material ratio is controlled at 7:1, the rotation speed is set at 300 r / min, and the grinding time is 4 hours to initially bring the slurry to a particle size range of 150 μm. The jet mill equipment is a flat jet mill. The compressed air pressure is controlled at 0.7 MPa, and the feeding speed is 9 kg / h.

[0078] The gradient temperature increase is specifically as follows: heating at a rate of 2 °C / min to 150 °C and holding for 30 min; then heating at a rate of 3 °C / min to 350 °C and holding for 30 min; finally heating at a rate of 5 °C / min to 500 °C and holding for 60 min. Nitrogen is introduced for protection throughout the process.

[0079] In the ink formulation of the present invention, a specific proportion of calcium fluoride or lithium carbonate is added as a flux, which can accurately control the melting temperature of the ink within the range of 440 °C to 470 °C, effectively inhibiting the crystallization phenomenon of the glass powder. In practical applications, the ink with an appropriate amount of flux added has significantly better fluidity than the traditional ink without addition during the sintering process. The edges of the printed pattern are clearer and smoother, and the surface quality is significantly improved, greatly enhancing the stability and uniformity of the ink.

[0080] The present invention uses an advanced zirconia coating technology to treat copper chromite black. The color difference ΔE of the zirconia-coated copper chromite black is less than 1.5, while the color difference of the untreated copper chromite black is as high as over 3.0. This method can significantly reduce the color change phenomenon of copper chromite black at high temperatures, ensuring that the ink color remains stable under various harsh conditions. At the same time, tested according to the ASTM C274-18 standard, its acid resistance is improved to level 4 or above, effectively guaranteeing the durability of automotive glass under complex road conditions and changing climates.

[0081] The present invention finely adjusts the component ratio of the Bi2O3-B2O3-SiO2-based glass and introduces ZrO2 low-melting glass. Through the synergistic effect between multiple glass phases, the accurate regulation of the CTE of the ink is realized. Finally, the CTE of the ink successfully drops to 3.0×10 -6 / °C, and the matching error with the substrate is less than 5%. Compared with traditional inks, the matching degree with glass is increased by more than 30%, greatly enhancing the bonding force between the two and effectively preventing interface problems caused by temperature changes.

[0082] The present invention innovatively combines a jet mill and a dry grinding process. Compared with the traditional single grinding method, the composite grinding improves the fineness of the ink by about 40% and reduces the energy consumption by nearly 30%. The finer and more uniform particles help to improve the printing resolution, improve the contact state between the ink and the glass substrate at the micro level, and lay a good foundation for subsequent sintering and curing. The ink coating prepared by composite grinding is denser and more uniform, significantly improving the product quality.

[0083] In the sintering stage of the present invention, a gradient heating method is adopted to induce the formation of columnar crystals. Actual tests show that, compared with the traditional process, the scratch resistance value of the ink is greater than 20 N, and the wear resistance is improved by about 50%.

[0084] The above are only the preferred embodiments of the present invention and are not used to limit the present invention. Those skilled in the art can make various modifications or equivalent replacements to the present invention within the essence and protection scope of the present invention, and such modifications or equivalent replacements should also be regarded as falling within the protection scope of the technical solution of the present invention.

Claims

1. A high-borosilicate glass ink, characterized in that, According to the number of parts by mass, it includes the following solid components: 12-18 parts of bismuth silicate crystal, 8-12 parts of Bi2O3-B2O3-SiO2 system glass, 1-3 parts of zinc oxide, 5-7 parts of boron oxide, 20-25 parts of copper oxide, 1-3 parts of chromium oxide, 20-25 parts of rosin modified phenolic resin, 1-3 parts of flux calcium fluoride or 5-15 parts of lithium carbonate, 20-25 parts of zirconia-coated copper chromite black, 0.3-0.5 parts of alumina, and 1-2 parts of titanium dioxide.

2. The high-borosilicate glass ink according to claim 1, wherein: The nodular fineness of the bismuth silicate crystal, Bi2O3-B2O3-SiO2 system glass and copper oxide is 300 mesh.

3. A high-borosilicate glass ink according to claim 1, characterized in that: The preparation method of the zirconia-coated copper chromite black is as follows: First, prepare a zirconium oxychloride solution with a concentration of 0.1-0.3 mol / L. Add the copper chromite black pigment to the zirconium oxychloride solution according to the solid-liquid volume-mass ratio of 1 g:10 mL-1 g:15 mL, stir evenly at a temperature of 40-60 °C, then slowly dropwise add an ammonia water solution with a pH value of 8-10, control the dropping speed at 2-5 mL / min, and continuously stir at the same time. Keep the system temperature constant during the reaction, the reaction time is 2-4 hours. After the reaction is completed, filter and wash with deionized water multiple times until no chloride ion impurities are detected in the washing solution. Finally, dry at 80-120 °C, and then add 2 wt%-4 wt% of high-temperature resistant pearlescent powder and calcine at 600 °C-800 °C for 1-3 h.

4. A sintering and curing process for high borosilicate glass ink, characterized in that: It includes the following steps: Accurately weigh each solid component according to the number of parts by mass and mix them, then add a dispersant and a bonding promoter into a stirring container, and stir slowly at 30 r / min at room temperature for 30 min to form a slurry evenly. After the stirring is completed, add an ultrasonic-assisted liquid, and turn on the ultrasonic device to further mix and disperse. After the ultrasonic treatment, carry out dry grinding and air flow grinding in sequence, control the final particle size and performance of the final slurry to meet the standards, and obtain high-borosilicate glass ink after filtration. Pour the high-borosilicate glass ink into a mold, put it into a sintering furnace, and complete sintering and curing in a gradient heating manner.

5. A sintering and curing process for a high-borosilicate glass ink according to claim 4, characterized in that: The dispersant is fatty acid polyethylene glycol ester, and the addition amount is 0.5%-1.5% of the total mass of the solid components.

6. A sintering and curing process for a high-borosilicate glass ink according to claim 4, characterized in that: The bonding promoter is a silane coupling agent, and the addition amount is 1%-3% of the total mass of the solid components.

7. A sintering and curing process for a high-borosilicate glass ink according to claim 4, characterized in that: The ultrasonic-assisted solution is a mixed solution of ethanol and water with a volume ratio of 1:

1. The addition amount of the ultrasonic-assisted solution is 30%-50% of the total volume of the slurry, the ultrasonic power is 500 W, and the ultrasonic time is 60 min.

8. A sintering and curing process for a high-borosilicate glass ink according to claim 4, characterized in that: The dry grinding equipment is a planetary ball mill, the grinding medium is zirconia balls, the ball-to-material ratio is controlled at 5:1-8:1, the rotation speed is set at 200-300 r / min, and the grinding time is 3-5 hours to make the slurry initially reach a particle size range of 100-200 μm. The air flow grinding equipment is a flat air flow mill, the compressed air pressure is controlled at 0.6-0.8 MPa, and the feeding speed is 5-10 kg / h.

9. A sintering and curing process for a high-borosilicate glass ink according to claim 4, characterized in that: The final particle size of the final slurry is 3 - 15 μm, the viscosity is 1000 - 3000 mPa·s, the light transmittance is higher than 85%, the haze is lower than 5%, the adhesion of the slurry on the glass substrate tested by the cross-cut method is not less than 5B, and the filtration accuracy is 100 μm.

10. A sintering and curing process for a high-borosilicate glass ink according to claim 4, characterized in that: The gradient temperature increase is specifically as follows: heat up to 150 °C at a rate of 2 °C / min and hold for 30 min; then heat up to 350 °C at a rate of 3 °C / min and hold for 30 min; finally heat up to 500 °C at a rate of 5 °C / min and hold for 60 min, and nitrogen is introduced for protection throughout the process.