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WO2017215111A1 - Bismuth-silicon-boron type low-melting-point ink for glass surface spray painting and printing and preparation method therefor - Google Patents

Bismuth-silicon-boron type low-melting-point ink for glass surface spray painting and printing and preparation method therefor Download PDF

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Publication number
WO2017215111A1
WO2017215111A1 PCT/CN2016/095624 CN2016095624W WO2017215111A1 WO 2017215111 A1 WO2017215111 A1 WO 2017215111A1 CN 2016095624 W CN2016095624 W CN 2016095624W WO 2017215111 A1 WO2017215111 A1 WO 2017215111A1
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Prior art keywords
low
suspension
melting
ink
solvent
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French (fr)
Chinese (zh)
Inventor
许晓静
丁清
朱金鑫
庞伟
吉顺青
叶书兵
刘庆辉
杨帆
王浩
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Jiangsu University
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Jiangsu University
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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C12/00—Powdered glass; Bead compositions
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/38—Inkjet printing inks characterised by non-macromolecular additives other than solvents, pigments or dyes

Definitions

  • the invention belongs to the technical field of high temperature glass ink, and particularly relates to a silicon germanium boron low melting point ink for six color glass surface printing and printing and a preparation method thereof.
  • Glass ink refers to ink that can be printed on glass and can be firmly attached. It is classified according to processing temperature. Glass ink can be divided into high temperature glass ink, glass baking ink, low temperature glass ink and ordinary glass ink, among which high temperature glass Ink, also known as high-temperature tempered glass ink, sintering temperature is 650-850 ° C, after high-temperature sintering, the ink and glass are firmly fused together, the color is bright, not suitable for fading and color loss. Widely used in the construction of glass curtain wall, automotive glass, glass floor tiles and other fields.
  • Glass digital inkjet printing which uses a digital inkjet printer with the support of computer software, inkjet printing a pre-set image onto the glass surface, followed by drying and sintering.
  • digital inkjet printing on glass surfaces is developing in the direction of large format, high precision and corrosion resistance.
  • the company has developed a variety of high-performance nozzles. These nozzles have nozzle diameters as low as micron or even nanometers, providing a high-resolution print for clearer and more beautiful images.
  • high-precision nozzles also place higher demands on the glass ink used in inkjet printing.
  • Patent No. CN104893405A discloses a method for preparing high temperature glass ink, wherein the glass powder is melted, dried, and pulverized by melting materials such as SiO 2 , B 2 O 3 , BaO, TiO 2 , Na 2 O, and the like.
  • the particle size of 200 to 400 mesh, that is, 38 to 75 ⁇ m, is far from meeting the needs of high-precision glass digital inkjet printing.
  • the maximum particle size of the solid phase component of the Sol-gel glass ink which is widely used now can be less than 1.5 ⁇ m, but the method has the problems of high manufacturing cost, high pollution, difficult particle size control, and unstable process.
  • An object of the present invention is to provide a silicon germanium-based low melting point ink for glass surface printing and printing and a preparation method thereof.
  • a silicon-on-silicon boron low-melting ink for glass surface printing characterized in that it is prepared by mixing a low-melting glass powder suspension with an inorganic pigment suspension; the low-melting glass powder suspension and the inorganic pigment suspension The volume ratio is 3 to 5:1.
  • the solid phase component glass powder in the low melting point glass frit suspension has two formulations.
  • the main components of Formula One are bismuth oxide (Bi 2 O 3 ), amorphous silica (SiO 2 ), boric acid (H 3 BO 3 ), lithium nitrate (LiNO 3 ), alumina (Al 2 O 3 ), and Zirconia (ZrO 2 ), wherein the mass percentage of bismuth oxide (Bi 2 O 3 ) is 27 to 32%, the mass percentage of amorphous silica (SiO 2 ) is 8 to 11%, and boric acid (H 3 BO 3 ) The mass percentage is 21 to 30%, the mass percentage of lithium nitrate (LiNO 3 ) is 29 to 33%, the mass percentage of alumina (Al 2 O 3 ) is 2 to 3%, and the mass of zirconium oxide (ZrO 2 ) The percentage is 0.5 to 2%, and the sum of the components is 100%.
  • the main components of Formulation 2 are bismuth oxide (Bi 2 O 3 ), amorphous silica (SiO 2 ), boron oxide (B 2 O 3 ), lithium nitrate (LiNO 3 ), and aluminum oxide (Al 2 O 3 ).
  • ZrO 2 And zirconium oxide (ZrO 2 ), wherein the mass percentage of bismuth oxide (Bi 2 O 3 ) is 34.9 to 43.3%, the mass percentage of amorphous silica (SiO 2 ) is 12.2 to 14.5%, and boron oxide (B 2 ) The mass percentage of O 3 ) is 8 to 13.7%, the mass percentage of lithium nitrate (LiNO 3 ) is 29.3 to 37%, and the mass percentage of alumina (Al 2 O 3 ) is 2.7 to 3.4%, and zirconium oxide (ZrO 2 ) The mass percentage is 1.2 to 1.5%, and the sum of the components is 100%.
  • the glass frit has a particle diameter of 1 to 5 ⁇ m.
  • the maximum particle size of the glass powder prepared according to the formula 1 can be reduced to less than 100 nm by means of solvent ball milling.
  • the maximum particle size of the glass powder prepared according to the formula 2 can be reduced to less than 1 ⁇ m by means of solvent ball milling.
  • the inorganic pigment suspension has six colors, and the solid phase component is six industrial pigments, wherein the white colorant is titanium oxide (TiO 2 ), the red color material is iron oxide (Fe 2 O 3 ), yellow color.
  • the material is titanium chrome yellow, the green color material is cobalt green, the blue color material is cobalt blue (CoAl 2 O 4 ), and the black color material is copper chrome black; the maximum particle size of the six industrial color materials needs to be less than 2 micrometers. And its maximum particle size can be reduced to below 100 nm by means of solvent ball milling.
  • the low-melting glass frit suspension and the inorganic pigment suspension have the same liquid component (solvent) composition as the mass percentage of each component, ranging from 68 to 78% of the main solvent, and 14 to 20% of the dispersing agent, 7 ⁇ 11% of a surfactant and 0.1 to 1% of a light stabilizer, the sum of the components is 100%;
  • the main solvent is 1,2-propylene glycol dimethyl ether, ethylene glycol monoethyl ether, cyclohexyl a mixture of one or any of several ketones;
  • the dispersant comprising diethylene glycol butyl ether and an acrylic resin, wherein the mass ratio of diethylene glycol butyl ether to acrylic resin is 15:1, and the acrylic resin
  • the average molecular weight is 5000-8000;
  • the surfactant is 1,2-propylene glycol diacetate; and
  • the light stabilizer is bismuth azelaic acid (1,2,2,6,6-pentylmethyl- 4-piperidiny
  • a method for preparing a silicon germanium-based low melting point ink for glass surface printing printing characterized in that it comprises the following steps:
  • Preparation of low-melting glass powder suspension firstly, according to the formula 1 or the formula 2, a low-melting glass powder is prepared, and then the solvent in the low-melting glass powder suspension is prepared, and finally the low-melting glass powder and the solvent mass ratio are 1: 3, the ball to material ratio of 5 ⁇ 8:1, the speed of 400 ⁇ 600r / min, weighing low-melting glass powder and solvent into the ball mill tank, ball milling using a planetary ball mill 12 ⁇ 48h, to obtain a low-melting glass powder suspension.
  • Preparation of inorganic pigment suspension firstly prepare the solvent in the inorganic pigment suspension, and then weigh a certain amount according to the mass ratio of the colorant to the solvent of 1:3, the ratio of the ball to the material of 5 to 8:1, and the rotation speed of 400 to 600 r/min.
  • the color pigment and solvent are poured into a ball mill jar, and ball milled for 12 to 48 hours using a planetary ball mill to obtain an inorganic pigment suspension.
  • the particle obtained by the step (3) is subjected to particle size detection using a laser particle size analyzer. If the particle size does not meet the requirements, the ball milling time is extended or filtration is performed using a filtering device.
  • the innovation of the invention mainly consists of mixing the solid phase component of the glass frit suspension and the pigment suspension with the liquid component by ball milling, and controlling the solidification of the two suspensions by setting the ball milling parameters.
  • the phase component particle size; in addition, the inventive concept also includes the composition of the six inorganic pigments and the composition of the liquid component in the two suspensions and the mass percentage of each component.
  • the silicon-on-silicon boron-based low-melting ink for glass surface printing printing provided by the present invention is prepared from a low-melting glass powder suspension and an inorganic pigment suspension, and is suspended in a low-melting glass powder suspension and an inorganic pigment suspension.
  • the maximum particle size of the solid phase component can be less than 100 nm, which can better meet the needs of high precision glass inkjet printing.
  • the silicon germanium-based low-melting ink for glass surface printing printing provided by the present invention has a lower sintering temperature than a general high-temperature glass ink, and a large melting start temperature is 600 to 650 °C.
  • the silicon-on-silicon boron-based low-melting ink for glass surface printing printing provided by the present invention has strong binding force with glass after sintering, and does not fade or fade.
  • the silicon germanium-based low-melting ink for glass surface printing and printing provided by the present invention has a manufacturing process Full, simple and stable, suitable for industrial mass production.
  • the silicon germanium-based low-melting ink for glass surface printing printing provided by the invention has the common raw materials for preparing the raw materials, and the raw material price is cheap, and the manufacturing cost of the product is much lower than that of the similar products.
  • the silicon-on-silicon boron low-melting ink for glass surface printing printing provided by the invention is prepared from a low-melting glass powder suspension and an inorganic pigment suspension, and the ratio of the low-melting glass powder suspension to the inorganic pigment suspension is adjustable. You can adjust the color depth by changing the scale, which can better match the computer software to achieve better printing results.
  • Fig. 1 is a graph showing the results of thermal analysis (DSC) of a silicon germanium-based low melting point green ink for glass surface printing printing prepared in the first embodiment.
  • FIG. 2 is a laser particle size detection diagram of a silicon germanium-based low melting point green ink for glass surface printing printing prepared in the first embodiment.
  • 3 is a laser particle size detection diagram of the obtained low-melting glass powder suspension obtained in the first embodiment.
  • Example 4 is a laser particle size detection diagram of the obtained inorganic green pigment suspension prepared in Example 1.
  • Figure 5 is a laser particle size detection diagram of the low-melting glass powder suspension obtained in the second embodiment.
  • Figure 6 is a laser particle size detection diagram of the inorganic red pigment suspension obtained in the second embodiment.
  • Figure 7 is a scanning electron microscope (SEM) image of the solid phase component after drying of the obtained inorganic red pigment suspension prepared in Example 2.
  • Fig. 8 is a graph showing the results of thermal analysis (DSC) of a silicon germanium-based low-melting white ink for glass surface printing printing prepared in the third embodiment.
  • Figure 9 is a laser particle size detection diagram of the inorganic white pigment suspension obtained in the third embodiment.
  • Fig. 10 is a laser particle size detection diagram of a silicon germanium boron-based low melting point yellow ink for glass surface printing printing prepared in the fourth embodiment.
  • Figure 11 is a laser particle size detection diagram of the inorganic yellow pigment suspension obtained in the fourth embodiment.
  • FIG. 12 is a laser particle size detection diagram of a silicon germanium boron-based low melting point blue ink for glass surface printing printing prepared in the fifth embodiment.
  • Figure 13 is a laser particle size detection diagram of the inorganic blue pigment suspension obtained in the fifth embodiment.
  • Figure 14 is a laser particle size detection diagram of a silicon germanium-based low melting point black ink for glass surface printing printing prepared in Example 6.
  • Figure 15 is a laser particle size detection diagram of the inorganic black pigment suspension obtained in Example 6.
  • the invention discloses a silicon-on-silicon boron-based low-melting green ink for printing on a glass surface, and the preparation process is as follows:
  • inorganic pigment suspension is exactly the same as the solvent in the low-melting glass powder suspension, so firstly, 150 g of the inorganic green pigment suspension is prepared according to the mass percentage of each component of the solvent in the step (1). Solvent, then according to the color to solvent mass ratio of 1:3, ball to material ratio of 5 ⁇ 8:1, speed 400 ⁇ 600r / min, weigh 50g cobalt green and 150g solvent into the ball mill tank, ball milling using a planetary ball mill 48h , obtained an inorganic green pigment suspension.
  • the particle obtained by the step (3) is subjected to particle size detection using a laser particle size analyzer. If the particle size does not meet the requirements, the ball milling time is extended or filtration is performed using a filtering device.
  • FIG. 2 is a laser particle size detection diagram of the green ink, and it can be seen that the particle size of the solid phase component in the ink is less than 1.1 ⁇ m;
  • FIG. 3 is a laser particle size detection diagram of the low-melting glass powder suspension prepared in the present embodiment. It can be seen that the particle size of the solid phase component in the low-melting glass frit suspension is less than 1.1 ⁇ m;
  • FIG. 4 shows the laser particle size detection of the inorganic green pigment suspension obtained in the present example, and it can be seen that the inorganic green pigment suspension The solid phase component particle size in the solution is all less than 500 nm.
  • the invention discloses a silicon-on-silicon boron low-melting red ink for printing on a glass surface, and the preparation process is as follows:
  • inorganic pigment suspension is exactly the same as the solvent in the low-melting glass powder suspension, so firstly, 150 g of the inorganic red pigment suspension is prepared according to the mass percentage of each component of the solvent in the step (1). Solvent, then according to the color to solvent mass ratio of 1:3, ball to material ratio of 5 ⁇ 8:1, speed 400 ⁇ 600r / min, weigh 50g of iron oxide (Fe 2 O 3 ) and 150g of solvent into the ball mill tank The ball was milled for 48 h using a planetary ball mill to obtain a nano-scale inorganic red pigment suspension.
  • the particle obtained by the step (3) is subjected to particle size detection using a laser particle size analyzer. If the particle size does not meet the requirements, the ball milling time is extended or filtration is performed using a filtering device.
  • the glass surface printing printing obtained in this example is a silicon germanium boron low melting point red ink, and the thermal analysis (DSC) result chart is similar to that of FIG.
  • FIG. 5 is a view showing the laser particle size detection of the obtained low-melting glass powder suspension prepared in the present example, and it can be seen that the particle size of the solid phase component in the low-melting glass powder suspension is less than 110 nm.
  • FIG. 6 is a view showing the laser particle size detection of the obtained inorganic red pigment suspension prepared in the present example, and it can be seen that the particle size of the solid phase component in the unagglomerated inorganic green pigment is substantially less than 100 nm.
  • FIG. 7 is a scanning electron microscopy (SEM) image of the solid phase component obtained after drying the obtained inorganic red pigment suspension prepared in the present embodiment, and it can be seen that the particle size of the solid phase component in the inorganic red pigment is substantially less than 100 nm, which can be confirmed.
  • Most of the particle size detection results in 6 are particle agglomeration, which can be broken up by ultrasonic waves before use.
  • the invention discloses a silicon-on-silicon boron low-melting white ink for printing on a glass surface, and the preparation process is as follows:
  • the inorganic pigment suspension is exactly the same as the solvent in the low-melting glass powder suspension, so firstly, 150 g of the inorganic white pigment suspension is prepared according to the mass percentage of each component of the solvent in the step (1).
  • the solvent is then poured into a ball mill tank according to a mass ratio of the colorant to the solvent of 1:3, a ball to material ratio of 5 to 8:1, a rotation speed of 400 to 600 r/min, and a weight of 50 g of titanium oxide (TiO 2 ) and 150 g of the solvent.
  • the ball mill was ball milled for 48 h to obtain an inorganic white pigment suspension.
  • the particle obtained by the step (3) is subjected to particle size detection using a laser particle size analyzer. If the particle size does not meet the requirements, the ball milling time is extended or filtration is performed using a filtering device.
  • the glass surface-printing printing obtained by the present embodiment uses a silicon germanium-boride low-melting white ink, and its thermal analysis (DSC) results are shown in Fig. 8.
  • the large-scale melting start temperature is about 650 °C.
  • the laser particle size detection chart of the obtained inorganic white pigment suspension prepared in this example is shown in Fig. 9. It can be seen that the particle size of the solid phase component in the unagglomerated white pigment suspension is less than 110 nm, and the particle size of the agglomerated particles is also Substantially less than 2 ⁇ m, the agglomerated particles can be broken up using ultrasonic waves.
  • a glass surface printing printing using silicon germanium boron low melting point yellow ink is as follows:
  • inorganic pigment suspension is exactly the same as the solvent in the low-melting glass powder suspension, so firstly, 150 g of the inorganic yellow pigment suspension is prepared according to the mass percentage of each component of the solvent in the step (1). Solvent, then according to the color to solvent mass ratio of 1:3, ball ratio of 5 ⁇ 8:1, speed 400 ⁇ 600r / min, weigh 50g of titanium chrome and 150g of solvent into the ball mill tank, using a planetary ball mill ball mill At 48h, an inorganic yellow pigment suspension was obtained.
  • the particle obtained by the step (3) is subjected to particle size detection using a laser particle size analyzer. If the particle size does not meet the requirements, the ball milling time is extended or filtration is performed using a filtering device.
  • the glass surface printing printing of the silicon germanium-based low melting point yellow ink obtained in the present embodiment has a laser particle size detection chart as shown in FIG. 10, and it can be seen that the particle diameter of the solid phase component in the ink is less than 600 nm.
  • the laser particle size detection chart of the obtained inorganic yellow pigment suspension prepared in this embodiment is shown in Fig. 11. It can be seen that the particle size of the solid phase component in the unagglomerated yellow pigment suspension is less than 110 nm, and the particle size of the agglomerated particles is also substantially less than 1 ⁇ m.
  • the agglomerated particles can be broken up by ultrasonic waves; the yellow ink thermal analysis (DSC) results obtained in this example are similar to those in FIG.
  • the invention discloses a silicon-on-silicon boron low-melting blue ink for printing on a glass surface, and the preparation process is as follows:
  • inorganic pigment suspension is exactly the same as the solvent in the low-melting glass powder suspension, so firstly, 150 g of the inorganic blue pigment suspension is prepared according to the mass percentage of each component of the solvent in the step (1). Solvent, then according to the mass ratio of pigment to solvent 1:3, ball to material ratio 5 ⁇ 8:1, speed 400 ⁇ 600r / min, weigh 50g cobalt blue (CoAl 2 O 4 ) and 150g solvent into the ball mill In the middle, ball milling was carried out for 48 h using a planetary ball mill to obtain an inorganic blue pigment suspension.
  • the particle obtained by the step (3) is subjected to particle size detection using a laser particle size analyzer. If the particle size does not meet the requirements, the ball milling time is extended or filtration is performed using a filtering device.
  • a silicon germanium-based low melting point blue ink is used, and the laser particle size detection chart is as shown in FIG. 12, and it can be seen that the particle diameter of the solid phase component in the ink is less than 700 nm.
  • the laser particle size detection chart of the obtained inorganic blue pigment suspension prepared in this example is shown in Fig. 13, and it can be seen that the solid phase component particle diameter in the blue pigment suspension is all less than 300 nm.
  • the invention discloses a silicon-on-silicon boron-based low melting point black ink for printing on a glass surface, and the preparation process is as follows:
  • inorganic pigment suspension is exactly the same as the solvent in the low-melting glass powder suspension, so firstly, 150 g of the inorganic black pigment suspension is prepared according to the mass percentage of the solvent components in the step (1). Solvent, then according to the color to solvent mass ratio 1:3, ball to material ratio of 5 ⁇ 8:1, speed 400 ⁇ 600r / min, weigh 50g (CoAl 2 O 4 ) and 150g solvent into the ball mill tank, use The ball mill was ball milled for 48 h to obtain an inorganic black pigment suspension.
  • the particle obtained by the step (3) is subjected to particle size detection using a laser particle size analyzer. If the particle size does not meet the requirements, the ball milling time is extended or filtration is performed using a filtering device.
  • the glass surface printing printing obtained by the present embodiment uses a silicon germanium boron-based low melting point black ink.
  • the laser particle size detection chart is shown in FIG. 14. It can be seen that the particle size of the unagglomerated solid phase component in the ink is less than 700 nm, and the agglomeration is achieved.
  • the solid phase component can be broken up using ultrasound prior to use.
  • the laser particle size detection chart of the obtained inorganic black pigment suspension prepared in this example is shown in Fig. 15. It can be seen that the solid phase component particle size in the unagglomerated black pigment suspension is all less than 1 ⁇ m, and the agglomerated particles can be broken up by ultrasonic waves.
  • a glass surface printing printing method prepared by the first embodiment is used for sintering a silicon germanium boron low melting point green ink onto a glass.
  • the specific steps are as follows:
  • Example 1 The green ink prepared in Example 1 was uniformly painted on the surface of the glass, and the glass used was an ordinary float glass.
  • the glass was placed in a muffle furnace at 700 ° C, sintered for 3 to 4 minutes, and taken out.
  • the sintering effect after cooling is that the glass powder in the ink envelops the inorganic pigment and the glass is integrated, and the binding ability is strong, and since the pigment used in the invention is a stable inorganic pigment, it is not easy to fade and discolor after sintering.
  • a glass surface printing printing method prepared by the second embodiment is used to sinter a silicon-boron-based low-melting red ink onto a glass.
  • the specific steps are as follows:
  • Example 2 The red ink prepared in Example 2 was uniformly painted on the surface of the glass, and the glass used was ordinary float glass.
  • the glass was placed in a muffle furnace at 700 ° C, sintered for 3 to 4 minutes, and taken out.
  • the sintering effect after cooling is that the glass powder in the ink after sintering encloses the inorganic pigment and the glass, and has strong bonding ability.
  • the pigments used in the present invention are all stable inorganic pigments, they are not easily faded and discolored after sintering.

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
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  • Organic Chemistry (AREA)
  • Wood Science & Technology (AREA)
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Abstract

Provided is a bismuth-silicon-boron type low-melting-point ink for glass surface spray painting and printing. The ink is formed by mixing a low-melting-point glass powder suspension and an inorganic pigment suspension. The ingredients of the glass powder are bismuth oxide, amorphous silica, boric acid, lithium nitrate, alumina and zirconium oxide; the boric acid therein can be replaced with boron oxide; and the particle sizes of the components of the solid phase in the two suspensions are controlled through setting ball milling parameters in order to adapt to the requirements of a high-precision glass spray painting and printing.

Description

玻璃表面喷绘打印用铋硅硼系低熔点油墨及其制备方法Silicon-silicon-boron low-melting ink for glass surface printing and printing and preparation method thereof 技术领域Technical field

本发明属于高温玻璃油墨技术领域，特别涉及六种颜色玻璃表面喷绘打印用铋硅硼系低熔点油墨及其制备方法。The invention belongs to the technical field of high temperature glass ink, and particularly relates to a silicon germanium boron low melting point ink for six color glass surface printing and printing and a preparation method thereof.

背景技术Background technique

玻璃油墨是指可在玻璃上进行印刷并能牢固附着的油墨，按照加工温度进行分类，玻璃油墨可分为：高温玻璃油墨、玻璃烤花油墨、低温玻璃油墨和普通玻璃油墨，其中的高温玻璃油墨，也称高温钢化玻璃油墨，烧结温度在650-850℃，经过高温烧结后，油墨与玻璃牢固熔结在一起，色泽鲜艳，不宜褪色、掉色。广泛用于建筑玻璃幕墙、汽车玻璃、玻璃地面砖等领域。Glass ink refers to ink that can be printed on glass and can be firmly attached. It is classified according to processing temperature. Glass ink can be divided into high temperature glass ink, glass baking ink, low temperature glass ink and ordinary glass ink, among which high temperature glass Ink, also known as high-temperature tempered glass ink, sintering temperature is 650-850 ° C, after high-temperature sintering, the ink and glass are firmly fused together, the color is bright, not suitable for fading and color loss. Widely used in the construction of glass curtain wall, automotive glass, glass floor tiles and other fields.

玻璃数码喷绘打印，即是使用数码喷绘打印机在计算机软件的支持下，将预先设定好的图片喷墨打印到玻璃表面，随后再进行烘干和烧结的过程。随着科技的进步，玻璃表面数码喷绘打印正在朝着大幅面、高精度、耐腐蚀的方向发展。为此，相关公司已经研制出多款高性能喷头。这些喷头的喷口直径低至微米级甚至纳米级，为高精度打印出更加清晰炫丽的图片提供了保障。同时，高精度的喷头也对喷绘打印使用的玻璃油墨提出了更高的要求。为适应高精度玻璃数码喷绘打印的需要，玻璃油墨中固相组份的粒径必须在2μm以下，最好小于500nm。专利号为CN104893405A的中国专利，公开了一种高温玻璃油墨制备方法，其中的玻璃粉通过SiO2、B2O3、BaO、TiO2、Na2O等原料熔融后水淬、干燥、粉碎至粒径200～400目，即38～75μm，远无法满足高精度玻璃数码喷绘打印的需要。现在被广泛使用的Sol-gel法玻璃油墨固相组份最大粒径最小可小于1.5μm，但该方法存在制造成本高、污染大、粒径不易控制、工艺过程不稳定等问题。Glass digital inkjet printing, which uses a digital inkjet printer with the support of computer software, inkjet printing a pre-set image onto the glass surface, followed by drying and sintering. With the advancement of technology, digital inkjet printing on glass surfaces is developing in the direction of large format, high precision and corrosion resistance. To this end, the company has developed a variety of high-performance nozzles. These nozzles have nozzle diameters as low as micron or even nanometers, providing a high-resolution print for clearer and more beautiful images. At the same time, high-precision nozzles also place higher demands on the glass ink used in inkjet printing. In order to meet the needs of high-precision glass digital inkjet printing, the particle size of the solid phase component in the glass ink must be 2 μm or less, preferably less than 500 nm. Patent No. CN104893405A, discloses a method for preparing high temperature glass ink, wherein the glass powder is melted, dried, and pulverized by melting materials such as SiO 2 , B 2 O 3 , BaO, TiO 2 , Na 2 O, and the like. The particle size of 200 to 400 mesh, that is, 38 to 75 μm, is far from meeting the needs of high-precision glass digital inkjet printing. The maximum particle size of the solid phase component of the Sol-gel glass ink which is widely used now can be less than 1.5 μm, but the method has the problems of high manufacturing cost, high pollution, difficult particle size control, and unstable process.

发明内容Summary of the invention

本发明的目的在于提供一种玻璃表面喷绘打印用铋硅硼系低熔点油墨及其制备方法。An object of the present invention is to provide a silicon germanium-based low melting point ink for glass surface printing and printing and a preparation method thereof.

本发明的技术方案之一是:One of the technical solutions of the present invention is:

一种玻璃表面喷绘打印用铋硅硼系低熔点油墨，其特征在于：它由低熔点玻璃粉悬浮液与无机颜料悬浮液混合而成；所述低熔点玻璃粉悬浮液与无机颜料悬浮液的体积比为3～5:1。A silicon-on-silicon boron low-melting ink for glass surface printing, characterized in that it is prepared by mixing a low-melting glass powder suspension with an inorganic pigment suspension; the low-melting glass powder suspension and the inorganic pigment suspension The volume ratio is 3 to 5:1.

所述低熔点玻璃粉悬浮液中的固相组份玻璃粉有两种配方。 The solid phase component glass powder in the low melting point glass frit suspension has two formulations.

配方一的主要成份为氧化铋(Bi2O3)、非晶态二氧化硅(SiO2)、硼酸(H3BO3)、硝酸锂(LiNO3)、氧化铝(Al2O3)和氧化锆(ZrO2)，其中氧化铋(Bi2O3)的质量百分比为27～32％，非晶态二氧化硅(SiO2)的质量百分比为8～11％，硼酸(H3BO3)的质量百分比为21～30％，硝酸锂(LiNO3)的质量百分比为29～33％，氧化铝(Al2O3)的质量百分比为2～3％，氧化锆(ZrO2)的质量百分比为0.5～2％，各组份之和为100％。The main components of Formula One are bismuth oxide (Bi 2 O 3 ), amorphous silica (SiO 2 ), boric acid (H 3 BO 3 ), lithium nitrate (LiNO 3 ), alumina (Al 2 O 3 ), and Zirconia (ZrO 2 ), wherein the mass percentage of bismuth oxide (Bi 2 O 3 ) is 27 to 32%, the mass percentage of amorphous silica (SiO 2 ) is 8 to 11%, and boric acid (H 3 BO 3 ) The mass percentage is 21 to 30%, the mass percentage of lithium nitrate (LiNO 3 ) is 29 to 33%, the mass percentage of alumina (Al 2 O 3 ) is 2 to 3%, and the mass of zirconium oxide (ZrO 2 ) The percentage is 0.5 to 2%, and the sum of the components is 100%.

配方二的主要成份为氧化铋(Bi2O3)、非晶态二氧化硅(SiO2)、氧化硼(B2O3)、硝酸锂(LiNO3)、氧化铝(Al2O3)和氧化锆(ZrO2)，其中氧化铋(Bi2O3)的质量百分比为34.9～43.3％，非晶态二氧化硅(SiO2)的质量百分比为12.2～14.5％，氧化硼(B2O3)的质量百分比为8～13.7％，硝酸锂(LiNO3)的质量百分比为29.3～37％，氧化铝(Al2O3)的质量百分比为2.7～3.4％，氧化锆(ZrO2)的质量百分比为1.2～1.5％，各组份之和为100％。The main components of Formulation 2 are bismuth oxide (Bi 2 O 3 ), amorphous silica (SiO 2 ), boron oxide (B 2 O 3 ), lithium nitrate (LiNO 3 ), and aluminum oxide (Al 2 O 3 ). And zirconium oxide (ZrO 2 ), wherein the mass percentage of bismuth oxide (Bi 2 O 3 ) is 34.9 to 43.3%, the mass percentage of amorphous silica (SiO 2 ) is 12.2 to 14.5%, and boron oxide (B 2 ) The mass percentage of O 3 ) is 8 to 13.7%, the mass percentage of lithium nitrate (LiNO 3 ) is 29.3 to 37%, and the mass percentage of alumina (Al 2 O 3 ) is 2.7 to 3.4%, and zirconium oxide (ZrO 2 ) The mass percentage is 1.2 to 1.5%, and the sum of the components is 100%.

所述玻璃粉粒径为1～5μm。The glass frit has a particle diameter of 1 to 5 μm.

按配方一制备所得玻璃粉最大粒径可通过加溶剂球磨的方式减小至100nm以下，按配方二制备所得玻璃粉最大粒径可通过加溶剂球磨的方式减小至1μm以下。The maximum particle size of the glass powder prepared according to the formula 1 can be reduced to less than 100 nm by means of solvent ball milling. The maximum particle size of the glass powder prepared according to the formula 2 can be reduced to less than 1 μm by means of solvent ball milling.

所述无机颜料悬浮液共有六种颜色，其固相组份为六种工业色料，其中白色色料为氧化钛(TiO2)，红色色料为氧化铁(Fe2O3)，黄色色料为钛铬黄，绿色色料为钴绿，蓝色色料为钴蓝(CoAl2O4)，黑色色料为铜铬黑；所述六种工业色料的最大粒径均需小于2微米，且其最大粒径可通过加溶剂球磨的方式减小至100nm以下。The inorganic pigment suspension has six colors, and the solid phase component is six industrial pigments, wherein the white colorant is titanium oxide (TiO 2 ), the red color material is iron oxide (Fe 2 O 3 ), yellow color. The material is titanium chrome yellow, the green color material is cobalt green, the blue color material is cobalt blue (CoAl 2 O 4 ), and the black color material is copper chrome black; the maximum particle size of the six industrial color materials needs to be less than 2 micrometers. And its maximum particle size can be reduced to below 100 nm by means of solvent ball milling.

所述低熔点玻璃粉悬浮液与无机颜料悬浮液，其液相组份(溶剂)的成份与各成份质量百分比相同，均由68～78％的主溶剂，14～20％的分散剂，7～11％的表面活性剂和0.1～1％的光稳定剂组成，各组份之和为100％；所述的主溶剂为1，2-丙二醇二甲醚，乙二醇单乙醚，环己酮中的一种或任意几种的混合物；所述的分散剂包含二乙二醇丁醚与丙烯酸树脂，其中二乙二醇丁醚与丙烯酸树脂的质量比为15:1，并且丙烯酸树脂的平均分子量为5000～8000；所述的表面活性剂为1，2-丙二醇二乙酸酯；所述的光稳定剂为癸二酸双(1,2,2,6,6-戊甲基-4-哌啶基)酯(HS-508)；所述的低熔点玻璃粉悬浮液与无机颜料悬浮液中固相组份与液相组份的质量比均为1:3。 The low-melting glass frit suspension and the inorganic pigment suspension have the same liquid component (solvent) composition as the mass percentage of each component, ranging from 68 to 78% of the main solvent, and 14 to 20% of the dispersing agent, 7 ～11% of a surfactant and 0.1 to 1% of a light stabilizer, the sum of the components is 100%; the main solvent is 1,2-propylene glycol dimethyl ether, ethylene glycol monoethyl ether, cyclohexyl a mixture of one or any of several ketones; the dispersant comprising diethylene glycol butyl ether and an acrylic resin, wherein the mass ratio of diethylene glycol butyl ether to acrylic resin is 15:1, and the acrylic resin The average molecular weight is 5000-8000; the surfactant is 1,2-propylene glycol diacetate; and the light stabilizer is bismuth azelaic acid (1,2,2,6,6-pentylmethyl- 4-piperidinyl)ester (HS-508); the mass ratio of the solid phase component to the liquid component in the low-melting glass powder suspension and the inorganic pigment suspension is 1:3.

本发明的技术方案之二是：The second technical solution of the present invention is:

一种玻璃表面喷绘打印用铋硅硼系低熔点油墨的制备方法，其特征是它包括以下步骤:A method for preparing a silicon germanium-based low melting point ink for glass surface printing printing, characterized in that it comprises the following steps:

(1)制备低熔点玻璃粉悬浮液：首先按照所述配方一或配方二制备低熔点玻璃粉，然后配制低熔点玻璃粉悬浮液中的溶剂，最后按低熔点玻璃粉与溶剂质量比1:3，球料比5～8:1，转速400～600r/min，称量低熔点玻璃粉与溶剂倒入球磨罐中，使用行星球磨机球磨12～48h，得低熔点玻璃粉悬浮液。(1) Preparation of low-melting glass powder suspension: firstly, according to the formula 1 or the formula 2, a low-melting glass powder is prepared, and then the solvent in the low-melting glass powder suspension is prepared, and finally the low-melting glass powder and the solvent mass ratio are 1: 3, the ball to material ratio of 5 ~ 8:1, the speed of 400 ~ 600r / min, weighing low-melting glass powder and solvent into the ball mill tank, ball milling using a planetary ball mill 12 ~ 48h, to obtain a low-melting glass powder suspension.

(2)制备无机颜料悬浮液：首先配制无机颜料悬浮液中的溶剂，然后按照色料与溶剂质量比1:3，球料比5～8:1，转速400～600r/min，称量某种颜色色料与溶剂倒入球磨罐中，使用行星球磨机球磨12～48h，得无机颜料悬浮液。(2) Preparation of inorganic pigment suspension: firstly prepare the solvent in the inorganic pigment suspension, and then weigh a certain amount according to the mass ratio of the colorant to the solvent of 1:3, the ratio of the ball to the material of 5 to 8:1, and the rotation speed of 400 to 600 r/min. The color pigment and solvent are poured into a ball mill jar, and ball milled for 12 to 48 hours using a planetary ball mill to obtain an inorganic pigment suspension.

(3)低熔点玻璃粉悬浮液与无机颜料悬浮液混合：按照低熔点玻璃粉悬浮液与无机颜料悬浮液体积比3～5:1，量取步骤(1)和(2)制备所得低熔点玻璃粉悬浮液与无机颜料悬浮液倒入烧杯中，使用电动恒速搅拌器，设定转速100r/min，搅拌30min。(3) Mixing the low-melting glass frit suspension with the inorganic pigment suspension: according to the volume ratio of the low-melting glass frit suspension to the inorganic pigment suspension of 3 to 5:1, the low melting point obtained by the steps (1) and (2) is measured. The glass frit suspension and the inorganic pigment suspension were poured into a beaker, and an electric constant speed stirrer was used to set the rotation speed of 100 r/min and stir for 30 min.

(4)对步骤(3)制备所得油墨使用激光粒度仪进行粒径检测，若粒径不符合要求，则延长球磨时间或使用过滤设备进行过滤。(4) The particle obtained by the step (3) is subjected to particle size detection using a laser particle size analyzer. If the particle size does not meet the requirements, the ball milling time is extended or filtration is performed using a filtering device.

本发明的创新性主要在于通过球磨的方式将玻璃粉悬浮液、颜料悬浮液中的固相组份与液相组份进行混合，同时可以通过球磨参数的设定控制两种悬浮液中的固相组份粒径；此外，本发明的创新性还包括六种无机颜料的成份及两种悬浮液中液相组份的成份及各成份质量百分比。The innovation of the invention mainly consists of mixing the solid phase component of the glass frit suspension and the pigment suspension with the liquid component by ball milling, and controlling the solidification of the two suspensions by setting the ball milling parameters. The phase component particle size; in addition, the inventive concept also includes the composition of the six inorganic pigments and the composition of the liquid component in the two suspensions and the mass percentage of each component.

本发明的有益效果是：The beneficial effects of the invention are:

(1)本发明提供的玻璃表面喷绘打印用铋硅硼系低熔点油墨，由低熔点玻璃粉悬浮液与无机颜料悬浮液配制而成，且低熔点玻璃粉悬浮液与无机颜料悬浮液中的固相组份最大粒径最小可小于100nm，可以更好的适应高精度玻璃喷绘打印的需要。(1) The silicon-on-silicon boron-based low-melting ink for glass surface printing printing provided by the present invention is prepared from a low-melting glass powder suspension and an inorganic pigment suspension, and is suspended in a low-melting glass powder suspension and an inorganic pigment suspension. The maximum particle size of the solid phase component can be less than 100 nm, which can better meet the needs of high precision glass inkjet printing.

(2)本发明提供的玻璃表面喷绘打印用铋硅硼系低熔点油墨，相较于一般的高温玻璃油墨烧结温度更低，大量熔化开始温度为600～650℃。(2) The silicon germanium-based low-melting ink for glass surface printing printing provided by the present invention has a lower sintering temperature than a general high-temperature glass ink, and a large melting start temperature is 600 to 650 °C.

(3)本发明提供的玻璃表面喷绘打印用铋硅硼系低熔点油墨，烧结之后与玻璃的结合力强，且不会褪色、掉色。(3) The silicon-on-silicon boron-based low-melting ink for glass surface printing printing provided by the present invention has strong binding force with glass after sintering, and does not fade or fade.

(4)本发明提供的玻璃表面喷绘打印用铋硅硼系低熔点油墨，制造工艺安 全、简单、稳定，适合工业化大批量生产。(4) The silicon germanium-based low-melting ink for glass surface printing and printing provided by the present invention has a manufacturing process Full, simple and stable, suitable for industrial mass production.

(5)本发明提供的玻璃表面喷绘打印用铋硅硼系低熔点油墨，制备所需原料均为常见工业原料，且原料价格便宜，产品制造成本远低于同类产品。(5) The silicon germanium-based low-melting ink for glass surface printing printing provided by the invention has the common raw materials for preparing the raw materials, and the raw material price is cheap, and the manufacturing cost of the product is much lower than that of the similar products.

(6)本发明提供的玻璃表面喷绘打印用铋硅硼系低熔点油墨，由低熔点玻璃粉悬浮液与无机颜料悬浮液配制而成，低熔点玻璃粉悬浮液与无机颜料悬浮液比例可调，可以通过比例的改变调节颜色深浅，可以更好地配合计算机软件调色，获得更好的打印效果。(6) The silicon-on-silicon boron low-melting ink for glass surface printing printing provided by the invention is prepared from a low-melting glass powder suspension and an inorganic pigment suspension, and the ratio of the low-melting glass powder suspension to the inorganic pigment suspension is adjustable. You can adjust the color depth by changing the scale, which can better match the computer software to achieve better printing results.

附图说明DRAWINGS

图1是实施例一制备所得一种玻璃表面喷绘打印用铋硅硼系低熔点绿色油墨热分析(DSC)结果图。BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a graph showing the results of thermal analysis (DSC) of a silicon germanium-based low melting point green ink for glass surface printing printing prepared in the first embodiment.

图2是实施例一制备所得一种玻璃表面喷绘打印用铋硅硼系低熔点绿色油墨激光粒度检测图。2 is a laser particle size detection diagram of a silicon germanium-based low melting point green ink for glass surface printing printing prepared in the first embodiment.

图3是实施例一制备所得低熔点玻璃粉悬浮液激光粒度检测图。3 is a laser particle size detection diagram of the obtained low-melting glass powder suspension obtained in the first embodiment.

图4是实施例一制备所得无机绿色颜料悬浮液激光粒度检测图。4 is a laser particle size detection diagram of the obtained inorganic green pigment suspension prepared in Example 1.

图5是实施例二制备所得低熔点玻璃粉悬浮液激光粒度检测图。Figure 5 is a laser particle size detection diagram of the low-melting glass powder suspension obtained in the second embodiment.

图6是实施例二制备所得无机红色颜料悬浮液激光粒度检测图。Figure 6 is a laser particle size detection diagram of the inorganic red pigment suspension obtained in the second embodiment.

图7是实施例二制备所得无机红色颜料悬浮液烘干后固相组份扫描电镜(SEM)图。Figure 7 is a scanning electron microscope (SEM) image of the solid phase component after drying of the obtained inorganic red pigment suspension prepared in Example 2.

图8是实施例三制备所得一种玻璃表面喷绘打印用铋硅硼系低熔点白色油墨热分析(DSC)结果图。Fig. 8 is a graph showing the results of thermal analysis (DSC) of a silicon germanium-based low-melting white ink for glass surface printing printing prepared in the third embodiment.

图9是实施例三制备所得无机白色颜料悬浮液激光粒度检测图。Figure 9 is a laser particle size detection diagram of the inorganic white pigment suspension obtained in the third embodiment.

图10是实施例四制备所得一种玻璃表面喷绘打印用铋硅硼系低熔点黄色油墨激光粒度检测图。Fig. 10 is a laser particle size detection diagram of a silicon germanium boron-based low melting point yellow ink for glass surface printing printing prepared in the fourth embodiment.

图11是实施例四制备所得无机黄色颜料悬浮液激光粒度检测图。Figure 11 is a laser particle size detection diagram of the inorganic yellow pigment suspension obtained in the fourth embodiment.

图12是实施例五制备所得一种玻璃表面喷绘打印用铋硅硼系低熔点蓝色油墨激光粒度检测图。12 is a laser particle size detection diagram of a silicon germanium boron-based low melting point blue ink for glass surface printing printing prepared in the fifth embodiment.

图13是实施例五制备所得无机蓝色颜料悬浮液激光粒度检测图。Figure 13 is a laser particle size detection diagram of the inorganic blue pigment suspension obtained in the fifth embodiment.

图14是实施例六制备所得一种玻璃表面喷绘打印用铋硅硼系低熔点黑色油墨激光粒度检测图。Figure 14 is a laser particle size detection diagram of a silicon germanium-based low melting point black ink for glass surface printing printing prepared in Example 6.

图15是实施例六制备所得无机黑色颜料悬浮液激光粒度检测图。 Figure 15 is a laser particle size detection diagram of the inorganic black pigment suspension obtained in Example 6.

具体实施方式detailed description

下面结合实施例和对应附图对本发明作进一步阐述。The present invention will be further described below in conjunction with the embodiments and corresponding drawings.

实施例一Embodiment 1

一种玻璃表面喷绘打印用铋硅硼系低熔点绿色油墨，其制备过程为:The invention discloses a silicon-on-silicon boron-based low-melting green ink for printing on a glass surface, and the preparation process is as follows:

(1)制备低熔点玻璃粉悬浮液：首先根据质量百分比氧化铋(α-型Bi2O3)28.3％、非晶态氧化硅(SiO2)9.6％，硼酸(H3BO3)29.8％、硝酸锂(LiNO3)29.1％、氧化铝(Al2O3)2.2％、氧化锆(ZrO2)1％，称量氧化铋(α-型Bi2O3)70.75g、非晶态氧化硅(SiO2)24g、硼酸(H3BO3)74.5g、硝酸锂(LiNO3)72.75g、氧化铝(Al2O3)5.5g、氧化锆(ZrO2)2.5g，制备低熔点玻璃粉250g；然后按份质量百分比1，2-丙二醇二甲醚50％、乙二醇单乙醚10％，环己酮15％、二乙二醇丁醚15％、丙烯酸树脂1％、1，2-丙二醇二乙酸酯8.5％、癸二酸双(1,2,2,6,6-戊甲基-4-哌啶基)酯(HS-508)0.5％，称量1，2-丙二醇二甲醚375g、乙二醇单乙醚75g，环己酮112.5g、二乙二醇丁醚112.5g、丙烯酸树脂7.5g、1，2-丙二醇二乙酸酯63.75g、癸二酸双(1,2,2,6,6-戊甲基-4-哌啶基)酯(HS-508)3.75g，配制750g低熔点玻璃粉悬浮液中的溶剂；最后按低熔点玻璃粉与溶剂质量比1:3，球料比5～8:1，转速400～600r/min，称量上述低熔点玻璃粉与溶剂倒入球磨罐中，使用行星球磨机球磨48h，得低熔点玻璃粉悬浮液。(1) Preparation of low-melting glass powder suspension: firstly, yttrium oxide (α-type Bi 2 O 3 ) 28.3%, amorphous silicon oxide (SiO 2 ) 9.6%, boric acid (H 3 BO 3 ) 29.8% according to the mass percentage Lithium nitrate (LiNO 3 ) 29.1%, alumina (Al 2 O 3 ) 2.2%, zirconia (ZrO 2 ) 1%, weighing yttrium oxide (α-type Bi 2 O 3 ) 70.75g, amorphous oxidation Low-melting glass was prepared by using 24 g of silicon (SiO 2 ), 74.5 g of boric acid (H 3 BO 3 ), 72.75 g of lithium nitrate (LiNO 3 ), 5.5 g of alumina (Al 2 O 3 ), and 2.5 g of zirconium oxide (ZrO 2 ). 250g of powder; then 50% by weight of 1,2-propylene glycol dimethyl ether, 10% of ethylene glycol monoethyl ether, 15% of cyclohexanone, 15% of diethylene glycol butyl ether, 1% of acrylic resin, 1, 2 - propylene glycol diacetate 8.5%, bis(1,2,2,6,6-pentylmethyl-4-piperidyl) sebacate (HS-508) 0.5%, weigh 1,2-propanediol 375g of dimethyl ether, 75g of ethylene glycol monoethyl ether, 112.5g of cyclohexanone, 112.5g of diethylene glycol butyl ether, 7.5g of acrylic resin, 63.75g of 1,2-propanediol diacetate, and bismuth azelate , 2,2,6,6-pentylmethyl-4-piperidinyl)ester (HS-508) 3.75g, prepared in 750g of low-melting glass powder suspension solvent; The ratio of the glass powder to the solvent is 1:3, the ratio of the ball to the material is 5-8:1, and the rotation speed is 400-600 r/min. The low-melting glass powder and the solvent are weighed into a ball mill jar and ball milled for 48 hours using a planetary ball mill to obtain a low melting point. Glass powder suspension.

(2)制备无机颜料悬浮液：无机颜料悬浮液与低熔点玻璃粉悬浮液中的溶剂完全相同，所以制备时首先按照步骤(1)中溶剂各组份质量百分比配制150g无机绿色颜料悬浮液中的溶剂，然后按照色料与溶剂质量比1:3，球料比5～8:1，转速400～600r/min，称量50g钴绿与150g溶剂倒入球磨罐中，使用行星球磨机球磨48h，得无机绿色颜料悬浮液。(2) Preparation of inorganic pigment suspension: The inorganic pigment suspension is exactly the same as the solvent in the low-melting glass powder suspension, so firstly, 150 g of the inorganic green pigment suspension is prepared according to the mass percentage of each component of the solvent in the step (1). Solvent, then according to the color to solvent mass ratio of 1:3, ball to material ratio of 5 ~ 8:1, speed 400 ~ 600r / min, weigh 50g cobalt green and 150g solvent into the ball mill tank, ball milling using a planetary ball mill 48h , obtained an inorganic green pigment suspension.

(3)低熔点玻璃粉悬浮液与无机颜料悬浮液混合：按照低熔点玻璃粉悬浮液与无机颜料悬浮液体积比5:1，量取步骤(1)和(2)制备所得低熔点玻璃粉悬浮液与无机绿色颜料悬浮液倒入烧杯中，使用电动恒速搅拌器，设定转速100r/min，搅拌30min，得到约1升玻璃表面喷绘打印用铋硅硼系低熔点绿色油墨。(3) mixing the low-melting glass frit suspension with the inorganic pigment suspension: according to the volume ratio of the low-melting glass frit suspension to the inorganic pigment suspension of 5:1, the obtained low-melting glass frit prepared in the steps (1) and (2) The suspension and the inorganic green pigment suspension were poured into a beaker, and an electric constant speed stirrer was used to set a rotation speed of 100 r/min and stirred for 30 minutes to obtain about 1 liter of a silicon-on-boron low-melting green ink for printing on a glass surface.

(4)对步骤(3)制备所得油墨使用激光粒度仪进行粒径检测，若粒径不符合要求，则延长球磨时间或使用过滤设备进行过滤。(4) The particle obtained by the step (3) is subjected to particle size detection using a laser particle size analyzer. If the particle size does not meet the requirements, the ball milling time is extended or filtration is performed using a filtering device.

本实施例获得的玻璃表面喷绘打印用铋硅硼系低熔点绿色油墨，其热分析 (DSC)结果图如图1所示，其大量熔化开始温度约为620℃。The thermal conductivity analysis of the silicon-on-silicon boron-based low-melting green ink for glass surface printing printing obtained in this embodiment The (DSC) results are shown in Figure 1, with a large number of melting onset temperatures of about 620 °C.

图2所示为该绿色油墨的激光粒度检测图，可以看出油墨中固相组份粒径全部小于1.1μm；图3所示为本实施例制备所得低熔点玻璃粉悬浮液激光粒度检测图，可以看出低熔点玻璃粉悬浮液中的固相组份粒径全部小于1.1μm；图4所示为本实施例制备所得无机绿色颜料悬浮液激光粒度检测图，可以看出无机绿色颜料悬浮液中的固相组份粒径全部小于500nm。FIG. 2 is a laser particle size detection diagram of the green ink, and it can be seen that the particle size of the solid phase component in the ink is less than 1.1 μm; FIG. 3 is a laser particle size detection diagram of the low-melting glass powder suspension prepared in the present embodiment. It can be seen that the particle size of the solid phase component in the low-melting glass frit suspension is less than 1.1 μm; FIG. 4 shows the laser particle size detection of the inorganic green pigment suspension obtained in the present example, and it can be seen that the inorganic green pigment suspension The solid phase component particle size in the solution is all less than 500 nm.

实施例二Embodiment 2

一种玻璃表面喷绘打印用铋硅硼系低熔点红色油墨，其制备过程为:The invention discloses a silicon-on-silicon boron low-melting red ink for printing on a glass surface, and the preparation process is as follows:

(1)制备低熔点玻璃粉悬浮液：首先根据质量百分比氧化铋(α-型Bi2O3)36％、非晶态氧化硅(SiO2)12.2％，氧化硼(B2O3)10.7％、硝酸锂(LiNO3)37％、氧化铝(Al2O3)2.8％、氧化锆(ZrO2)1.3％，称量氧化铋(α-型Bi2O3)90g、非晶态氧化硅(SiO2)30.5g、氧化硼(B2O3)26.75g、硝酸锂(LiNO3)92.5g、氧化铝(Al2O3)7g、氧化锆(ZrO2)3.25g，制备低熔点玻璃粉250g；然后按份质量百分比1，2-丙二醇二甲醚50％、乙二醇单乙醚10％，环己酮15％、二乙二醇丁醚15％、丙烯酸树脂1％、1，2-丙二醇二乙酸酯8.5％、癸二酸双(1,2,2,6,6-戊甲基-4-哌啶基)酯(HS-508)0.5％，称量1，2-丙二醇二甲醚375g、乙二醇单乙醚75g，环己酮112.5g、二乙二醇丁醚112.5g、丙烯酸树脂7.5g、1，2-丙二醇二乙酸酯63.75g、癸二酸双(1,2,2,6,6-戊甲基-4-哌啶基)酯(HS-508)3.75g，配制750g低熔点玻璃粉悬浮液中的溶剂；最后按低熔点玻璃粉与溶剂质量比1:3，球料比5～8:1，转速400～600r/min，称量上述低熔点玻璃粉与溶剂倒入球磨罐中，使用行星球磨机球磨48h，得纳米级低熔点玻璃粉悬浮液。(1) Preparation of low-melting glass powder suspension: firstly, according to the mass percentage, yttrium oxide (α-type Bi 2 O 3 ) 36%, amorphous silicon oxide (SiO 2 ) 12.2%, boron oxide (B 2 O 3 ) 10.7 %, lithium nitrate (LiNO 3 ) 37%, alumina (Al 2 O 3 ) 2.8%, zirconia (ZrO 2 ) 1.3%, weighed yttrium oxide (α-type Bi 2 O 3 ) 90 g, amorphous oxidation Preparation of low melting point of 30.5 g of silicon (SiO 2 ), 26.75 g of boron oxide (B 2 O 3 ), 92.5 g of lithium nitrate (LiNO 3 ), 7 g of alumina (Al 2 O 3 ), and 3.25 g of zirconium oxide (ZrO 2 ) Glass powder 250g; then, according to the parts by mass of 1,2-propylene glycol dimethyl ether 50%, ethylene glycol monoethyl ether 10%, cyclohexanone 15%, diethylene glycol butyl ether 15%, acrylic resin 1%, 1, 2-propanediol diacetate 8.5%, bis(1,2,2,6,6-pentylmethyl-4-piperidyl) sebacate (HS-508) 0.5%, weigh 1,2- Propylene glycol dimethyl ether 375g, ethylene glycol monoethyl ether 75g, cyclohexanone 112.5g, diethylene glycol butyl ether 112.5g, acrylic resin 7.5g, 1,2-propylene glycol diacetate 63.75g, azelaic acid bis ( 1.25g of 1,2,2,6,6-pentylmethyl-4-piperidinyl)ester (HS-508), prepared as a solvent in 750g of low-melting glass powder suspension; The mass ratio of glass powder to solvent is 1:3, the ratio of ball to material is 5-8:1, the rotation speed is 400-600r/min, and the above low-melting glass powder and solvent are weighed into a ball mill jar, and ball milled for 48 hours using a planetary ball mill to obtain nanometer scale. Low melting glass powder suspension.

(2)制备无机颜料悬浮液：无机颜料悬浮液与低熔点玻璃粉悬浮液中的溶剂完全相同，所以制备时首先按照步骤(1)中溶剂各组份质量百分比配制150g无机红色颜料悬浮液中的溶剂，然后按照色料与溶剂质量比1:3，球料比5～8:1，转速400～600r/min，称量50g氧化铁(Fe2O3)与150g溶剂倒入球磨罐中，使用行星球磨机球磨48h，得纳米级无机红色颜料悬浮液。(2) Preparation of inorganic pigment suspension: The inorganic pigment suspension is exactly the same as the solvent in the low-melting glass powder suspension, so firstly, 150 g of the inorganic red pigment suspension is prepared according to the mass percentage of each component of the solvent in the step (1). Solvent, then according to the color to solvent mass ratio of 1:3, ball to material ratio of 5 ~ 8:1, speed 400 ~ 600r / min, weigh 50g of iron oxide (Fe 2 O 3 ) and 150g of solvent into the ball mill tank The ball was milled for 48 h using a planetary ball mill to obtain a nano-scale inorganic red pigment suspension.

(3)低熔点玻璃粉悬浮液与无机颜料悬浮液混合：按照低熔点玻璃粉悬浮液与无机颜料悬浮液体积比5:1，量取步骤(1)和(2)制备所得纳米级低熔点玻璃粉悬浮液与纳米级无机红色颜料悬浮液倒入烧杯中，使用电动恒速搅拌器，设定转速100r/min，搅拌30min，得到约1升玻璃表面喷绘打印用铋硅硼系低熔点红 色油墨。(3) mixing the low-melting glass frit suspension with the inorganic pigment suspension: according to the volume ratio of the low-melting glass frit suspension to the inorganic pigment suspension of 5:1, the nano-level low melting point prepared by the steps (1) and (2) is measured. The glass powder suspension and the nano-inorganic red pigment suspension are poured into a beaker, and an electric constant-speed agitator is used to set the rotation speed of 100 r/min and stirred for 30 minutes to obtain about 1 liter of glass surface printing and printing with silicon germanium-based low melting red. Color ink.

(4)对步骤(3)制备所得油墨使用激光粒度仪进行粒径检测，若粒径不符合要求，则延长球磨时间或使用过滤设备进行过滤。(4) The particle obtained by the step (3) is subjected to particle size detection using a laser particle size analyzer. If the particle size does not meet the requirements, the ball milling time is extended or filtration is performed using a filtering device.

本实施例获得的玻璃表面喷绘打印用铋硅硼系低熔点红色油墨，其热分析(DSC)结果图与图1相似。The glass surface printing printing obtained in this example is a silicon germanium boron low melting point red ink, and the thermal analysis (DSC) result chart is similar to that of FIG.

图5所示为本实施例制备所得低熔点玻璃粉悬浮液激光粒度检测图，可以看出低熔点玻璃粉悬浮液中固相组份的粒径全部小于110nm。FIG. 5 is a view showing the laser particle size detection of the obtained low-melting glass powder suspension prepared in the present example, and it can be seen that the particle size of the solid phase component in the low-melting glass powder suspension is less than 110 nm.

图6所示为本实施例制备所得无机红色颜料悬浮液激光粒度检测图，可以看出未团聚的无机绿色颜料中的固相组份粒径基本小于100nm。FIG. 6 is a view showing the laser particle size detection of the obtained inorganic red pigment suspension prepared in the present example, and it can be seen that the particle size of the solid phase component in the unagglomerated inorganic green pigment is substantially less than 100 nm.

图7所示为本实施例制备所得无机红色颜料悬浮液烘干后固相组份扫描电镜(SEM)图，可以看出无机红色颜料中的固相组份粒径基本小于100nm，可以印证图6中粒径检测结果偏大部分为颗粒团聚，在使用前可利用超声波打散。7 is a scanning electron microscopy (SEM) image of the solid phase component obtained after drying the obtained inorganic red pigment suspension prepared in the present embodiment, and it can be seen that the particle size of the solid phase component in the inorganic red pigment is substantially less than 100 nm, which can be confirmed. Most of the particle size detection results in 6 are particle agglomeration, which can be broken up by ultrasonic waves before use.

实施例三Embodiment 3

一种玻璃表面喷绘打印用铋硅硼系低熔点白色油墨，其制备过程为:The invention discloses a silicon-on-silicon boron low-melting white ink for printing on a glass surface, and the preparation process is as follows:

(1)制备低熔点玻璃粉悬浮液：制备过程与实施例一步骤(1)完全相同。(1) Preparation of a low-melting glass frit suspension: The preparation process is identical to the first step (1) of the first embodiment.

(2)制备无机颜料悬浮液：无机颜料悬浮液与低熔点玻璃粉悬浮液中的溶剂完全相同，所以制备时首先按照步骤(1)中溶剂各组份质量百分比配制150g无机白色颜料悬浮液中的溶剂，然后按照色料与溶剂质量比1:3，球料比5～8:1，转速400～600r/min，称量50g氧化钛(TiO2)与150g溶剂倒入球磨罐中，使用行星球磨机球磨48h，得无机白色颜料悬浮液。(2) Preparation of inorganic pigment suspension: The inorganic pigment suspension is exactly the same as the solvent in the low-melting glass powder suspension, so firstly, 150 g of the inorganic white pigment suspension is prepared according to the mass percentage of each component of the solvent in the step (1). The solvent is then poured into a ball mill tank according to a mass ratio of the colorant to the solvent of 1:3, a ball to material ratio of 5 to 8:1, a rotation speed of 400 to 600 r/min, and a weight of 50 g of titanium oxide (TiO 2 ) and 150 g of the solvent. The ball mill was ball milled for 48 h to obtain an inorganic white pigment suspension.

(3)低熔点玻璃粉悬浮液与无机颜料悬浮液混合：按照低熔点玻璃粉悬浮液与无机颜料悬浮液体积比5:1，量取步骤(1)和(2)制备所得低熔点玻璃粉悬浮液与无机白色颜料悬浮液倒入烧杯中，使用电动恒速搅拌器，设定转速100r/min，搅拌30min，得到约1升玻璃表面喷绘打印用铋硅硼系低熔点白色油墨；(3) mixing the low-melting glass frit suspension with the inorganic pigment suspension: according to the volume ratio of the low-melting glass frit suspension to the inorganic pigment suspension of 5:1, the obtained low-melting glass frit prepared in the steps (1) and (2) The suspension and the inorganic white pigment suspension are poured into a beaker, and an electric constant speed stirrer is used, the rotation speed is set to 100 r/min, and the mixture is stirred for 30 minutes to obtain about 1 liter of a silicon-on-boron low-melting white ink for printing on a glass surface.

(4)对步骤(3)制备所得油墨使用激光粒度仪进行粒径检测，若粒径不符合要求，则延长球磨时间或使用过滤设备进行过滤。(4) The particle obtained by the step (3) is subjected to particle size detection using a laser particle size analyzer. If the particle size does not meet the requirements, the ball milling time is extended or filtration is performed using a filtering device.

本实施例获得的玻璃表面喷绘打印用铋硅硼系低熔点白色油墨，其热分析(DSC)结果图如图8所示，其大量熔化开始温度约为650℃。The glass surface-printing printing obtained by the present embodiment uses a silicon germanium-boride low-melting white ink, and its thermal analysis (DSC) results are shown in Fig. 8. The large-scale melting start temperature is about 650 °C.

本实施例制备所得无机白色颜料悬浮液激光粒度检测图如图9所示，可以看出未团聚的白色颜料悬浮液中的固相组份粒径全部小于110nm，团聚颗粒粒径也 基本小于2μm，团聚颗粒可利用超声波打散。The laser particle size detection chart of the obtained inorganic white pigment suspension prepared in this example is shown in Fig. 9. It can be seen that the particle size of the solid phase component in the unagglomerated white pigment suspension is less than 110 nm, and the particle size of the agglomerated particles is also Substantially less than 2 μm, the agglomerated particles can be broken up using ultrasonic waves.

实施例四Embodiment 4

一种玻璃表面喷绘打印用铋硅硼系低熔点黄色油墨，其制备过程为:A glass surface printing printing using silicon germanium boron low melting point yellow ink, the preparation process is as follows:

(1)制备低熔点玻璃粉悬浮液：制备过程与实施例一步骤(1)完全相同。(1) Preparation of a low-melting glass frit suspension: The preparation process is identical to the first step (1) of the first embodiment.

(2)制备无机颜料悬浮液：无机颜料悬浮液与低熔点玻璃粉悬浮液中的溶剂完全相同，所以制备时首先按照步骤(1)中溶剂各组份质量百分比配制150g无机黄色颜料悬浮液中的溶剂，然后按照色料与溶剂质量比1:3，球料比5～8:1，转速400～600r/min，称量50g钛铬黄与150g溶剂倒入球磨罐中，使用行星球磨机球磨48h，得无机黄色颜料悬浮液。(2) Preparation of inorganic pigment suspension: The inorganic pigment suspension is exactly the same as the solvent in the low-melting glass powder suspension, so firstly, 150 g of the inorganic yellow pigment suspension is prepared according to the mass percentage of each component of the solvent in the step (1). Solvent, then according to the color to solvent mass ratio of 1:3, ball ratio of 5 ~ 8:1, speed 400 ~ 600r / min, weigh 50g of titanium chrome and 150g of solvent into the ball mill tank, using a planetary ball mill ball mill At 48h, an inorganic yellow pigment suspension was obtained.

(3)低熔点玻璃粉悬浮液与无机颜料悬浮液混合：按照低熔点玻璃粉悬浮液与无机颜料悬浮液体积比5:1，量取步骤(1)和(2)制备所得低熔点玻璃粉悬浮液与无机黄色颜料悬浮液倒入烧杯中，使用电动恒速搅拌器，设定转速100r/min，搅拌30min，得到约1升玻璃表面喷绘打印用铋硅硼系低熔点黄色油墨。(3) mixing the low-melting glass frit suspension with the inorganic pigment suspension: according to the volume ratio of the low-melting glass frit suspension to the inorganic pigment suspension of 5:1, the obtained low-melting glass frit prepared in the steps (1) and (2) The suspension and the inorganic yellow pigment suspension were poured into a beaker, and an electric constant speed stirrer was used to set the rotation speed of 100 r/min, and the mixture was stirred for 30 minutes to obtain about 1 liter of a silicon-on-boron low-melting yellow ink for printing on a glass surface.

(4)对步骤(3)制备所得油墨使用激光粒度仪进行粒径检测，若粒径不符合要求，则延长球磨时间或使用过滤设备进行过滤。(4) The particle obtained by the step (3) is subjected to particle size detection using a laser particle size analyzer. If the particle size does not meet the requirements, the ball milling time is extended or filtration is performed using a filtering device.

本实施例获得的玻璃表面喷绘打印用铋硅硼系低熔点黄色油墨，其激光粒度检测图如图10所示，可以看出该油墨中固相组份粒径全部小于600nm。The glass surface printing printing of the silicon germanium-based low melting point yellow ink obtained in the present embodiment has a laser particle size detection chart as shown in FIG. 10, and it can be seen that the particle diameter of the solid phase component in the ink is less than 600 nm.

本实施例制备所得无机黄色颜料悬浮液激光粒度检测图如图11所示，可以看出未团聚的黄色颜料悬浮液中的固相组份粒径全部小于110nm，团聚颗粒粒径也基本小于1μm，团聚颗粒可利用超声波打散；本实施例制备所得黄色油墨热分析(DSC)结果图与图1相似。The laser particle size detection chart of the obtained inorganic yellow pigment suspension prepared in this embodiment is shown in Fig. 11. It can be seen that the particle size of the solid phase component in the unagglomerated yellow pigment suspension is less than 110 nm, and the particle size of the agglomerated particles is also substantially less than 1 μm. The agglomerated particles can be broken up by ultrasonic waves; the yellow ink thermal analysis (DSC) results obtained in this example are similar to those in FIG.

实施例五Embodiment 5

一种玻璃表面喷绘打印用铋硅硼系低熔点蓝色油墨，其制备过程为:The invention discloses a silicon-on-silicon boron low-melting blue ink for printing on a glass surface, and the preparation process is as follows:

(1)制备低熔点玻璃粉悬浮液：制备过程与实施例一步骤(1)完全相同。(1) Preparation of a low-melting glass frit suspension: The preparation process is identical to the first step (1) of the first embodiment.

(2)制备无机颜料悬浮液：无机颜料悬浮液与低熔点玻璃粉悬浮液中的溶剂完全相同，所以制备时首先按照步骤(1)中溶剂各组份质量百分比配制150g无机蓝色颜料悬浮液中的溶剂，然后按照色料与溶剂质量比1:3，球料比5～8:1，转速400～600r/min，称量50g钴蓝(CoAl2O4)与150g溶剂倒入球磨罐中，使用行星球磨机球磨48h，得无机蓝色颜料悬浮液。(2) Preparation of inorganic pigment suspension: The inorganic pigment suspension is exactly the same as the solvent in the low-melting glass powder suspension, so firstly, 150 g of the inorganic blue pigment suspension is prepared according to the mass percentage of each component of the solvent in the step (1). Solvent, then according to the mass ratio of pigment to solvent 1:3, ball to material ratio 5 ~ 8:1, speed 400 ~ 600r / min, weigh 50g cobalt blue (CoAl 2 O 4 ) and 150g solvent into the ball mill In the middle, ball milling was carried out for 48 h using a planetary ball mill to obtain an inorganic blue pigment suspension.

(3)低熔点玻璃粉悬浮液与无机颜料悬浮液混合：按照低熔点玻璃粉悬浮液与 无机颜料悬浮液体积比5:1，量取步骤(1)和(2)制备所得低熔点玻璃粉悬浮液与无机蓝色颜料悬浮液倒入烧杯中，使用电动恒速搅拌器，设定转速100r/min，搅拌30min，得到约1升玻璃表面喷绘打印用铋硅硼系低熔点蓝色油墨。(3) mixing of low-melting glass powder suspension with inorganic pigment suspension: according to low-melting glass powder suspension and The inorganic pigment suspension has a volume ratio of 5:1, and the obtained low-melting glass powder suspension prepared by the steps (1) and (2) and the inorganic blue pigment suspension are poured into a beaker, and an electric constant-speed stirrer is used to set the rotation speed. At 100 r/min, the mixture was stirred for 30 minutes to obtain about 1 liter of a silicon-on-silicon boron-based low melting point blue ink for inkjet printing.

(4)对步骤(3)制备所得油墨使用激光粒度仪进行粒径检测，若粒径不符合要求，则延长球磨时间或使用过滤设备进行过滤。(4) The particle obtained by the step (3) is subjected to particle size detection using a laser particle size analyzer. If the particle size does not meet the requirements, the ball milling time is extended or filtration is performed using a filtering device.

本实施例获得的玻璃表面喷绘打印用铋硅硼系低熔点蓝色油墨，其激光粒度检测图如图12所示，可以看出该油墨中固相组份粒径全部小于700nm。In the glass surface printing printing obtained in this embodiment, a silicon germanium-based low melting point blue ink is used, and the laser particle size detection chart is as shown in FIG. 12, and it can be seen that the particle diameter of the solid phase component in the ink is less than 700 nm.

本实施例制备所得无机蓝色颜料悬浮液激光粒度检测图如图13所示，可以看出蓝色颜料悬浮液中的固相组份粒径全部小于300nm。The laser particle size detection chart of the obtained inorganic blue pigment suspension prepared in this example is shown in Fig. 13, and it can be seen that the solid phase component particle diameter in the blue pigment suspension is all less than 300 nm.

本实施例制备所得蓝色油墨热分析(DSC)结果图与图1相似。The blue ink thermal analysis (DSC) results obtained in this example are similar to those in FIG.

实施例六Embodiment 6

一种玻璃表面喷绘打印用铋硅硼系低熔点黑色油墨，其制备过程为：The invention discloses a silicon-on-silicon boron-based low melting point black ink for printing on a glass surface, and the preparation process is as follows:

(1)制备低熔点玻璃粉悬浮液：制备过程与实施例一步骤(1)完全相同。(1) Preparation of a low-melting glass frit suspension: The preparation process is identical to the first step (1) of the first embodiment.

(2)制备无机颜料悬浮液：无机颜料悬浮液与低熔点玻璃粉悬浮液中的溶剂完全相同，所以制备时首先按照步骤(1)中溶剂各组份质量百分比配制150g无机黑色颜料悬浮液中的溶剂，然后按照色料与溶剂质量比1:3，球料比5～8:1，转速400～600r/min，称量50g(CoAl2O4)与150g溶剂倒入球磨罐中，使用行星球磨机球磨48h，得无机黑色颜料悬浮液。(2) Preparation of inorganic pigment suspension: The inorganic pigment suspension is exactly the same as the solvent in the low-melting glass powder suspension, so firstly, 150 g of the inorganic black pigment suspension is prepared according to the mass percentage of the solvent components in the step (1). Solvent, then according to the color to solvent mass ratio 1:3, ball to material ratio of 5 ~ 8:1, speed 400 ~ 600r / min, weigh 50g (CoAl 2 O 4 ) and 150g solvent into the ball mill tank, use The ball mill was ball milled for 48 h to obtain an inorganic black pigment suspension.

(3)低熔点玻璃粉悬浮液与无机颜料悬浮液混合：按照低熔点玻璃粉悬浮液与无机颜料悬浮液体积比5:1，量取步骤(1)和(2)制备所得低熔点玻璃粉悬浮液与无机黑色颜料悬浮液倒入烧杯中，使用电动恒速搅拌器，设定转速100r/min，搅拌30min，得到约1升玻璃表面喷绘打印用铋硅硼系低熔点黑色油墨。(3) mixing the low-melting glass frit suspension with the inorganic pigment suspension: according to the volume ratio of the low-melting glass frit suspension to the inorganic pigment suspension of 5:1, the obtained low-melting glass frit prepared in the steps (1) and (2) The suspension and the inorganic black pigment suspension were poured into a beaker, and an electric constant speed agitator was used to set the rotation speed of 100 r/min, and the mixture was stirred for 30 minutes to obtain about 1 liter of a silicon-on-silicon boron-based low melting point black ink for inkjet printing.

(4)对步骤(3)制备所得油墨使用激光粒度仪进行粒径检测，若粒径不符合要求，则延长球磨时间或使用过滤设备进行过滤。(4) The particle obtained by the step (3) is subjected to particle size detection using a laser particle size analyzer. If the particle size does not meet the requirements, the ball milling time is extended or filtration is performed using a filtering device.

本实施例获得的玻璃表面喷绘打印用铋硅硼系低熔点黑色油墨，其激光粒度检测图如图14所示，可以看出该油墨中未团聚的固相组份粒径全部小于700nm，团聚的固相组份可在使用前利用超声波进行打散。The glass surface printing printing obtained by the present embodiment uses a silicon germanium boron-based low melting point black ink. The laser particle size detection chart is shown in FIG. 14. It can be seen that the particle size of the unagglomerated solid phase component in the ink is less than 700 nm, and the agglomeration is achieved. The solid phase component can be broken up using ultrasound prior to use.

本实施例制备所得无机黑色颜料悬浮液激光粒度检测图如图15所示，可以看出未团聚的黑色颜料悬浮液中的固相组份粒径全部小于1μm，团聚颗粒可利用超声波打散。 The laser particle size detection chart of the obtained inorganic black pigment suspension prepared in this example is shown in Fig. 15. It can be seen that the solid phase component particle size in the unagglomerated black pigment suspension is all less than 1 μm, and the agglomerated particles can be broken up by ultrasonic waves.

本实施例制备所得黑色油墨热分析(DSC)结果图与图1相似。The black ink thermal analysis (DSC) results obtained in this example are similar to those in FIG.

实施例七。Example VII.

本实施例将实施例一制备所得一种玻璃表面喷绘打印用铋硅硼系低熔点绿色油墨烧结到玻璃上，具体的步骤为：In this embodiment, a glass surface printing printing method prepared by the first embodiment is used for sintering a silicon germanium boron low melting point green ink onto a glass. The specific steps are as follows:

(1)将实施例一制备所得绿色油墨均匀地涂画在玻璃表面，所用玻璃为普通的浮法玻璃。(1) The green ink prepared in Example 1 was uniformly painted on the surface of the glass, and the glass used was an ordinary float glass.

(2)使用电吹风将涂画在玻璃上的油墨进行吹干，使油墨液相组份挥发。(2) The ink coated on the glass is blown dry using a hair dryer to volatilize the liquid component of the ink.

(3)油墨吹干后，将玻璃放入到700℃的马弗炉中，烧结3～4分钟，取出。冷却后的烧结效果为油墨中的玻璃粉包裹着无机颜料与玻璃融为一体，结合能力强，且由于本发明使用的颜料均为稳定的无机颜料，故烧结后不易褪色、变色。(3) After the ink was dried, the glass was placed in a muffle furnace at 700 ° C, sintered for 3 to 4 minutes, and taken out. The sintering effect after cooling is that the glass powder in the ink envelops the inorganic pigment and the glass is integrated, and the binding ability is strong, and since the pigment used in the invention is a stable inorganic pigment, it is not easy to fade and discolor after sintering.

实施例八。Example VIII.

本实施例将实施例二制备所得一种玻璃表面喷绘打印用铋硅硼系低熔点红色油墨烧结到玻璃上，具体的步骤为：In this embodiment, a glass surface printing printing method prepared by the second embodiment is used to sinter a silicon-boron-based low-melting red ink onto a glass. The specific steps are as follows:

(1)将实施例二制备所得红色油墨均匀地涂画在玻璃表面，所用玻璃为普通的浮法玻璃。(1) The red ink prepared in Example 2 was uniformly painted on the surface of the glass, and the glass used was ordinary float glass.

(2)使用电吹风将涂画在玻璃上的油墨进行吹干，使油墨液相组份挥发。(2) The ink coated on the glass is blown dry using a hair dryer to volatilize the liquid component of the ink.

(3)油墨吹干后，将玻璃放入到700℃的马弗炉中，烧结3～4分钟，取出。冷却后的烧结效果为烧结后油墨中的玻璃粉包裹着无机颜料与玻璃融为一体，结合能力强。且由于本发明使用的颜料均为稳定的无机颜料，故烧结后不易褪色、变色。 (3) After the ink was dried, the glass was placed in a muffle furnace at 700 ° C, sintered for 3 to 4 minutes, and taken out. The sintering effect after cooling is that the glass powder in the ink after sintering encloses the inorganic pigment and the glass, and has strong bonding ability. Moreover, since the pigments used in the present invention are all stable inorganic pigments, they are not easily faded and discolored after sintering.

Claims (9)

玻璃表面喷绘打印用铋硅硼系低熔点油墨，由低熔点玻璃粉悬浮液与无机颜料悬浮液混合而成；其特征在于：所述低熔点玻璃粉悬浮液中的固相组份玻璃粉有两种配方；The surface of the glass surface is printed with a silicon germanium-based low melting point ink mixed with a low-melting glass powder suspension and an inorganic pigment suspension; characterized in that the solid phase component glass powder in the low-melting glass powder suspension has Two formulations; 配方一的成份为氧化铋、非晶态二氧化硅、硼酸、硝酸锂、氧化铝和氧化锆，其中氧化铋的质量百分比为27～32％，非晶态二氧化硅的质量百分比为8～11％，硼酸的质量百分比为21～30％，硝酸锂的质量百分比为29～33％，氧化铝的质量百分比为2～3％，氧化锆的质量百分比为0.5～2％，各组份之和为100％；The composition of the first component is cerium oxide, amorphous silica, boric acid, lithium nitrate, aluminum oxide and zirconium oxide, wherein the mass percentage of cerium oxide is 27 to 32%, and the mass percentage of amorphous silica is 8 ～. 11%, the mass percentage of boric acid is 21 to 30%, the mass percentage of lithium nitrate is 29 to 33%, the mass percentage of alumina is 2 to 3%, and the mass percentage of zirconia is 0.5 to 2%, and each component is And 100%; 配方二的成份为氧化铋、非晶态二氧化硅、氧化硼、硝酸锂、氧化铝和氧化锆，其中氧化铋的质量百分比为34.9～43.3％，非晶态二氧化硅的质量百分比为12.2～14.5％，氧化硼的质量百分比为8～13.7％，硝酸锂的质量百分比为29.3～37％，氧化铝的质量百分比为2.7～3.4％，氧化锆的质量百分比为1.2～1.5％，各组份之和为100％；The composition of the formula 2 is cerium oxide, amorphous silica, boron oxide, lithium nitrate, aluminum oxide and zirconium oxide, wherein the mass percentage of cerium oxide is 34.9 to 43.3%, and the mass percentage of amorphous silica is 12.2. ～14.5%, the mass percentage of boron oxide is 8 to 13.7%, the mass percentage of lithium nitrate is 29.3 to 37%, the mass percentage of alumina is 2.7 to 3.4%, and the mass percentage of zirconia is 1.2 to 1.5%. The sum of shares is 100%; 所述玻璃粉粒径为1～5μm；The glass powder has a particle size of 1 to 5 μm; 所述无机颜料悬浮液共有六种颜色，其固相组份为六种工业色料，其中白色色料为氧化钛，红色色料为氧化铁，黄色色料为钛铬黄，绿色色料为钴绿，蓝色色料为钴蓝，黑色色料为铜铬黑；The inorganic pigment suspension has six colors, and the solid phase component thereof is six industrial pigments, wherein the white color material is titanium oxide, the red color material is iron oxide, the yellow color material is titanium chrome yellow, and the green color material is Cobalt green, blue color is cobalt blue, black color is copper chrome black; 所述六种工业色料的最大粒径均需小于2微米。The maximum particle size of the six industrial colorants needs to be less than 2 microns. 如权利要求1所述的玻璃表面喷绘打印用铋硅硼系低熔点油墨，其特征在于：所述低熔点玻璃粉悬浮液与无机颜料悬浮液，其液相组份的成份与各成份质量百分比相同，均由68～78％的主溶剂，14～20％的分散剂，7～11％的表面活性剂和0.1～1％的光稳定剂组成，各组份之和为100％；所述的主溶剂为1，2-丙二醇二甲醚，乙二醇单乙醚，环己酮中的一种或任意几种的混合物；所述的分散剂包含二乙二醇丁醚与丙烯酸树脂，其中二乙二醇丁醚与丙烯酸树脂的质量比为15:1，并且丙烯酸树脂的平均分子量为5000～8000；所述的表面活性剂为1，2-丙二醇二乙酸酯；所述的光稳定剂为癸二酸双(1,2,2,6,6-戊甲基-4-哌啶基)酯(HS-508)；所述的低熔点玻璃粉悬浮液与无机颜料悬浮液中固相组份与液相组份的质量比均为1:3。The bismuth silicon boron based low melting point ink for glass surface printing printing according to claim 1, wherein the composition of the liquid component of the low melting point glass frit suspension and the inorganic pigment suspension and the mass percentage of each component The same, each consists of 68 to 78% of the main solvent, 14 to 20% of the dispersant, 7 to 11% of the surfactant and 0.1 to 1% of the light stabilizer, and the sum of the components is 100%; The main solvent is 1,2-propylene glycol dimethyl ether, ethylene glycol monoethyl ether, cyclohexanone or a mixture of any of the following; the dispersing agent comprises diethylene glycol butyl ether and acrylic resin, wherein The mass ratio of diethylene glycol butyl ether to acrylic resin is 15:1, and the average molecular weight of the acrylic resin is 5000-8000; the surfactant is 1,2-propylene glycol diacetate; The agent is bis(1,2,2,6,6-pentylmethyl-4-piperidinyl) sebacate (HS-508); the low-melting glass powder suspension and the inorganic pigment suspension are solid The mass ratio of the phase component to the liquid component was 1:3. 如权利要求1所述的玻璃表面喷绘打印用铋硅硼系低熔点油墨，其特征在于：按配方一制备所得玻璃粉最大粒径可通过加溶剂球磨的方式减小至100nm 以下，按配方二制备所得玻璃粉最大粒径可通过加溶剂球磨的方式减小至1μm以下。The bismuth silicon boron based low melting point ink for glass surface printing printing according to claim 1, wherein the maximum particle diameter of the glass powder prepared according to the formula 1 can be reduced to 100 nm by solvent ball milling. Hereinafter, the maximum particle diameter of the obtained glass powder prepared according to the formula 2 can be reduced to less than 1 μm by means of solvent addition ball milling. 如权利要求1所述的玻璃表面喷绘打印用铋硅硼系低熔点油墨，其特征在于：所述无机颜料固相组份的最大粒径可通过加溶剂球磨的方式减小至100nm以下。The bismuth silicon boron-based low melting point ink for glass surface printing printing according to claim 1, wherein the maximum particle diameter of the inorganic pigment solid phase component can be reduced to 100 nm or less by means of solvent ball milling. 如权利要求1所述的玻璃表面喷绘打印用铋硅硼系低熔点油墨，其特征在于：所述低熔点玻璃粉悬浮液与无机颜料悬浮液的体积比为3～5:1。The silicon germanium-based low-melting ink for glass surface printing printing according to claim 1, wherein a volume ratio of the low-melting glass frit suspension to the inorganic pigment suspension is from 3 to 5:1. 如权利要求1所述的玻璃表面喷绘打印用铋硅硼系低熔点油墨的制备方法，其特征在于步骤如下：The method for preparing a silicon germanium-based low-melting ink for glass surface printing printing according to claim 1, wherein the steps are as follows: (1)制备低熔点玻璃粉悬浮液：首先按照所述配方一或配方二制备低熔点玻璃粉，然后配制低熔点玻璃粉悬浮液中的溶剂，最后按低熔点玻璃粉与溶剂质量比1:3，称量低熔点玻璃粉与溶剂倒入球磨罐中，使用行星球磨机球磨得到低熔点玻璃粉悬浮液；(1) Preparation of low-melting glass powder suspension: firstly, according to the formula 1 or the formula 2, a low-melting glass powder is prepared, and then the solvent in the low-melting glass powder suspension is prepared, and finally the low-melting glass powder and the solvent mass ratio are 1: 3. Weigh the low-melting glass powder and the solvent into a ball-milling jar, and use a planetary ball mill to obtain a low-melting glass powder suspension by ball milling; (2)制备无机颜料悬浮液：首先配制无机颜料悬浮液中的溶剂，然后按照色料与溶剂质量比1:3，称量六种工业色料中的一种与溶剂倒入球磨罐中，使用行星球磨机球磨得到无机颜料悬浮液；(2) Preparation of inorganic pigment suspension: firstly preparing a solvent in the inorganic pigment suspension, and then weighing one of the six industrial colorants and the solvent into the ball mill tank according to the mass ratio of the colorant to the solvent of 1:3. Ball milling using a planetary ball mill to obtain an inorganic pigment suspension; (3)低熔点玻璃粉悬浮液与无机颜料悬浮液混合：按照低熔点玻璃粉悬浮液与无机颜料悬浮液体积比3～5:1，量取步骤(1)和(2)制备所得低熔点玻璃粉悬浮液与无机颜料悬浮液倒入烧杯中搅拌混合均匀；(3) Mixing the low-melting glass frit suspension with the inorganic pigment suspension: according to the volume ratio of the low-melting glass frit suspension to the inorganic pigment suspension of 3 to 5:1, the low melting point obtained by the steps (1) and (2) is measured. The glass powder suspension and the inorganic pigment suspension are poured into a beaker and stirred and mixed uniformly; (4)对步骤(3)制备所得油墨使用激光粒度仪进行粒径检测，若粒径不符合要求，则延长球磨时间或使用过滤设备进行过滤。(4) The particle obtained by the step (3) is subjected to particle size detection using a laser particle size analyzer. If the particle size does not meet the requirements, the ball milling time is extended or filtration is performed using a filtering device. 如权利要求6所述的玻璃表面喷绘打印用铋硅硼系低熔点油墨的制备方法，其特征在于，步骤(1)中的球磨工艺参数为：球料比5～8:1，转速400～600r/min，球磨时间为12～48h。The method for preparing a silicon germanium-based low-melting ink for glass surface printing printing according to claim 6, wherein the ball milling process parameter in the step (1) is: a ball to material ratio of 5 to 8:1, and a rotation speed of 400 to 600r/min, ball milling time is 12 ~ 48h. 如权利要求6所述的玻璃表面喷绘打印用铋硅硼系低熔点油墨的制备方法，其特征在于，步骤(2)中的球磨工艺参数为：球料比5～8:1，转速400～600r/min，球磨时间为12～48h。The method for preparing a silicon germanium-based low-melting ink for glass surface printing printing according to claim 6, wherein the ball milling process parameter in the step (2) is: a ball to material ratio of 5 to 8:1, and a rotation speed of 400 to 600r/min, ball milling time is 12 ~ 48h. 如权利要求6所述的玻璃表面喷绘打印用铋硅硼系低熔点油墨的制备方法，其特征在于，步骤(3)中，搅拌使用电动恒速搅拌器，设定转速100r/min，搅拌30min。 The method for preparing a silicon germanium-based low-melting ink for glass surface printing printing according to claim 6, wherein in the step (3), the electric constant speed agitator is used for stirring, and the rotation speed is set to 100 r/min, and the mixture is stirred for 30 minutes. .
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