Low-temperature cold-color glass ink and preparation method thereof

Abstract

The invention relates to the technical field of glass printing ink, and provides low-temperature cold-color glass printing ink and a preparation method thereof.The low-temperature cold-color glass printing ink comprises cold-color glass powder and an organic solvent, and the cold-color glass powder comprises, by weight, 70-90% of first glass powder, 8-30% of second glass powder and 1-3% of a first coloring agent; the first glass powder comprises lead oxide, a second coloring agent, aluminum oxide, silicon oxide and boron oxide; the second glass powder comprises lead oxide, aluminum oxide, silicon oxide and boron oxide. The thermal expansion coefficient of the cold-color glass powder in the low-temperature cold-color glass ink provided by the invention is close to that of a glass matrix, and the cold-color glass ink has the characteristics of low softening temperature and high color and chemical stability.

Description

Technical Field

[0001] The present application belongs to the technical field of glass inks, and in particular relates to a low-temperature cold-color glass ink and a preparation method thereof. Background Art

[0002] Colored glass ink is a kind of ink that can be printed or printed on various smooth substrates such as glass. It can be firmly bonded to the substrate after drying and sintering. Because of its low raw material price and good decorative properties, it is widely used in the sealing of electronic LEDs, automotive glass, household appliance panels, architectural decoration and other industries, playing a decorative and protective role.

[0003] Existing colored glass inks usually contain low-melting-point glass powder, colorants, and organic polymer solvents, and the preparation methods thereof mainly include the following two methods: one is to directly ball-mill and mix the low-melting-point glass powder, colorants, and organic polymer solvents to form colored glass inks; the other is to first ball-mill the low-melting-point glass powder and colorants to form low-temperature secondary colorants, and then ball-mill and mix the low-temperature secondary colorants and organic polymer solvents to form colored glass inks. However, both methods simply physically mix the low-melting-point glass powder and colorants, and it is difficult to evenly disperse the colorants in the low-melting-point glass powder. In this way, after sintering and curing, the colored glass ink will cause the low-melting-point glass powder and colorants to present two forms, resulting in a large difference in expansion coefficients, resulting in poor adhesion of the ink layer and poor color stability, which will ultimately affect the corrosion resistance and service life of the colored glass. Summary of the invention

[0004] The purpose of the present application is to provide a low-temperature cold-color glass ink and a preparation method thereof, aiming to solve the problems of poor color stability of glass powder and large thermal expansion coefficient affecting the bonding of glass ink with substrate in existing low-temperature cold-color glass inks.

[0005] In order to achieve the above application purpose, the technical solution adopted in this application is as follows: In a first aspect, the present application provides a low-temperature cold-color glass ink, comprising cold-color glass powder and an organic solvent, wherein the total weight of the cold-color glass powder is 100%, and the cold-color glass powder comprises the following components: 70-90% of a first glass powder, 8-30% of a second glass powder, and 1-3% of a first dye; The first glass powder includes lead oxide, a second coloring agent, aluminum oxide, silicon oxide and boron oxide; The second glass frit includes lead oxide, aluminum oxide, silicon oxide and boron oxide.

[0006] Optionally, in the first glass powder, the mass ratio of the lead oxide, the second coloring agent, the aluminum oxide, the silicon oxide and the boron oxide is (50-70) / (2-4) / (2-5) / (10-20) / (5-10); And / or, in the second glass powder, the mass ratio of lead oxide, aluminum oxide, silicon oxide and boron oxide is (70-80) / (2-5) / (1-5) / (15-20).

[0007] Optionally, the first dye and the second dye are each independently selected from one or more of CoO, Co2O3, CuO, and MnO2.

[0008] Optionally, the average particle size of the cool-color glass powder is 1.5-2.5 μm.

[0009] Optionally, the mass ratio of the cool-color glass powder to the organic solvent is (6-8) / (2-4).

[0010] Optionally, the organic solvent includes terpineol, butyl carbitol acetate, ethyl cellulose and hydrogenated castor oil in a mass ratio of (65-80) / (10-30) / (1-5) / (1-5).

[0011] In a second aspect, the present application provides a method for preparing a low-temperature cold-color glass ink, comprising the following steps: Lead oxide, a second dye, aluminum oxide, silicon oxide and boron oxide are mixed and subjected to a first smelting process, and then cooled and crushed to obtain a first glass powder; The lead oxide, aluminum oxide, silicon oxide and boron oxide are mixed and subjected to a second smelting process, and then cooled and crushed to obtain a second glass powder; The first glass powder, the second glass powder and the first dye are added into a solvent, ball-milled and mixed, and then dried to obtain a cold-color glass powder; The cold color glass powder is added into an organic solvent for mixing, degassing and pulping to obtain a low temperature cold color glass ink.

[0012] Optionally, the temperature of the first smelting treatment and the second smelting treatment is 1000-1200° C., and the time is 10-60 min.

[0013] Optionally, the step of adding the first glass powder, the second glass powder and the first dye into a solvent, ball-milling and mixing, and then drying to obtain the cold-color glass powder includes: Mixing the first glass powder and the second glass powder by ball milling to obtain a mixed glass powder; The first dye and the solvent are added to the mixed glass powder, ball-milled and mixed, and then dried to obtain the cold-color glass powder.

[0014] Optionally, before the steps of adding the cool-color glass powder to the organic solvent for mixing, degassing and slurrying, the method further comprises: passing the cool-color glass powder through a 200-300 mesh sieve; And / or, before the step of adding the first glass powder, the second glass powder and the first dye into a solvent for ball milling and mixing, the step further includes: passing the first glass powder and the second glass powder through a 50-mesh sieve respectively.

[0015] Optionally, the solvent is a 70-80% alcohol solution.

[0016] Compared with the prior art, this application has the following beneficial effects: The low-temperature cold-color glass ink provided in the first aspect of the present application, on the one hand, has a second dye evenly distributed in the first glass powder, which can adjust the color stability of the cold-color glass powder. The second glass powder does not contain colorant and is milky white, and has a low softening temperature. It can effectively adjust the transparency and color brilliance of the cold-color glass powder, and at the same time adjust the softening temperature and expansion coefficient of the cold-color glass powder. The first dye can color the glass coating to produce covering and protection. On the other hand, by controlling the ratio of the first glass powder and the second glass powder, the thermal expansion coefficient of the cold-color glass powder can also be adjusted to match the thermal expansion coefficient of the printed glass substrate, and the thermal stress of the two is smaller, so that the glass coating formed by the low-temperature cold-color glass ink after printing and sintering has better adhesion and can be firmly combined with the printed glass substrate, so it has better impact resistance. In addition, by adjusting the ratio of the first glass powder and the second glass powder, the chemical stability of the cold-color glass powder can be improved, and the glass coating can be prevented from being corroded by acids, alkalis, and salts and gradually losing gloss, discoloring, or even falling off, thereby extending the service life of the colored glass. Furthermore, the low-temperature cold-color glass ink of the present application can also be used for sealing and connecting electronic equipment, as well as automotive glass, and has a wide range of applications.

[0017] The second aspect of the present application provides a method for preparing a low-temperature, cold-colored glass ink. The method comprises dividing a glass powder raw material into two parts, melting a part of the glass powder raw material with a second dye, and making the dye evenly adhere to the glass matrix in the form of ions, so that a first glass powder with stable color can be formed after cooling, while the other part of the glass powder raw material is directly melted to form a milky white second glass powder. The color-stable first glass powder, the colorless and transparent second glass powder, and the first dye are then ball-milled and mixed to form a cold-colored glass powder, so that the first dye and the second dye in the low-temperature, cold-colored glass ink are evenly distributed in the cold-colored glass powder, thereby effectively improving the color temperature of the low-temperature, cold-colored glass ink and making the prepared low-temperature, cold-colored glass ink bright in color and high in gloss. BRIEF DESCRIPTION OF THE DRAWINGS

[0018] Figure 1It is a schematic diagram of a colored glass ink after printing provided by Examples 1 to 11 of the present invention and Comparative Examples 1 to 5. DETAILED DESCRIPTION

[0019] In order to make the technical problems, technical solutions and beneficial effects to be solved by the present application more clearly understood, the present application is further described in detail below in conjunction with the embodiments. It should be understood that the specific embodiments described herein are only used to explain the present application and are not used to limit the present application.

[0020] A first aspect of the embodiment of the present application provides a low-temperature cold-color glass ink, comprising cold-color glass powder and an organic solvent, and based on the total weight of the cold-color glass powder being 100%, comprising the following components: 70-90% of the first glass powder, 8-30% of the second glass powder, and 1-3% of the first dye; The first glass powder includes lead oxide, a second coloring agent, aluminum oxide, silicon oxide and boron oxide; The second glass powder includes lead oxide, aluminum oxide, silicon oxide and boron oxide; The low-temperature cold-color glass ink provided in the embodiment of the present application has a second dye evenly distributed in the first glass powder, which can adjust the color stability of the cold-color glass powder. The second glass powder does not contain colorant and is milky white, which can effectively adjust the transparency and color brilliance of the cold-color glass powder, and at the same time adjust the softening temperature and expansion coefficient of the cold-color glass powder. The first dye can color the glass coating to provide covering and protection. On the other hand, by controlling the ratio of the first glass powder and the second glass powder, the thermal expansion coefficient of the cold-color glass powder can also be adjusted to match the thermal expansion coefficient of the printed glass substrate, and the thermal stress of the two is smaller, so that the glass coating formed by the low-temperature cold-color glass ink after printing and sintering has better adhesion and can be firmly combined with the printed glass substrate, so it has better impact resistance. In addition, by adjusting the ratio of the first glass powder and the second glass powder, the chemical stability of the cold-color glass powder can be improved, and the glass coating can be prevented from being corroded by acids, alkalis and salts and gradually losing gloss, changing color, or even falling off, thereby extending the service life of the colored glass.

[0021] In some embodiments, the first dye and the second dye are independently selected from one or more of CoO, Co2O3, CuO, and MnO2. For example, a mixture of CoO and Al2O3 can be a light blue dye, a mixture of Co2O3 and Al2O3 can be a dark blue dye, a mixture of Co2O3 and CuO can be a navy blue dye, CuO can be a green dye, a mixture of CuO and MnO2 can be a purple dye, and a mixture of Co2O3 and MnO can be a dark purple dye.

[0022] Specifically, the content of the first glass powder may be 70%, 73%, 76%, 79%, 82%, 85%, 88% or 90%, etc. The content of the second glass powder may be 8-17%, and further may be 8%, 10%, 13%, 16%, 19%, 22%, 25%, 28% or 30%, etc. The content of the first coloring agent may be 1%, 1.2%, 1.4%, 1.6%, 1.8%, 2%, 2.2%, 2.4%, 2.6%, 2.8% or 3%, etc.

[0023] In some embodiments, in the first glass powder, the mass ratio of lead oxide, the second coloring agent, aluminum oxide, silicon oxide and boron oxide is (50-70) / (2-4) / (2-5) / (10-20) / (5-10). Specifically, the mass ratio of lead oxide, the second coloring agent, aluminum oxide, silicon oxide and boron oxide can be 70 / 3 / 5 / 15 / 7, 50 / 2 / 3 / 20 / 5, 60 / 4 / 2 / 10 / 10, 60 / 3 / 5 / 15 / 7, 50 / 3 / 5 / 15 / 7, 70 / 4 / 5 / 15 / 7, 70 / 2 / 5 / 15 / 7, 70 / 3 / 2 / 15 / 7, 70 / 3 / 5 / 10 / 7, 70 / 3 / 5 / 20 / 7, 70 / 3 / 5 / 15 / 5 or 70 / 3 / 5 / 15 / 20, etc. In the first glass powder of this embodiment, the lead oxide, the second dye, aluminum oxide, silicon oxide and boron oxide are within a specific proportion range, so that a first glass powder with a low melting point, a thermal expansion coefficient close to that of the glass matrix, a low softening temperature and high chemical stability can be obtained, and the first glass powder can also be attached to a cold color under the action of the second dye to form a cold-colored glass powder.

[0024] In some embodiments, in the second glass powder, the mass ratio of lead oxide, aluminum oxide, silicon oxide and boron oxide is (70-80) / (2-5) / (1-5) / (15-20). Specifically, the mass ratio of lead oxide, aluminum oxide, silicon oxide and boron oxide can be 75 / 2 / 5 / 15, 70 / 5 / 1 / 20, 80 / 3 / 3 / 17, 70 / 2 / 5 / 15, 80 / 2 / 5 / 15, 75 / 5 / 5 / 15, 75 / 2 / 1 / 15 or 75 / 2 / 5 / 20, etc. In the second glass powder of this embodiment, the lead oxide, aluminum oxide, silicon oxide and boron oxide in a specific ratio range can obtain a second glass powder with a low melting point, a thermal expansion coefficient close to that of the glass matrix, a low softening temperature and high chemical stability, and a colorless state.

[0025] In some embodiments, the average particle size of the cold-color glass powder is 1.5-2.5 μm. Selecting the cold-color glass powder in this particle size range facilitates the formation of uniformly dispersed low-temperature cold-color glass ink.

[0026] In some embodiments, the mass ratio of the cold-color glass powder to the organic solvent is (6-8) / (2-4). Specifically, the mass ratio of the cold-color glass powder to the organic solvent may be 7 / 3, 6 / 2, 6 / 4, 8 / 2 or 8 / 4. By adjusting the mass ratio of the organic solvent to the cold-color glass powder, the viscosity of the low-temperature cold-color glass ink meets the printing requirements.

[0027] In some embodiments, the organic solvent includes pine alcohol, butyl carbitol acetate, ethyl cellulose and hydrogenated castor oil in a mass ratio of (65-80) / (10-30) / (1-5) / (1-5). Pineneol is easy to volatilize and is not suitable for use as a main solvent from the perspective of volatility, but in this embodiment, the total volatilization amount of the low-temperature cold-color glass ink is adjusted by adjusting the content of pine alcohol. The low-temperature cold-color glass ink of this embodiment uses a mixed solvent. The relative content of each solvent in the mixed solvent determines the relative ratio of its vapor pressure. When the relative content of butyl carbitol acetate and pine alcohol is lower than a certain value, the vapor pressure of pine alcohol is higher, and the volatilization is mainly pine alcohol; when the content of butyl carbitol acetate increases, the vapor pressure of pine alcohol decreases and the volatilization amount decreases. Therefore, in this embodiment, by adjusting the relative content of butyl carbitol acetate and pine alcohol, the volatility of the low-temperature cold-color glass ink during drying can also be adjusted. Ethyl cellulose is added to increase the viscosity of low-temperature cold-color glass ink to meet the requirements of fine line printing. Hydrogenated castor oil is added to ensure the viscosity stability of low-temperature cold-color glass ink.

[0028] The volatility characteristics of the organic solvent in the low-temperature cold-color glass ink determine the volatility characteristics of the low-temperature cold-color glass ink, and the volatility characteristics of the low-temperature cold-color glass ink directly determine the quality of the glass film. If the organic solvent evaporates too quickly, the viscosity of the low-temperature cold-color glass ink increases during printing, which is easy to clog the screen; if the organic solvent evaporates too concentratedly, the low-temperature cold-color glass ink on the glass substrate is dried and sintered, and defects such as holes and microcracks are easily formed on the surface of the glass film; if the organic solvent evaporates too slowly, it is not easy to dry after screen printing, resulting in defects on the surface of the glass film after sintering. Therefore, this embodiment adjusts the volatility characteristics of the organic solvent by adjusting the components and content of the organic solvent.

[0029] The low-temperature cold-color glass ink can be prepared by the following method for preparing the low-temperature cold-color glass ink.

[0030] A second aspect of the embodiment of the present application provides a method for preparing a low-temperature cold-color glass ink, comprising the following steps: Step S1: Lead oxide, a second dye, aluminum oxide, silicon oxide and boron oxide are mixed and subjected to a first smelting treatment, and then cooled and crushed to obtain a first glass powder; through the smelting treatment, the dye is uniformly adhered to the glass matrix in the form of ions, and a cold-colored glass powder can be formed after cooling.

[0031] Step S2: mixing lead oxide, aluminum oxide, silicon oxide and boron oxide, performing a second smelting process, and then cooling and crushing the mixture to obtain a second glass powder; Step S3: adding the first glass powder, the second glass powder and the first dye into a solvent, ball-milling and mixing, and then drying to obtain a cold-color glass powder; Step S4: adding the cold-color glass powder into the organic solvent for mixing, degassing and pulping to obtain low-temperature cold-color glass ink.

[0032] The preparation method of the low-temperature cold-color glass ink provided in the embodiment of the present application is as follows: the glass powder raw material is divided into two parts, and one part of the glass powder raw material is melted with the second dye so that the dye is uniformly adhered to the glass matrix in the form of ions, and a first glass powder with stable color can be formed after cooling, while the other part of the glass powder raw material is directly melted to form a milky white second glass powder, and then the color-stable first glass powder, the milky white second glass powder, and the first dye are ball-milled and mixed to form a cold-color glass powder. In this way, on the one hand, the first glass powder can adjust the color stability of the cold-color glass powder, the second glass powder can adjust the transparency and bright color of the cold-color glass powder, and the first dye can color the glass coating to provide covering and protection. On the other hand, by controlling the ratio of the first glass powder to the second glass powder, the thermal expansion coefficient of the cold-color glass powder can be adjusted to match the thermal expansion coefficient of the printing glass substrate, and the thermal stress of the two is smaller, so that the glass coating formed by the low-temperature cold-color glass ink after printing and sintering has better adhesion and can be firmly combined with the printing glass substrate, so it has better impact resistance. In addition, by adjusting the ratio of the first glass powder to the second glass powder, the chemical stability of the cold-colored glass powder can be improved, preventing the glass coating from being corroded by acids, alkalis, and salts and gradually losing its luster, changing color, or even falling off, thereby extending the service life of the colored glass.

[0033] In the above step S1, the temperature of the first smelting treatment is 1000-1200°C and the time is 10-60 minutes, so that each component is fully mixed and uniform when in a molten state.

[0034] In an embodiment, before the step of adding the first glass powder, the second glass powder and the first dye to the solvent for ball milling and mixing, the step further includes: passing the first glass powder through a 50-mesh sieve, so as to facilitate further grinding of the first glass powder, reduce the loss of the ball mill, and further facilitate the preparation of evenly dispersed low-temperature cold-color glass ink.

[0035] In the above step S2, the temperature of the second smelting treatment is 1000-1200°C and the time is 10-60 minutes, so that the various components are fully mixed and uniform when in a molten state.

[0036] In an embodiment, before the step of adding the first glass powder, the second glass powder and the first dye into a solvent for ball milling and mixing, it also includes: passing the second glass powder through a 50-mesh sieve to facilitate subsequent further grinding of the second glass powder, reduce the loss of the ball mill jar, and further facilitate the preparation of evenly dispersed low-temperature cold-color glass ink.

[0037] In the above step S3, the step of adding the first glass powder, the second glass powder and the first dye into a solvent, ball-milling and mixing, and then drying to obtain a cold-colored glass powder includes: ball-milling and mixing the first glass powder and the second glass powder to obtain a mixed glass powder; adding the first dye and the solvent into the mixed glass powder, ball-milling and mixing, and then drying to obtain a cold-colored glass powder.

[0038] In this embodiment, the first glass powder and the second glass powder are first mixed, and then the first dye is added. The second glass powder is dyed by using the first dye in combination with the second dye in the first glass powder.

[0039] In a specific embodiment, the first glass powder and the second glass powder are mixed in a mass ratio of 85:15.

[0040] In some embodiments, the solvent is a 70-80% alcohol solution to facilitate subsequent drying.

[0041] In some embodiments, before the steps of adding the cold-color glass powder to the organic solvent for mixing, degassing and slurrying, the step further includes: passing the cold-color glass powder through a 200-300 mesh sieve. By sieving the cold-color glass powder, it is convenient to obtain a cold-color glass powder with an average particle size of 1.5-2.5 μm, and further facilitate the formation of a uniformly dispersed low-temperature cold-color glass ink.

[0042] In the above step S4, an organic solvent is prepared according to the percentage content of 65-80% of pine alcohol, 10-30% of butyl carbitol acetate, 1-5% of ethyl cellulose, and 1-5% of hydrogenated castor oil. After the above organic solvent is stirred evenly in a stirrer, the cold-color glass powder and the organic solvent are weighed according to the mass ratio of the cold-color glass powder to the organic solvent being (6-8) / (2-4), and the cold-color glass powder is added to the organic solvent for mixing, degassing and slurrying to obtain a low-temperature cold-color glass ink.

[0043] Specifically, the low-temperature cold-color glass ink is screen-printed and then baked at 550° C. for 5 minutes, and the cold-color glass powder in the low-temperature cold-color glass ink is melted into an indigo glass film.

[0044] The following describes the invention in conjunction with specific embodiments.

[0045] Example 1 This embodiment provides a low-temperature cold-color glass ink and a preparation method thereof.

[0046] Low-temperature cold-color glass ink, including cold-color glass powder and organic solvent in a mass ratio of 7 / 3; wherein, the cold-color glass powder contains 70% of the first glass powder, 27% of the second glass powder and 3% of Co2O3+Al2O3, the first glass powder includes lead oxide, Co2O3+Al2O3, aluminum oxide, silicon oxide and boron oxide in a mass ratio of 70 / 3 / 5 / 15 / 7, the second glass powder includes lead oxide, aluminum oxide, silicon oxide and boron oxide in a mass ratio of 75 / 2 / 5 / 15; the organic solvent includes pineneol, butyl carbitol acetate, ethyl cellulose and hydrogenated castor oil in a mass ratio of 75 / 20.5 / 2.5 / 2.

[0047] The preparation method of low-temperature cold-color glass ink comprises the following steps: S1: Lead oxide, Co2O3+Al2O3, aluminum oxide, silicon oxide and boron oxide in a mass ratio of 70 / 3 / 5 / 15 / 7 are mixed, and then smelted at 1100° C. for 30 minutes, poured into deionized water for water quenching, and then dried, crushed and sieved through a 50-mesh sieve to obtain a first glass powder; S2: Lead oxide, aluminum oxide, silicon oxide and boron oxide in a mass ratio of 75 / 2 / 5 / 15 are mixed, and then smelted at 1100° C. for 30 minutes, poured into deionized water for water quenching, and then dried, crushed and sieved through a 50-mesh sieve to obtain a second glass powder; S3: according to the mass ratio of the first glass powder, the second glass powder and cobalt blue being 70 / 27 / 3, weigh appropriate amounts of the first glass powder, the second glass powder and Co2O3+Al2O3; ball-mill the first glass powder and the second glass powder to mix evenly, then add Co2O3+Al2O3 and 80% alcohol solution and continue ball-milling until the D50 particle size of the solid particles is ≤2.0μm, then dry and pass through a 300-mesh sieve to obtain a cold-color glass powder; S4: After mixing the cold-color glass powder and the organic solvent in a mass ratio of 7 / 3, degassing is performed in a degassing machine, and then slurrying is performed on a three-roller machine to obtain a low-temperature cold-color glass ink.

[0048] Example 2 This embodiment provides a low-temperature cold-color glass ink and a preparation method thereof, which is different from Embodiment 1 in that the glass powder contains 80% of the first glass powder, 17% of the second glass powder, and 3% of Co2O3+Al2O3.

[0049] Example 3 This embodiment provides a low-temperature cold-color glass ink and a preparation method thereof. The difference from Embodiment 1 is that the cold-color glass powder contains 90% of the first glass powder, 8% of the second glass powder, and 2% of Co2O3+Al2O3.

[0050] Example 4 This embodiment provides a low-temperature cold-color glass ink and a preparation method thereof. The difference from Embodiment 1 is that the cold-color glass powder contains 70% of the first glass powder, 29% of the second glass powder, and 1% of Co2O3+Al2O3.

[0051] Example 5 This embodiment provides a low-temperature cold-color glass ink and a preparation method thereof. The difference from Embodiment 1 is that the first glass powder includes lead oxide, Co2O3+Al2O3, aluminum oxide, silicon oxide and boron oxide in a mass ratio of 50 / 2 / 3 / 20 / 5; the second glass powder includes lead oxide, aluminum oxide, silicon oxide and boron oxide in a mass ratio of 80 / 3 / 3 / 17.

[0052] Example 6 This embodiment provides a low-temperature cold-color glass ink and a preparation method thereof. The difference from Embodiment 1 is that the first glass powder includes lead oxide, Co2O3+Al2O3, aluminum oxide, silicon oxide and boron oxide in a mass ratio of 60 / 4 / 2 / 10 / 10; the second glass powder includes lead oxide, aluminum oxide, silicon oxide and boron oxide in a mass ratio of 70 / 5 / 1 / 20.

[0053] Example 7 This embodiment provides a low-temperature cold-color glass ink and a preparation method thereof. The difference from Embodiment 1 is that the first glass powder includes lead oxide, Co2O3+Al2O3, aluminum oxide, silicon oxide and boron oxide in a mass ratio of 70 / 4 / 5 / 15 / 7.

[0054] Example 8 This embodiment provides a low-temperature cold-color glass ink and a preparation method thereof. The difference from Embodiment 1 is that the first glass powder includes lead oxide, Co2O3+Al2O3, aluminum oxide, silicon oxide and boron oxide in a mass ratio of 70 / 2 / 5 / 15 / 7.

[0055] Example 9 This embodiment provides a low-temperature cold-color glass ink and a preparation method thereof. The difference from Embodiment 1 is that the first glass powder includes lead oxide, Co2O3+Al2O3, aluminum oxide, silicon oxide and boron oxide in a mass ratio of 70 / 5 / 5 / 15 / 7.

[0056] Example 10 This embodiment provides a low-temperature cold-color glass ink and a preparation method thereof. The difference from Embodiment 1 is that the first glass powder includes lead oxide, Co2O3+Al2O3, aluminum oxide, silicon oxide and boron oxide in a mass ratio of 70 / 1 / 5 / 15 / 7.

[0057] Embodiment 11 This embodiment provides a low-temperature, cold-color glass ink and a preparation method thereof. The difference from Embodiment 1 is that the cold-color glass powder contains 70% of the first glass powder, 27% of the second glass powder and 3% of CoO+Al2O3, and the first glass powder includes lead oxide, CoO+Al2O3, aluminum oxide, silicon oxide and boron oxide in a mass ratio of 70 / 3 / 5 / 15 / 7.

[0058] Comparative Example 1 This comparative example provides a low-temperature cold-color glass ink and a preparation method thereof, which is different from Example 1 in that in the low-temperature cold-color glass ink, the cold-color glass powder does not include the first glass powder.

[0059] The preparation method of low-temperature cold-color glass ink does not include step S1, and in step S3, according to the mass ratio of the second glass powder and Co2O3+Al2O3 being 97 / 3, appropriate amounts of the second glass powder and Co2O3+Al2O3 are weighed; the second glass powder, Co2O3+Al2O3 and 80% alcohol solution are ball-milled until the D50 particle size of the solid particles is ≤2.0μm.

[0060] Comparative Example 2 This comparative example provides a low-temperature cold-color glass ink and a preparation method thereof, which is different from Example 1 in that the cold-color glass powder contains 70% of the first glass powder, 26% of the second glass powder, and 4% of Co2O3+Al2O3.

[0061] Comparative Example 3 This comparative example provides a low-temperature cold-color glass ink and a preparation method thereof, which is different from Example 1 in that the cold-color glass powder contains 72.5% of the first glass powder, 27% of the second glass powder, and 0.5% of Co2O3+Al2O3.

[0062] Comparative Example 4 This comparative example provides a low-temperature cold-color glass ink and a preparation method thereof, which is different from Example 1 in that the cold-color glass powder contains 91% of the first glass powder, 6% of the second glass powder, and 3% of Co2O3+Al2O3.

[0063] Comparative Example 5 This comparative example provides a low-temperature cold-color glass ink and a preparation method thereof, which is different from Example 1 in that the cold-color glass powder contains 60% of the first glass powder, 37% of the second glass powder, and 3% of Co2O3+Al2O3.

[0064] Related performance test analysis: The performance of the low-temperature cold-color glass ink provided in each embodiment and comparative example was tested, and the evaluation method was as follows: 1. Evaluation method of expansion coefficient and glass transition temperature: accurately weigh 3g of cold-colored glass powder and put it into a stainless steel mold for compaction to make a cylindrical sample with a length of about 25mm and a diameter of about 8mm; then put it into a muffle furnace and sinter it into a glass state at 570℃, and grind the two ends of the sample after natural cooling; then use a DIL-402 thermal expansion instrument to test it, with a heating rate of 5k / min. After the test is completed, the expansion coefficient and glass transition temperature values ​​are obtained. Among them, the expansion coefficient is read as the average expansion coefficient value of 294~304℃.

[0065] 2. Color stability test: Screen print low-temperature cold-color glass ink, bake at 550℃ for 5 minutes, and observe its glossiness and transparency. The test results are as follows: Figure 1 shown.

[0066] The test results are shown in Table 1 below: Table 1 From Table 1 and Figure 1 It can be seen that the low-temperature cold-color glass ink layer obtained in Examples 1 to 3 and 5 to 9 has a low glass transition temperature, a thermal expansion coefficient close to that of the glass matrix, and good color stability. However, the thermal expansion coefficient of the low-temperature cold-color glass ink layer obtained in Comparative Examples 1 and Comparative Examples 3 to 5 is quite different from that of the glass matrix, and the color is quite different from the effect to be achieved by the first dye. This is mainly due to the fact that in the embodiment of the present invention, the glass powder raw material is divided into two parts, a part of the glass powder raw material is melted with the second dye, so that the dye is uniformly adhered to the glass matrix in the form of ions, and a color-stable first glass powder can be formed after cooling, while the other part of the glass powder raw material is directly melted to form a colorless and transparent second glass powder, and then the color-stable first glass powder, the colorless and transparent second glass powder, and the first dye are ball-milled and mixed in a specific ratio to form a cold-color glass powder, so as to adjust the color stability and thermal expansion coefficient of the cold-color glass powder so that it matches the thermal expansion coefficient of the printing glass matrix.

[0067] The color stability of the low-temperature cold-color glass ink layer obtained in Example 1 is significantly better than that of Examples 2 to 4 and Comparative Examples 2 to 5. This is mainly due to the fact that the content of the first glass powder in Example 1 is in the range of 70 to 90%, and the content of the first dye is in the range of 1 to 3%. Within this range, the first glass powder and the first dye can more effectively improve the color stability of the cold-color glass powder. When the content of the first dye, i.e., Co2O3+Al2O3, in Comparative Example 3 is less than 1%, it is not conducive to the color stability of the glass ink, and the glass ink obtained therefrom finally presents a gray color after printing and baking. In Comparative Example 2, the content of the first dye is higher than 3%, resulting in uneven dispersion in the first glass powder and the second glass powder, affecting the expansion coefficient of the cold-color glass powder, so that the expansion coefficient of the glass ink layer is too different from that of Example 1, thereby affecting the bonding problem between the glass ink and the glass substrate. In Comparative Example 5, the first glass powder is reduced compared with Example 1, and its glass transition temperature and thermal expansion coefficient are reduced accordingly.

[0068] The glass transition temperature and thermal expansion coefficient of the low-temperature cold-color glass ink layer obtained in Example 1 are similar to those of Examples 5 to 10, but the colors they present are different. The main reason is that the content of Co2O3+Al2O3 in the first glass powder is different. When the mass ratio of lead oxide, the second dye, aluminum oxide, silicon oxide and boron oxide in the first glass powder is in the range of (50~70) / (2~4) / (2~5) / (10~20) / (5~10), the low-temperature cold-color glass ink layer obtained can be seen to be blue.

[0069] It can be seen from the test results of Example 1 and Example 11 that different combinations of dyes can present different low-temperature cold-color glass ink layers.

[0070] Therefore, under the combined effect of specific components, specific contents and specific preparation methods, the low-temperature cold-color glass ink of the embodiment of the present invention has good color stability, the prepared glass ink layer matches the thermal expansion coefficient of the printed glass substrate, the thermal stress is smaller, the formed glass ink layer has better adhesion, and can be firmly bonded to the printed glass substrate, and therefore has better impact resistance.

[0071] The above are only preferred embodiments of the present application and are not intended to limit the present application. Any modifications, equivalent substitutions and improvements made within the spirit and principles of the present application should be included in the protection scope of the present application.

Claims

1. A low-temperature cold-color glass ink, characterized in that: It comprises cold-color glass powder and an organic solvent. Taking the total weight of the cold-color glass powder as 100%, the cold-color glass powder comprises the following components: 70-90% of the first glass powder, 8-30% of the second glass powder, and 1-3% of the first dye. The first glass powder includes lead oxide, a second coloring agent, aluminum oxide, silicon oxide and boron oxide; The second glass frit includes lead oxide, aluminum oxide, silicon oxide and boron oxide.

2. The low temperature cold color glass ink according to claim 1, characterized in that: In the first glass powder, the mass ratio of the lead oxide, the second dye, the aluminum oxide, the silicon oxide and the boron oxide is (50-70) / (2-4) / (2-5) / (10-20) / (5-10); And / or, in the second glass powder, the mass ratio of lead oxide, aluminum oxide, silicon oxide and boron oxide is (70-80) / (2-5) / (1-5) / (15-20).

3. The low temperature cold color glass ink according to claim 1, characterized in that: The average particle size of the cold-color glass powder is 1.5-2.5 μm; And / or, the first colorant and the second colorant are each independently selected from one or more combinations of CoO, Co2O3, CuO, and MnO2.

4. The low-temperature cold-color glass ink according to any one of claims 1 to 3, characterized in that: The mass ratio of the cool-color glass powder to the organic solvent is (6-8) / (2-4).

5. The low temperature cold color glass ink according to claim 4, characterized in that: The organic solvent comprises terpineol, butyl carbitol acetate, ethyl cellulose and hydrogenated castor oil in a mass ratio of (65-80) / (10-30) / (1-5) / (1-5).

6. A method for preparing a low-temperature cold-color glass ink according to any one of claims 1 to 5, characterized in that: The following steps are involved: Lead oxide, a second dye, aluminum oxide, silicon oxide and boron oxide are mixed and subjected to a first smelting process, and then cooled and crushed to obtain a first glass powder; The lead oxide, aluminum oxide, silicon oxide and boron oxide are mixed and subjected to a second smelting process, and then cooled and crushed to obtain a second glass powder; The first glass powder, the second glass powder and the first dye are added into a solvent, ball-milled and mixed, and then dried to obtain a cold-color glass powder; The cold color glass powder is added into an organic solvent for mixing, degassing and pulping to obtain a low temperature cold color glass ink.

7. The preparation method according to claim 6, characterized in that: The temperature of the first smelting treatment and the second smelting treatment is 1000-1200° C., and the time is 10-60 minutes.

8. The preparation method according to claim 6, characterized in that: The steps of adding the first glass powder, the second glass powder and the first dye into a solvent, ball-milling and mixing, and then drying to obtain a cold-color glass powder include: Mixing the first glass powder and the second glass powder by ball milling to obtain a mixed glass powder; The first dye and the solvent are added to the mixed glass powder, ball-milled and mixed, and then dried to obtain the cold-color glass powder.

9. The preparation method according to claim 8, characterized in that: Before the steps of adding the cold-color glass powder into the organic solvent for mixing, degassing and slurrying, the method further comprises: passing the cold-color glass powder through a 200-300 mesh sieve; And / or, before the step of adding the first glass powder, the second glass powder and the first dye into a solvent for ball milling and mixing, the step further includes: passing the first glass powder and the second glass powder through a 50-mesh sieve respectively.

10. The preparation method according to claims 6 to 9, characterized in that: The solvent is 70-80% alcohol solution.

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