A glass ink and a method of making the same

Abstract

The application belongs to the technical field of ink, and particularly relates to a glass ink and a preparation method thereof. The glass ink comprises the following components in parts by weight: glass powder 45-60 parts, inorganic copper-chromium-cobalt black 13-25 parts, carrier resin 3-12 parts, solvent 5-16 parts and diamond powder 2-6 parts. The ink of the application completely covers the silver line from the surface, has a uniform shiny appearance, and does not affect other acid resistance, adhesion and other properties. The application combines stirring, mixing, dispersion and grinding methods to prepare the ink which can effectively cover the silver line, and the preparation process is simple, the operation difficulty is low, and the application is suitable for industrial production. The ink of the application can ensure the adhesion and the uniformity of the printing ink while having high solid content, solves the bottleneck of insufficient covering power of the existing glass ink, and can be applied to screen printing or preparation of mobile phone back cover, mobile phone lens, automobile accessories and other glass materials, and has a wide application.

Description

Technical Field

[0001] This invention belongs to the field of ink technology, specifically relating to a glass ink and its preparation method. Background Technology

[0002] In recent years, research on glass inks has mainly focused on adjusting the composition of glass pigments to improve the ink's acid and alkali resistance, sintering and melting temperature, and adjusting the crystallinity and anti-sticking properties of low-melting-point glass powders. Some of these studies also involve slip properties.

[0003] In addition to printing ink, automotive rear windshields also require screen printing of conductive silver lines. These silver lines conduct electricity and generate heat to improve the fogging effect of the glass. However, for aesthetic reasons, the ends of the silver lines should not be visible to the naked eye from the front of the glass. Therefore, the glass ink also needs to have the function of concealing the silver lines, but existing glass inks do not meet the requirements. Summary of the Invention

[0004] The purpose of this invention is to provide a glass ink capable of concealing silver lines and a method for preparing the same.

[0005] To solve the above-mentioned technical problems, the technical solution of the present invention is as follows:

[0006] A glass ink comprising the following components by weight: 45-60 parts glass powder, 13-25 parts inorganic copper chromium cobalt black, 3-12 parts carrier resin, 5-16 parts solvent and 2-6 parts diamond.

[0007] This invention prepares a glass ink that can cover silver lines by optimizing raw materials and proportions, using diamond powder to enhance the metallic texture of the glass, and making beautiful sparkling spots appear on the sintered glass to cover the silver lines.

[0008] In one preferred embodiment, the blackness L value of the inorganic copper chromium cobalt black is 3-5.

[0009] Glass pigments are a crucial component of glass inks, playing a key role in determining the acid and alkali resistance, coefficient of thermal expansion, and scratch resistance of automotive tempered glass inks. They can even affect the ink's anti-sticking properties. Automotive tempered glass pigments are composed of low-melting-point glass powder and inorganic pigments, typically oxides. From a technological perspective, the melting point of the tempered glass pigment must be lower than the softening temperature of the substrate glass. This ensures that the substrate glass only begins to soften when the glass pigment has completely melted, allowing it to penetrate the substrate and achieve a strong bond between the glass enamel and the tempered glass. This invention uses inorganic copper-chromium-cobalt black with appropriate blackness. Extensive experimental verification shows that copper oxide is black, while crystalline copper appears red in the presence of non-oxides, and chromium oxide is green. Green and red are mutually destructive. When a small portion remains undestructed during sintering, the cobalt oxide fully demonstrates its blackening effect. Therefore, after sintering, the a-value will not exceed ±1, resulting in a red or green color.

[0010] In one preferred embodiment, the glass powder is a mixture of ZnO, B2O3, SiO2, KO2, BaO and MgO, wherein the mass ratio of ZnO, B2O3, SiO2, KO2, BaO and MgO is 60-75%:15-30%:50-70%:4-8%:1-5%:0.3-1%.

[0011] In one preferred embodiment, the glass powder has a particle size of 5-15 micrometers.

[0012] In one preferred embodiment, the carrier resin is one or more of rosin resin, PVB resin, modified ethylene-vinyl acetate resin, and acrylic polyester.

[0013] In one preferred embodiment, the solvent is one or more of diethylene glycol butyl ether, kerosene, divalent ester, terpineol, ethylene glycol, turpentine, diethylene glycol monohydrate, n-pentanol, ethylene glycol, n-octanol, and n-butanol.

[0014] In one preferred embodiment, the solvent is a mixed solution of diethylene glycol butyl ether, terpineol, and kerosene in a mass ratio of 55-65:25-35:5-15.

[0015] The solvents of this invention are formulated by combining the slowest, medium-slowest, and fastest evaporation rates, which is beneficial for the screen printing effect and for accelerating the evaporation rate during ink drying.

[0016] In one preferred embodiment, the glass ink further includes 3-8 parts of nanosphere silica powder.

[0017] Adding an appropriate weight of nanosphere silica powder can effectively improve the feel of ink.

[0018] In one preferred embodiment, the nanosphere silicon powder has a fineness of less than 15 micrometers.

[0019] In one preferred embodiment, the gloss of the glass ink after adding the nanosphere silicon powder is maintained at 2-3°.

[0020] In one preferred embodiment, the glass ink further includes 10-20 parts of bismuth oxide.

[0021] Adding an appropriate amount of bismuth oxide can prevent silver wire migration, thus ensuring the aesthetic appearance of the sintered glass surface.

[0022] In one preferred embodiment, the glass ink further includes a silicone-free dispersant.

[0023] In one preferred embodiment, the silicone-free dispersant is a CONHP-type silicone-free dispersant.

[0024] In one preferred embodiment, the diamond has a fineness of less than 15 micrometers.

[0025] In one preferred embodiment, the viscosity of the glass ink is 75000±10000cps (25℃, 7# rotor, 20RPM).

[0026] Excessively fine particles will negatively impact the smoothness and appearance of the ink. Ink viscosity that is too high or too low is also detrimental to both appearance and performance.

[0027] In one preferred embodiment, the coefficient of thermal expansion of the glass ink is 8*10. -6 -10*10 -6 / ℃.

[0028] This invention also claims a method for preparing the glass ink, comprising the following steps:

[0029] S1. After fully dispersing the glass powder, carrier resin, solvent, and inorganic copper chromium cobalt black, grind them to obtain component 1;

[0030] S2. Add nanosphere silicon powder and diamond to component 1 and grind them to obtain glass ink.

[0031] In one preferred embodiment, bismuth oxide is added to component 1 and dispersed with a silicon-free dispersant before proceeding to step S2.

[0032] In one preferred embodiment, bismuth oxide and a silicon-free dispersant are added to component 1 and then dispersed at a speed of 600-1000 r / min for 5-10 min.

[0033] In one preferred embodiment, the dispersion speed in step S1 is 600-1000 r / min, and the dispersion time is 15-20 min.

[0034] In one preferred embodiment, the grinding time in step S1 is 30-50 minutes.

[0035] In one preferred embodiment, the fineness of component 1 is below 15 μm.

[0036] In one preferred embodiment, the grinding time in step S2 is 30-50 minutes.

[0037] In one preferred embodiment, the glass ink has a fineness of less than 15 μm.

[0038] This preparation method aims to fully mix glass powder and copper chromate black under the wetting of resin and solvent, allowing the inorganic pigments to fully open. Since the inorganic and organic resins form the carrier ink in this system, no chemical reaction will occur at room temperature or under stirring. Spherical silica powder and diamond need to be added last. The spherical silica powder needs to float on top to provide a tactile feel, while the diamond has a specific gravity of about 2-6 and will be at the bottom after sintering. The metallic luster can be seen from the glass surface (not the ink surface). Adding different weight parts will produce different levels of high gloss.

[0039] This invention also claims protection for the use of the glass ink in the preparation of 3C electronic glass, automotive rear window glass, and coated sunroof glass.

[0040] The beneficial effects of this invention are as follows:

[0041] The ink of this invention completely covers the silver lines on the surface, providing a uniform, shimmering appearance without affecting other properties such as acid resistance and adhesion. This invention employs a combination of stirring, mixing, dispersing, and grinding methods to prepare an ink that effectively covers silver lines. The preparation process is simple, easy to operate, and suitable for industrial production. The ink of this invention maintains high solids content while ensuring adhesion and printing ink uniformity, overcoming the bottleneck of insufficient hiding power in existing glass inks. It can be applied to screen printing or the preparation of glass materials such as mobile phone back covers, mobile phone lenses, and automotive parts, with a wide range of uses. Detailed Implementation

[0042] To enable those skilled in the art to better understand the technical solution of the present invention, the present invention will be further described in detail below with reference to embodiments.

[0043] The glass powder, model 480, is from Foshan Taoyise Glaze Co., Ltd., with a particle size of 5-15 micrometers. The carrier resin, model GEMR-85, is from Guangxi Wuzhou Richeng Forest Products Chemical Co., Ltd. The copper chromium cobalt black is from Jiangxi Jinhuan Pigment Co., Ltd. The silicon-free dispersant is sodium tripolyphosphate from Jiangxi Sangao Polymer Materials Co., Ltd. The nanosphere silica powder, bismuth oxide, and diamond powder are all commercially available. The solvent is a mixed solution of diethylene glycol butyl ether, terpineol, and kerosene in a mass ratio of 60:30:10. The fineness of the nanosphere silica powder is less than 15 micrometers. The gloss of the glass ink after adding the nanosphere silica powder is 2-3°. The fineness of the diamond powder is less than 15 micrometers.

[0044] Example 1

[0045] A glass ink, by weight, comprises 53 parts glass powder, 15 parts carrier resin, 15 parts solvent, 17 parts inorganic copper chromate black, 5 parts nanosphere silica powder, 15 parts bismuth oxide, 3 parts silicon-free dispersant, and 3 parts diamond powder. The solvent is a mixture of diethylene glycol butyl ether, terpineol, and kerosene in a ratio of 60:30:10.

[0046] The preparation method is as follows:

[0047] 53 parts of glass powder, 15 parts of carrier resin, 15 parts of solvent, and 17 parts of inorganic copper chromium black were thoroughly dispersed using a disperser at a speed of 600-1000 r / min for 15-20 min. Then, the mixture was ground using a three-roll mill for 30-50 min to achieve a fineness of less than 15 μm. Next, 15 parts of bismuth oxide and 3 parts of silicone-free dispersant (CONHP) were added and thoroughly dispersed using a disperser at a speed of 600-1000 r / min for 5-10 min. Finally, 5 parts of nanosphere silica powder and 3 parts of diamond powder were added and ground using a three-roll mill for 30-50 min to achieve a fineness of less than 15 μm.

[0048] The glass ink is screen-printed onto the glass and then sintered at a temperature of 530℃.

[0049] Comparative Example 1

[0050] The formulation of the glass ink is the same as in Example 1, except that 53 parts of glass powder, 15 parts of carrier resin, 15 parts of solvent, and 17 parts of inorganic copper chromium black are thoroughly dispersed using a disperser at a speed of 600-1000 r / min for 15-20 mins. Then, 15 parts of bismuth oxide and 3 parts of silicone-free dispersant (CONHP) are added and thoroughly dispersed using a disperser at a speed of 600-1000 r / min for 5-10 mins. Finally, 5 parts of nanosphere silica powder and 3 parts of diamond powder are added, and the mixture is ground using a three-roll mill for 30-50 mins to maintain a fineness below 15 μm. After screen printing the glass ink onto glass, it is sintered at a sintering temperature of 530℃.

[0051] The performance of the glass inks in the test examples and Comparative Example 1 was tested, and the test results are shown in Table 1.

[0052] The flickering sensation was tested using a BYK colorimeter; the OD value was measured using an X-Rite 341C transmission density meter; for black printed edges: ≤0.3% for laminated products (i.e., OD value ≥2.5); the brightness (L value) after sintering was measured using an EXACT colorimeter, L* ≤5; cross-cut (with glass): at least 10 parallel lines were drawn on the black edge with a scalpel, with a 1mm interval between the parallel lines. Adhesive tape was then attached to the squares, and the tape was quickly peeled off. The cut edges were smooth, and no squares in the cross-cut area fell off.

[0053] Table 1. Performance results of the glass inks in Examples and Comparative Example 1

[0054]

[0055]

[0056] The coefficient of thermal expansion of the glass ink in Example 1 is 8*10. -6 -10*10 -6 / ℃.

[0057] The test results of Example 1 and Comparative Example 1 show that the performance of sintered inks prepared by different processes differs significantly. Example 1 is significantly superior to Comparative Example 1. Under the wetting of the organic carrier, the glass powder and copper chromium black powder can be mixed evenly, avoiding the problem of uneven mixing caused by the glass powder forming small clumps with the silica powder when adding a silicone-free dispersant. The G-value of Example 1 is significantly greater than that of Comparative Example 1. A higher G-value indicates better shimmer and a better high-brightness effect.

[0058] Example 2

[0059] A glass ink, by weight, comprises the formulation shown in Table 2. The solvent is a mixture of diethylene glycol butyl ether: terpineol: kerosene = 60:30:10.

[0060] Table 2 Formulations of Example 2 and Comparative Examples 2-4

[0061] glass powder 50 0 50 50 50 Bismuth oxide 15 15 0 15 15 Nanosphere silica powder 5 5 5 0 5 Diamond powder 3 3 3 3 0 Carrier resin 15 15 15 15 15 solvent 15 15 15 15 15 Inorganic copper chromium black 17 17 17 17 17 Silicone-free dispersant 3 3 3 3 3 solvent 12 62 27 17 15 Sintering temperature (°C) 560℃ 560℃ 560℃ 560℃ 560℃

[0062] The glass powder, carrier resin, solvent, and copper chromium black are fully dispersed using a disperser at a speed of 600-1000 r / min for 15-20 mins, and then ground using a three-roll mill to a fineness of less than 15 μm. Then, bismuth oxide and silicon-free dispersant (CONHP) are added and fully dispersed using a disperser at a speed of 600-1000 r / min for 5-10 mins. Finally, nanosphere silica powder and diamond powder are added and ground using a three-roll mill to a fineness of less than 15 μm.

[0063] The sintering ink in Example 2 turns black after the addition of inorganic copper chromium black. The glass ink is screen-printed onto glass and then sintered at a temperature of 560°C. During this process, glass powder crystallizes and melts into the glass material, while diamond remains relatively stable and does not undergo a chemical reaction. Due to its high specific gravity, diamond exhibits high gloss at the bottom layer of the ink. Nanosphere silica powder is lightly coated on the surface of the ink by the glass powder, forming a matte layer that provides a smooth feel.

[0064] Performance tests were conducted on Example 2 and Comparative Examples 2-4, and the results are shown in Table 3.

[0065] Table 3 Performance test results of Example 2 and Comparative Examples 2-4

[0066]

[0067] After sintering at 560℃ in Examples 2 and Comparative Examples 2, 3, 4, and 5, the glass ink of Example 2 completed sintering and exhibited excellent performance. However, the glass powder and inorganic pigments, after screen printing and sintering with resin and solvent as carriers, had poor tactile feel and no high-gloss spots on the glass surface. Similarly, the bismuth powder and inorganic pigments, after screen printing and sintering with resin and solvent as carriers, also had poor tactile feel and no high-gloss spots on the glass surface. Furthermore, the nanosphere silicon powder and inorganic pigments, after screen printing and sintering with resin and solvent as carriers, also had poor tactile feel and no high-gloss spots on the glass surface. Finally, the diamond powder and inorganic pigments, after screen printing and sintering with resin and solvent as carriers, also had poor tactile feel and no high-gloss spots on the glass surface.

[0068] The above description of the embodiments is intended to facilitate understanding and use of the present invention by those skilled in the art. Those skilled in the art can readily make various modifications to these embodiments and apply the general principles described herein to other embodiments without inventive effort. Therefore, the present invention is not limited to the above embodiments. Improvements and modifications made by those skilled in the art based on the principles of the present invention, without departing from the scope of the invention, should be within the protection scope of the present invention.

Claims

1. A glass ink, characterized in that, By weight, it includes the following components: 45-60 parts glass powder, 13-25 parts inorganic copper chromium cobalt black, 3-12 parts carrier resin, 5-16 parts solvent, 2-6 parts diamond powder, 10-20 parts bismuth oxide and 3-8 parts nanosphere silica powder. The glass powder is a mixture of ZnO, B2O3, SiO2, KO2, BaO, and MgO, wherein the mass ratio of ZnO, B2O3, SiO2, KO2, BaO, and MgO is 60-75%:15-30%:50-70%:4-8%:1-5%:0.3-1%; the carrier resin is GEMR. 85, produced by Guangxi Wuzhou Richeng Forest Products Chemical Co., Ltd.

2. The glass ink according to claim 1, characterized in that, The glass powder has a particle size of 5-15 micrometers.

3. The glass ink according to claim 1, characterized in that, The solvent is one or more of diethylene glycol butyl ether, kerosene, divalent ester, terpineol, turpentine, diethylene glycol, n-pentanol, ethylene glycol, n-octanol, and n-butanol.

4. The glass ink according to claim 1, characterized in that, The solvent is a mixed solution of diethylene glycol butyl ether, terpineol, and kerosene in a mass ratio of 55-65:25-35:5-15.

5. The glass ink according to claim 1, characterized in that, The fineness of the nanosphere silicon powder is less than 15 micrometers.

6. The glass ink according to claim 1, characterized in that, Diamond powder has a fineness of less than 15 micrometers.

7. The method for preparing glass ink according to any one of claims 1-6, characterized in that, Includes the following steps: S1. After fully dispersing the glass powder, carrier resin, solvent, and inorganic copper chromium cobalt black, grind them to obtain component 1; S2. Add nanosphere silicon powder and diamond to component 1 and grind them to obtain glass ink.

8. The preparation method according to claim 7, characterized in that, The dispersion speed in step S1 is 600-1000 r / min, the dispersion time is 15-20 min, and the grinding time is 30-50 min.

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