High-stability glaze and preparation method and application thereof

Abstract

This invention discloses a high-stability glaze, its preparation method, and its application. The high-stability glaze, by weight, comprises the following raw materials: 10-20 parts of ink oil, 50-70 parts of glass powder, and 20-30 parts of titanium dioxide. The ink oil contains water-soluble polyurethane, which is prepared by the following method: diisocyanate and polyethylene glycol are mixed uniformly, and the mixture is slowly heated to 80-90°C and kept at this temperature for 2-3 hours; a chain extender is added, and the reaction is continued at 80-90°C for another 2-3 hours. The chain extender is a diol containing a tertiary amine; an end-capping agent is added, and the reaction is continued at 80-90°C for another 2-3 hours to obtain the water-soluble polyurethane. The end-capping agent is a monofunctional secondary aminosilane. The high-stability glaze of this invention exhibits good storage stability under high-temperature conditions.

Description

Technical Field

[0001] This invention belongs to the field of glaze technology, specifically relating to a high-stability glaze, a method for preparing the high-stability glaze, and the application of the high-stability glaze. Background Technology

[0002] A double-glass photovoltaic module consists of a front-pane coated glass, crystalline silicon solar cells, and a back-pane enamel-coated glass. The crystalline silicon solar cells are connected in series and parallel by wires to form the photovoltaic module. On the back-pane glass, enamel is screen-printed onto the light-transmitting areas connecting the crystalline silicon solar cells. This enamel is then cured and tempered to create a high-reflectivity enamel layer, resulting in the enamel-coated back-pane glass. This high-reflectivity enamel layer reflects transmitted light back to the crystalline silicon solar cells for reuse, achieving "secondary light absorption." Currently, mainstream enamel-coated back-pane glass has a reflectivity of ≥75%, effectively increasing the output power of the photovoltaic module.

[0003] The glaze is mainly composed of low-melting-point glass powder, titanium dioxide, and ink oil. The resin in the ink oil acts as a binder, carrying the glaze to specific areas of the backing glass during screen printing. After heat curing (180-220℃), it provides good adhesion. However, existing glazes generally suffer from poor storage stability at high temperatures (50℃), mainly manifested as agglomeration and sedimentation within a short period (7 days); easy clogging during screen printing; and numerous particles or even lumps in the resulting glaze layer, causing product quality issues. Summary of the Invention

[0004] In view of this, in order to overcome the shortcomings of the prior art, the purpose of this invention is to provide an improved high-stability glaze, its preparation method and application.

[0005] To achieve the above objectives, the present invention adopts the following technical solution: This invention provides a highly stable glaze, comprising, by weight, the following raw material components: 10-20 parts of ink-mixing oil, 50-70 parts of glass powder, and 20-30 parts of titanium dioxide. The ink-mixing oil comprises water-soluble polyurethane, which is prepared by the following method: Diisocyanate and polyethylene glycol are mixed evenly, and the mixture is slowly heated to 80-90℃ and kept at that temperature for 2-3 hours. Polyethylene glycol is used to achieve water solubility and provide hydroxyl groups to synthesize water-soluble polyurethanes with urethane bonds. Add a chain extender and continue the reaction at 80-90℃ for 2-3 hours. The chain extender is a diol containing a tertiary amine. Add a capping agent and continue the reaction at 80-90℃ for 2-3 hours to obtain the water-soluble polyurethane. The capping agent is a monofunctional secondary aminosilane.

[0006] During the research, it was discovered that the resin used in the ink-mixing oil plays a crucial role in the storage stability of the glaze under high-temperature (50°C) conditions. Therefore, the resin used in the ink-mixing oil of the high-stability glaze of this invention is a water-soluble polyurethane. In the preparation process of this water-soluble polyurethane, a diol containing a tertiary amine is used as a chain extender. The nitrogen atoms in the tertiary amine can form a hydrogen bond network with the urethane bonds in the final water-soluble polyurethane, thereby buffering the damage to the dispersion structure caused by thermal disturbances. On the other hand, the water-soluble polyurethane uses a monofunctional secondary aminosilane as a capping agent during its preparation. The siloxy groups in the capping agent can undergo transesterification with the hydroxyl groups on the surface of glass powder and titanium dioxide in the glaze, forming covalent bonds (Si-O-Si, Ti-O-Si). This anchors the water-soluble polyurethane to the particle surface ("particles" refers to the functional solid powders in the glaze, specifically including glass powder, which acts as the main skeleton and serves as a binder; titanium dioxide and other fillers play a high reflective role, i.e., the key to "secondary light absorption"). This suppresses particle migration in the glaze under high temperature (50°C) conditions, which is beneficial to improving the storage stability of the glaze under high temperature (50°C) conditions. The water-soluble polyurethane prepared in this invention contains aminosiloxane.

[0007] Specifically, the dispersion structure refers to the suspended distribution of solid particles (glass powder and titanium dioxide) in a liquid medium (inking oil) within a glaze system. In an ideal glaze, the fine solid powders should be uniformly suspended in the liquid, maintaining a certain distance from each other and not clumping together. This uniform suspension state is the desired ideal "dispersion structure." Damage to the dispersion structure refers to the following: when the temperature rises to 50°C, the thermal motion of molecules intensifies (i.e., "thermal disturbance"). If the binder (water-soluble polyurethane) cannot hold the particles, the particles will collide and aggregate due to violent movement, leading to "agglomeration" or "precipitation," which is the "damage to the dispersion structure" mentioned earlier.

[0008] According to some preferred embodiments of the present invention, the chain extender is selected from one or more of N-methyldiethanolamine, N-ethyldiethanolamine, and N-butyldiethanolamine, by weight.

[0009] According to some preferred embodiments of the present invention, the capping agent is selected from one or both of N-methyl-3-aminopropyltrimethoxysilane and N-phenyl-3-aminopropyltrimethoxysilane.

[0010] According to some preferred embodiments of the present invention, the raw material components of the ink oil, by weight, include 70-80 parts of alcohol ether solvent, 20-30 parts of the water-soluble polyurethane, and 1-5 parts of dispersant.

[0011] According to some preferred embodiments of the present invention, the alcohol ether solvent is selected from one or more of dipropylene glycol methyl ether, dipropylene glycol butyl ether, and ethylene glycol tert-butyl ether.

[0012] According to some preferred embodiments of the present invention, the diisocyanate is selected from one or two of 4,4'-dicyclohexylmethane diisocyanate and isophorone diisocyanate; the polyethylene glycol is selected from one or more of polyethylene glycol PEG-1000, polyethylene glycol PEG-1500, and polyethylene glycol PEG-2000.

[0013] According to some preferred embodiments of the present invention, the mass ratio of the chain extender to polyethylene glycol is 1:10-75, and the mass ratio of the end-capping agent to the chain extender is 1-10:1.

[0014] According to some preferred embodiments of the present invention, the total melting temperature of the glass powder is 650-700°C, and the average linear expansion coefficient of the glass powder is 80 × 10⁻⁶. -7 -90×10 -7 / K.

[0015] Preferably, the titanium dioxide is selected from one or more of the following: titanium dioxide R-900, titanium dioxide R-931, and titanium dioxide R-960 from Chemours Corporation, USA.

[0016] This invention further provides a method for preparing a highly stable glaze, used to prepare the highly stable glaze as described above, the method comprising the following steps: The alcohol ether solvent, water-soluble polyurethane, and dispersant are mixed evenly to obtain the ink oil; Glass powder and titanium dioxide are added to the ink oil, mixed evenly, and then ground to obtain a highly stable glaze with a fineness of less than 10μm.

[0017] The present invention also provides an application of the high-stability glaze described above in the printing of photovoltaic backsheet glass. Specifically, after screen printing the high-stability glaze of the present invention on the light-transmitting part of the crystalline silicon solar cell connection on the surface of the photovoltaic backsheet glass, it is cured (process temperature range of 180-220℃) and tempered (process temperature range of 600-720℃) to form a high-reflection glaze layer, thereby obtaining photovoltaic backsheet glazed glass.

[0018] Due to the adoption of the above technical solutions, the advantages of this invention compared to the prior art are as follows: the resin in the ink-adjusting oil raw material of the glaze of this invention is an improved water-soluble polyurethane, the chain extender in the preparation of water-soluble polyurethane is a diol containing a tertiary amine, and the end-capping agent is a monofunctional secondary aminosilane. Through the formation of a hydrogen bond network between the nitrogen atom in the tertiary amine and the urethane bond in the water-soluble polyurethane, and the formation of covalent bonds through the transesterification reaction between the siloxy group in the end-capping agent and the hydroxyl groups on the surface of the glass powder and titanium dioxide in the glaze, the effects of buffering the damage of thermal disturbance to the dispersion structure and anchoring the water-soluble polyurethane on the particle surface are achieved, thereby inhibiting particle migration under high temperature conditions and improving the storage stability of the glaze under high temperature conditions. Detailed Implementation

[0019] To enable those skilled in the art to better understand the technical solutions of the present invention, the technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort should fall within the scope of protection of the present invention.

[0020] The high-stability glaze of this embodiment comprises, by weight, the following raw materials: 10-20 parts of ink-mixing oil, 50-70 parts of glass powder, and 20-30 parts of titanium dioxide. The selected glass powder has a melting temperature of 650-700℃ and an average coefficient of linear expansion of 80×10⁻⁶. -7 -90×10 -7 / K; The titanium dioxide is selected from one or more of the following titanium dioxide R-900, titanium dioxide R-931, and titanium dioxide R-960 from Chemours Corporation, USA.

[0021] By weight, the ink oil comprises the following raw material components: 70-80 parts alcohol ether solvent, 20-30 parts water-soluble polyurethane, and 1-5 parts dispersant.

[0022] The alcohol ether solvent is selected from one or more of dipropylene glycol methyl ether, dipropylene glycol butyl ether, and ethylene glycol tert-butyl ether; the dispersant is selected from TEGO Dispers 760W from German company TEGO.

[0023] By weight, water-soluble polyurethane comprises the following raw material components: 15-25 parts of diisocyanate, 65-75 parts of polyethylene glycol, 1-5 parts of chain extender and 5-10 parts of end-capping agent, wherein the chain extender is a diol containing tertiary amine and the end-capping agent is a monofunctional secondary amine silane.

[0024] The diisocyanate is selected from one or two of 4,4'-dicyclohexylmethane diisocyanate and isophorone diisocyanate; the polyethylene glycol is selected from one or more of polyethylene glycol PEG-1000, polyethylene glycol PEG-1500, and polyethylene glycol PEG-2000; the chain extender is selected from one or more of N-methyldiethanolamine, N-ethyldiethanolamine, and N-butyldiethanolamine; and the end-capping agent is selected from one or two of N-methyl-3-aminopropyltrimethoxysilane and N-phenyl-3-aminopropyltrimethoxysilane.

[0025] The method for preparing a highly stable glaze as described above in this embodiment includes the following steps: The alcohol ether solvent, water-soluble polyurethane, and dispersant are mixed evenly to obtain the ink oil; Glass powder and titanium dioxide are added to the ink oil, mixed evenly, and then ground to obtain a highly stable glaze with a fineness of less than 10μm.

[0026] Water-soluble polyurethane is prepared by the following method: Mix diisocyanate and polyethylene glycol evenly, slowly heat to 80-90℃ and keep warm for 2-3 hours; Add chain extender and continue the reaction at 80-90℃ for 2-3 hours; Add the end-capping agent and continue the reaction at 80-90℃ for 2-3 hours to obtain water-soluble polyurethane.

[0027] Specifically, polyethylene glycol is added during the preparation of water-soluble polyurethane to achieve water solubility and provide hydroxyl groups, thereby synthesizing water-soluble polyurethane with urethane bonds. This allows the nitrogen atoms in the tertiary amine of the chain extender to form a hydrogen bond network with the urethane bonds in the water-soluble polyurethane, which can buffer the damage to the dispersion structure caused by thermal disturbances. The siloxy groups in the end-capping agent can undergo transesterification with the hydroxyl groups on the surface of glass powder and titanium dioxide in the glaze to form covalent bonds (Si-O-Si, Ti-O-Si), which anchors the water-soluble polyurethane on the particle surface. This can suppress the problem of particle migration in the glaze under high temperature conditions and is beneficial to improving the storage stability of the glaze under high temperature conditions.

[0028] Example 1: This example provides a method for preparing a highly stable glaze, comprising the following steps: Step 1: Prepare water-soluble polyurethane.

[0029] By weight, 20 parts of 4,4′-dicyclohexylmethane diisocyanate and 72 parts of polyethylene glycol PEG-1500 were stirred to make them evenly mixed, and then the temperature was slowly raised to 85°C and kept at that temperature for 2 hours. Under stirring conditions, add 2 parts of N-methyldiethanolamine and continue the reaction at 85°C for 2 hours. Under stirring conditions, 6 parts of N-methyl-3-aminopropyltrimethoxysilane were added, and the reaction was continued at 85°C for 2 hours to obtain water-soluble polyurethane.

[0030] Step 2: Prepare the ink oil.

[0031] By weight, 75 parts of dipropylene glycol methyl ether, 20 parts of water-soluble polyurethane from step 1, and 5 parts of dispersant are mixed evenly to obtain ink oil, wherein the dispersant is TEGO Dispers 760W.

[0032] Step 3: Prepare the glaze.

[0033] By weight, under stirring conditions, 55 parts of glass powder and 25 parts of titanium dioxide were added to 20 parts of the ink-mixing oil in step 2. After mixing evenly, the mixture was then ground by a three-roll mill to obtain a highly stable glaze with a fineness of less than 10 μm.

[0034] Example 2: This example provides a method for preparing a highly stable glaze, including the following steps: Step 1: Prepare water-soluble polyurethane.

[0035] By weight, 25 parts of 4,4′-dicyclohexylmethane diisocyanate and 65 parts of polyethylene glycol PEG-1000 were stirred to make them evenly mixed, and then the mixture was slowly heated to 85°C and kept at that temperature for 2 hours. Under stirring conditions, 2.5 parts of N-methyldiethanolamine were added, and the reaction was continued at 85°C for 2 hours. Under stirring conditions, 7.5 parts of N-methyl-3-aminopropyltrimethoxysilane were added, and the reaction was continued at 85°C for 2 hours to obtain water-soluble polyurethane.

[0036] Step 2: Prepare the ink oil.

[0037] By weight, 75 parts of dipropylene glycol methyl ether, 20 parts of water-soluble polyurethane from step 1, and 5 parts of dispersant are mixed evenly to obtain ink oil, wherein the dispersant is TEGO Dispers 760W.

[0038] Step 3: Prepare the glaze.

[0039] By weight, under stirring conditions, 55 parts of glass powder and 25 parts of titanium dioxide were added to 20 parts of the ink-mixing oil in step 2. After mixing evenly, the mixture was then ground by a three-roll mill to obtain a highly stable glaze with a fineness of less than 10 μm.

[0040] Example 3: This example provides a method for preparing a highly stable glaze, comprising the following steps: Step 1: Prepare water-soluble polyurethane.

[0041] By weight, 15 parts of 4,4′-dicyclohexylmethane diisocyanate and 68 parts of polyethylene glycol PEG-2000 were stirred to make them evenly mixed, and then the mixture was slowly heated to 85°C and kept at that temperature for 2 hours. Under stirring conditions, add 2 parts of N-methyldiethanolamine and continue the reaction at 85°C for 2 hours. Under stirring conditions, 5 parts of N-methyl-3-aminopropyltrimethoxysilane were added, and the reaction was continued at 85°C for 2 hours to obtain water-soluble polyurethane.

[0042] Step 2: Prepare the ink oil.

[0043] By weight, 75 parts of dipropylene glycol methyl ether, 20 parts of water-soluble polyurethane from step 1, and 5 parts of dispersant are mixed evenly to obtain ink oil, wherein the dispersant is TEGO Dispers 760W.

[0044] Step 3: Prepare the glaze.

[0045] By weight, under stirring conditions, 55 parts of glass powder and 25 parts of titanium dioxide were added to 20 parts of the ink-mixing oil in step 2. After mixing evenly, the mixture was then ground by a three-roll mill to obtain a highly stable glaze with a fineness of less than 10 μm.

[0046] Comparative Example 1: The only difference from Example 1 is that the raw material component N-methyldiethanolamine in the water-soluble polyurethane is 8 parts.

[0047] Comparative Example 2: The only difference from Example 1 is that the raw material component N-methyl-3-aminopropyltrimethoxysilane in the water-soluble polyurethane is 2 parts.

[0048] Comparative Example 3: The only difference from Example 1 is that the water-soluble polyurethane in the raw material components of the ink oil is replaced with conventional water-soluble polyurethane without aminosiloxanes, specifically the HUX-541 water-soluble polyurethane from Idico Corporation of Japan.

[0049] Comparative Example 4: The only difference from Example 1 is that 2 parts of N-methyldiethanolamine in the raw material composition of water-soluble polyurethane are replaced with 2 parts of 1,4-butanediol.

[0050] Comparative Example 5: The only difference from Example 1 is that 6 parts of N-methyl-3-aminopropyltrimethoxysilane in the raw material composition of water-soluble polyurethane were replaced with 6 parts of n-butanol.

[0051] Tests and Results: The stability of the glazes prepared in Examples 1 to 3 and Comparative Examples 1 to 5 was tested. The glazes prepared in Examples 1 to 3 and Comparative Examples 1 to 5 were screen-printed onto the light-transmitting part of the crystalline silicon solar cell connection of the backplate glass, and then cured and tempered to form a glaze layer, thus obtaining photovoltaic backplate glazed glass. The test results are shown in Table 1 below.

[0052] Table 1 Test Results

[0053] The relevant performance tests in Table 1 above were conducted using the following methods: Reflectivity: Tested according to T / CPIA 0028.2-2021 "Glass for photovoltaic modules - Part 2: Anti-reflective coating glass for backsheets of double-glass modules".

[0054] Adhesion: Tested according to GB / T 9286-2021 "Paints and Varnishes Cross-cut Test".

[0055] The results in Table 1 show that the glazes in Examples 1 to 3 of the present invention have high stability. After being placed at a temperature of 50°C for 30 days, the glazes still have no agglomerated particles or sediment. Furthermore, when the glazes are used for screen printing, they do not clog the plate, do not have jagged edges or burrs, and are easy to wash. Moreover, the glazed layer produced after screen printing is smooth and free of impurities. The glazed layer produced after curing and tempering has high reflectivity and high adhesion.

[0056] The glazes in Comparative Examples 1 to 5, after being placed at 50°C for 30 days, all showed agglomerated particles and sedimentation. When the glazes were further used for screen printing, problems such as plate clogging, jagged edges, and burrs occurred. In addition, the glazed layer produced after screen printing had a large number of particles. Blocky objects also appeared in Comparative Examples 1 and 2. It can be seen that the glazes prepared in Comparative Examples 1 to 5 have poor stability, which further leads to poor product quality.

[0057] In summary, the glaze of the present invention uses an improved water-soluble polyurethane as the resin in the ink oil, and a diol containing a tertiary amine as the chain extender and a monofunctional secondary aminosilane as the end-capping agent during the preparation of the water-soluble polyurethane. This is achieved by forming a hydrogen bond network between the nitrogen atoms in the tertiary amine and the urethane bonds in the water-soluble polyurethane, and by forming covalent bonds through transesterification reactions between the siloxy groups in the end-capping agent and the hydroxyl groups on the surfaces of the glass powder and titanium dioxide in the glaze. This buffers the damage to the dispersion structure caused by thermal disturbances, anchors the water-soluble polyurethane to the particle surface, and inhibits particle migration under high-temperature conditions, thereby effectively improving the storage stability of the glaze under high-temperature conditions.

[0058] The above embodiments of the present invention are only for illustrating the technical concept and features of the present invention, and are intended to enable those skilled in the art to understand the content of the present invention and implement it accordingly. They should not be construed as limiting the scope of protection of the present invention. All equivalent changes or modifications made in accordance with the spirit and essence of the present invention should be covered within the scope of protection of the present invention.

Claims

1. A highly stable glaze, characterized in that, The ink comprises, by weight, the following raw material components: 10-20 parts of ink oil, 50-70 parts of glass powder, and 20-30 parts of titanium dioxide. The ink oil contains water-soluble polyurethane, which is prepared by the following method: Mix diisocyanate and polyethylene glycol evenly, slowly heat to 80-90℃ and keep warm for 2-3 hours; Add a chain extender and continue the reaction at 80-90℃ for 2-3 hours. The chain extender is a diol containing a tertiary amine. Add a capping agent and continue the reaction at 80-90℃ for 2-3 hours to obtain the water-soluble polyurethane. The capping agent is a monofunctional secondary aminosilane.

2. The high-stability glaze according to claim 1, characterized in that, The chain extender is selected from one or more of N-methyldiethanolamine, N-ethyldiethanolamine, and N-butyldiethanolamine, based on parts by weight.

3. The high-stability glaze according to claim 1, characterized in that, The end-capping agent is selected from one or both of N-methyl-3-aminopropyltrimethoxysilane and N-phenyl-3-aminopropyltrimethoxysilane.

4. The high-stability glaze according to claim 1, characterized in that, By weight, the raw material components of the ink oil include 70-80 parts of alcohol ether solvent, 20-30 parts of water-soluble polyurethane, and 1-5 parts of dispersant.

5. The high-stability glaze according to claim 4, characterized in that, The alcohol ether solvent is selected from one or more of dipropylene glycol methyl ether, dipropylene glycol butyl ether, and ethylene glycol tert-butyl ether.

6. The high-stability glaze according to claim 1, characterized in that, The diisocyanate is selected from one or two of 4,4'-dicyclohexylmethane diisocyanate and isophorone diisocyanate; the polyethylene glycol is selected from one or more of polyethylene glycol PEG-1000, polyethylene glycol PEG-1500, and polyethylene glycol PEG-2000.

7. The high-stability glaze according to claim 1, characterized in that, The mass ratio of the chain extender to polyethylene glycol is 1:10-75, and the mass ratio of the end-capping agent to the chain extender is 1-10:

1.

8. The high-stability glaze according to claim 1, characterized in that, The glass powder has a melting temperature of 650-700℃ and an average coefficient of linear expansion of 80×10⁻⁶. -7 -90×10 -7 / K.

9. A method for preparing a highly stable glaze, characterized in that, The method for preparing the high-stability glaze as described in any one of claims 1-8 comprises the following steps: The alcohol ether solvent, water-soluble polyurethane, and dispersant are mixed evenly to obtain the ink oil; Glass powder and titanium dioxide are added to the ink oil, mixed evenly, and then ground to obtain a highly stable glaze with a fineness of less than 10μm.

10. The application of a highly stable glaze as described in any one of claims 1-8 in photovoltaic backsheet glass printing.