Water-soluble acrylic resin, method for preparing the same, and ink vehicle for photovoltaic glass enamel

Abstract

The application discloses a water-soluble acrylic resin, a preparation method thereof and an ink adjusting oil for photovoltaic glass glaze, and the water-soluble acrylic resin comprises the following components: 20-30 parts of methyl methacrylate, 10-20 parts of butyl acrylate, 5-10 parts of hydroxyethyl acrylate, 2-5 parts of acrylic acid, 1-5 parts of a copolymerization functional monomer, 2-5 parts of methoxy polyethylene glycol acrylate, 40-60 parts of an alcohol ether solvent or 0.002-0.1 parts of an initiator. The water-soluble acrylic resin prepared by the application can be dissolved in water and alcohol ether solvent, the ink adjusting oil prepared by using the water-soluble acrylic resin has good wettability and dispersibility, good wrapping property, can reduce or even not add a dispersant, has good wettability and dispersibility, and therefore, cost can be saved; in addition, the ink coating after drying has good adhesion to glass, has few ash and carbon residues after high-temperature sintering, and has little influence on the color of a glaze layer.

Description

Technical Field

[0001] This invention belongs to the field of photovoltaic module technology, specifically relating to a water-soluble acrylic resin and its preparation method, and an ink oil for photovoltaic glass glaze. Background Technology

[0002] Currently, high-reflectivity inks for photovoltaic glass are generally formulated from low-melting-point glass powder, titanium dioxide, and ink binder, with powder content exceeding 70%. Ink binder, also called squeegee oil (bonding material), is a crucial component of printing inks. The rheological properties, viscosity, drying properties, film-forming properties, and printing performance of the ink all depend on the ink binder, making it key to ink quality. Its main components are various organic resins, high-boiling-point organic solvents, and additives. In glass screen printing ink formulations, its primary role is to mix powdered low-melting-point glass powder and pigments such as titanium dioxide into a paste for easy screen printing. Furthermore, its viscosity temporarily adheres the glass powder and titanium dioxide to the smooth surface of glass products. During the high-temperature baking (firing) process, it must completely volatilize and burn off. The sintering process for high-reflectivity inks for photovoltaic glass typically involves sintering at 680–750℃ for 2–6 minutes. The softening point of the low-melting-point glass powder used in these inks is generally between 450–600℃. During glass tempering, the resin rapidly decomposes at high temperatures, while the low-melting-point glass powder melts and softens, replacing the resin as a binder to form the enamel, thus playing a "secondary film-forming" role. This transforms the ink from an organic binder to an inorganic binder, firmly bonding it to the glass. To achieve good sintering performance (high reflectivity and ink layer density) and acid resistance, the resin and low-melting-point glass powder need to have good compatibility, ensuring that the low-melting-point glass powder begins to melt and flow when the resin has completely decomposed. Therefore, the final decomposition temperature of the resin and the softening point of the low-melting-point glass powder need to be similar; simultaneously, the softening point and crystallization temperature of the low-melting-point glass powder need to be lower than the sintering temperature to ensure that the ink can fully melt and flow during sintering, spreading into a dense surface layer, and crystallizing on the surface to achieve good reflectivity and weather resistance. This requires a matching between the decomposition temperature of the ink resin and the melting temperature of the selected low-melting-point glass powder and the tempering furnace temperature. It cannot decompose too early, because the glass powder has not yet melted, and the ink layer is prone to powdering and falling off. It also cannot decompose too late, because the molten glass powder will cover and encapsulate the organic matter, which will cause the color glaze to scorch and turn black.

[0003] Furthermore, for inks with such high powder content, the ink-adjusting resin must have excellent wetting and dispersing ability for the powder, be able to quickly wet and coat the powder surface and penetrate into the powder clumps to quickly open them up, thereby improving the powder dispersion and grinding efficiency, resulting in smaller powder particle size, and preventing powder agglomeration. Otherwise, inorganic powders are prone to sedimentation and stratification, which will affect the storage stability and printing adaptability of the ink. Summary of the Invention

[0004] The present invention aims to solve at least one of the technical problems existing in the prior art. To this end, the present invention proposes a water-soluble acrylic resin.

[0005] The present invention also proposes a method for preparing the above-mentioned water-soluble acrylic resin.

[0006] The present invention also proposes an application of a water-soluble acrylic resin.

[0007] This invention also proposes an ink for adjusting photovoltaic glass glaze.

[0008] The present invention also proposes a method for preparing ink for photovoltaic glass glaze.

[0009] This invention also proposes an application of ink for photovoltaic glass glaze.

[0010] According to one aspect of the present invention, a water-soluble acrylic resin is provided, comprising, by weight, the following components: 20-30 parts of methyl methacrylate, 10-20 parts of butyl acrylate, 5-10 parts of hydroxyethyl acrylate, 2-5 parts of acrylic acid, 1-5 parts of comonomer, 2-5 parts of methoxy polyethylene glycol acrylate, 40-60 parts of alcohol ether solvent, or 0.002-0.1 parts of initiator.

[0011] In some embodiments of the present invention, the copolymer functional monomer includes a phosphate functional monomer.

[0012] In some embodiments of the present invention, the phosphate ester functional monomer includes at least one selected from: methacryloyloxyethyl phosphate, ethylene glycol methacrylate phosphate, alkyl acrylate phosphate, allyl polyether phosphate, and methacrylate polyether phosphate. The introduction of the phosphate ester functional monomer enhances the water solubility of the acrylic resin and its adhesion to glass, and also improves its ability to adsorb pigments.

[0013] In some embodiments of the present invention, the methoxy polyethylene glycol acrylate includes at least one selected from methoxy polyethylene glycol (350) acrylate, methoxy polyethylene glycol (400) acrylate, methoxy polyethylene glycol (550) acrylate, and methoxy polyethylene glycol (1000) acrylate. Because the molecular chain of methoxy polyethylene glycol acrylate contains a large number of ether bonds, it can increase the solubility of the resin in the dispersion medium. Simultaneously, the relatively long polyether segments can stabilize the powder particles through steric hindrance.

[0014] In some embodiments of the present invention, the alcohol ether solvent is at least one selected from propylene glycol methyl ether, propylene glycol butyl ether, diethylene glycol butyl ether, dipropylene glycol methyl ether, tripropylene glycol methyl ether, dipropylene glycol butyl ether, and tripropylene glycol butyl ether.

[0015] In some embodiments of the present invention, the initiator is at least one selected from azobisisobutyronitrile, azobisisobutyramidine hydrochloride, benzoyl peroxide, and tert-butyl peroxide.

[0016] In some embodiments of the present invention, the solid content of the water-soluble acrylic resin is 40-60%.

[0017] In some embodiments of the present invention, the water-soluble acrylic resin has a weight-average molecular weight of 5,000 to 100,000 MW; if the molecular weight is too low, the continuous film-forming property is poor, and if the molecular weight is too high, the wetting and dispersion effect on the powder will be poor, and the decomposition temperature will be too high.

[0018] According to a second aspect of the present invention, a method for preparing a water-soluble acrylate is provided, the method comprising the following steps:

[0019] (1) Mix methyl methacrylate, butyl acrylate, hydroxyethyl acrylate, acrylic acid, comonomer, and methoxy polyethylene glycol acrylate to obtain a mixed solution;

[0020] (2) After adding the mixed solution and initiator to the alcohol ether solvent in batches for reaction, the pH is adjusted to 8-9 to obtain water-soluble acrylate.

[0021] In some embodiments of the present invention, the mixed solution is added in batches at least twice.

[0022] In some embodiments of the present invention, the mixed solution is added in batches twice.

[0023] In some embodiments of the present invention, the amount of the mixed solution added for the first time is 1 / 6 to 1 / 2 of the total amount of the mixed solution.

[0024] In some embodiments of the present invention, the amount of the mixed solution added a second time is the remainder of the amount added a first time.

[0025] In some embodiments of the present invention, the initiator is added in batches at least three times.

[0026] In some embodiments of the present invention, the amount added for the first time is 1 / 8 to 3 / 8 of the total amount of initiator.

[0027] In some embodiments of the present invention, the amount of the second addition is 1 / 8 to 1 / 2 of the total amount of initiator.

[0028] In some embodiments of the present invention, the amount added for the third time is the remainder after the second addition of the initiator.

[0029] In some embodiments of the present invention, after the first addition of the mixed solution and initiator to the alcohol ether solvent, the reaction is carried out for 12 to 18 minutes to obtain reaction solution A.

[0030] In some embodiments of the present invention, the temperature of the alcohol ether solvent is 88–92°C.

[0031] In some embodiments of the present invention, before the second addition of the mixed solution and the initiator, the remaining mixed solution is mixed with the initiator and added dropwise to the reaction solution B to obtain reaction solution B, which is then reacted at 88-92°C for 4-6 hours.

[0032] In some embodiments of the present invention, the third addition of the initiator is to add the remaining initiator to the reaction solution B and react at 88-92°C for 1-3 hours.

[0033] In some embodiments of the present invention, the solution temperature is 40–50°C when adjusting the pH.

[0034] In some embodiments of the present invention, the pH adjuster used for adjusting the pH includes at least one of ammonia, N,N-dimethylethanolamine, and AMP95 (2-amino-2-methyl-1-propanol).

[0035] According to a third aspect of the invention, an application of a water-soluble acrylic resin is provided, said application being its use in the preparation of ink oils.

[0036] In some embodiments of the present invention, the ink oil is an ink oil for photovoltaic glass glaze.

[0037] In some embodiments of the present invention, the application is an application in the preparation of photovoltaic glass.

[0038] According to a fourth aspect of the present invention, an ink oil for photovoltaic glass glaze is provided, the ink oil for photovoltaic glass glaze comprising the above-mentioned water-soluble acrylic resin.

[0039] In some embodiments of the present invention, the ink for photovoltaic glass glaze further includes alcohol ether solvent, thickener and anti-settling agent and additives.

[0040] In some embodiments of the present invention, the alcohol ether solvent is at least one selected from diethylene glycol butyl ether, dipropylene glycol methyl ether, tripropylene glycol methyl ether, dipropylene glycol butyl ether, tripropylene glycol butyl ether, and diethylene glycol tert-butyl ether.

[0041] In some embodiments of the present invention, the thickening and anti-settling agent is one or more of polyamide wax, cellulose, and modified polyurea solution.

[0042] In some embodiments of the present invention, the additive is one or more of a wetting and dispersing agent, an antifoaming agent, and a leveling agent. It is used to adjust the dispersibility of the ink oil with pigments and fillers, prevent air bubbles, or improve leveling properties.

[0043] In some embodiments of the present invention, the wetting and dispersing agent is one or more of BYK-180, BYK-182, TEGO750W, TEGO755W, and TEGO760W.

[0044] In some embodiments of the present invention, the defoamer includes non-silicone defoamers.

[0045] In some embodiments of the present invention, the non-silicone defoamer includes one or more of BYK1790, BYK-A501, TEGOFoamex 830, TEGO 936, and TEGO 920.

[0046] In some embodiments of the present invention, the leveling agent includes a non-silicone leveling agent.

[0047] In some embodiments of the present invention, the leveling agent includes a water-oil universal non-silicone leveling agent.

[0048] In some embodiments of the present invention, the water-oil universal non-silicone leveling agent includes one or more of BYK358N, BYK380N, and BYK381.

[0049] In some embodiments of the present invention, the ink for photovoltaic glass glaze comprises the following components by weight: 1-10 parts of water-soluble acrylic resin, 80-95 parts of alcohol ether solvent, 0.5-5 parts of thickener and anti-settling agent, 1-2 parts of wetting and dispersing agent, 0-0.5 parts of defoamer and 0-2 parts of leveling agent.

[0050] According to a fifth aspect of the present invention, a method for preparing the above-mentioned ink oil for photovoltaic glass glaze is provided, the method comprising the following steps: adding a thickening and anti-settling agent to an alcohol ether solvent, dissolving it, and then adding a water-soluble acrylic resin to obtain a mixed solution; adding an additive to the mixed solution, and mixing to obtain the ink oil for photovoltaic glass glaze.

[0051] In some embodiments of the present invention, the step of adding the thickening and anti-settling agent to the alcohol ether solvent is carried out by low-speed stirring.

[0052] In some embodiments of the present invention, the dissolution is performed by stirring for a period of 30 to 60 minutes.

[0053] In some embodiments of the present invention, the ink used to adjust the photovoltaic glass glaze is a uniform and transparent liquid.

[0054] According to a sixth aspect of the present invention, an application of an ink for photovoltaic glass glaze is provided, wherein the application is in the preparation of high reflectivity ink for photovoltaic glass.

[0055] According to some embodiments of the present invention, at least the following beneficial effects are achieved: The water-soluble acrylic resin prepared by the present invention is prepared by free radical copolymerization of phosphate ester functional monomers and methoxy polyethylene glycol acrylate with conventional acrylic / acrylate monomers (excluding monomers containing benzene rings and organosilicon double bonds) to produce a water-soluble acrylic resin with a weight average molecular weight of 5000-100000MW. The introduction of phosphate ester functional monomers enhances the water solubility and adhesion of the acrylic resin to glass, and also improves its adsorption capacity for pigments; at the same time, the introduction of methoxy polyethylene glycol acrylate, due to the large number of ether bonds in the molecular chain, enhances the solubility of the resin in the dispersion medium, and the long polyether chain segments can stabilize the powder particles through steric hindrance. Therefore, this resin is soluble in both water and alcohol ether solvents. The ink oil prepared with it not only has good wetting and dispersibility of powder and good encapsulation properties, but also reduces or eliminates the need for dispersants. It also has excellent wetting and dispersibility, thus saving costs. Moreover, the ink coating has good adhesion to glass after drying, and after high-temperature sintering, it has less ash content, less carbon residue, and has little impact on the color of the glaze. Attached Figure Description

[0056] The present invention will be further described below with reference to the accompanying drawings and embodiments, wherein:

[0057] Figure 1 The images show the residual carbon content of the ink oil after high-temperature sintering in the test examples of this invention. Specifically, A is the residual carbon content of the ink oil prepared in Example 5 after high-temperature sintering, B is the residual carbon content of the ink oil prepared in Example 6 after high-temperature sintering, C is the residual carbon content of the ink oil prepared in Example 7 after high-temperature sintering, and D is the residual carbon content of the ink oil prepared in Example 8 after high-temperature sintering.

[0058] Figure 2 The images show the residual carbon content of the ink oil after high-temperature sintering in the test examples of this invention. In particular, A is the residual carbon content of the ink oil prepared in Comparative Example 2 after high-temperature sintering, and B is the residual carbon content of the ink oil prepared in Comparative Example 4 after high-temperature sintering. Detailed Implementation

[0059] The following will describe the concept and technical effects of the present invention clearly and completely with reference to embodiments, so as to fully understand the purpose, features and effects of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, not all embodiments. Other embodiments obtained by those skilled in the art based on the embodiments of the present invention without creative effort are all within the scope of protection of the present invention.

[0060] Example 1

[0061] This embodiment prepares a water-soluble acrylic resin, and the specific process is as follows:

[0062] (1) Weigh 25g of methyl methacrylate, 10g of butyl acrylate, 10g of hydroxyethyl acrylate, 4g of acrylic acid, 2g of allyl polyether phosphate, and 4g of methoxy polyethylene glycol (400) acrylate and mix them evenly to obtain mixed monomer A.

[0063] (2) Weigh 0.22g of azobisisobutyronitrile and dissolve it in 5g of propylene glycol methyl ether to obtain initiator solution B;

[0064] (3) Add 15g of propylene glycol methyl ether and 25g of diethylene glycol butyl ether to a four-necked flask, start stirring (250rpm) and heat to 90℃. Add 1 / 3 of the mixed monomer A and 1 / 4 of the initiator solution B to the four-necked flask. After reacting for 15min, add the remaining mixed monomer A and 1 / 2 of the initiator solution B dropwise to the four-necked flask over 3-4h. After the dropwise addition is complete, keep the reaction at the temperature for 5h. Then add the remaining 1 / 4 of the initiator solution B and continue to keep the reaction at the temperature for 2h. After cooling to 45℃ (40-50℃ is acceptable), add the pH adjuster N,N-dimethylethanolamine to adjust the pH of the system to 8.5 (8-9 is acceptable). Stir the reaction for 0.5h to obtain water-soluble acrylic resin.

[0065] Example 2

[0066] This embodiment prepares a water-soluble acrylic resin, and the specific process is as follows:

[0067] (1) Weigh 20g of methyl methacrylate, 10g of butyl acrylate, 8g of hydroxyethyl acrylate, 4g of acrylic acid, 4g of ethylene glycol methacrylate phosphate, and 4g of methoxy polyethylene glycol (350) acrylate and mix them evenly to obtain mixed monomer A.

[0068] (2) Weigh 0.5g of azobisisobutyronitrile and dissolve it in 5g of propylene glycol methyl ether to obtain initiator solution B;

[0069] (3) Add 20g of propylene glycol methyl ether and 25g of diethylene glycol butyl ether to a four-necked flask, start stirring (250rpm) and heat to 90℃. Add 1 / 3 of the mixed monomer A and 1 / 4 of the initiator solution B to the four-necked flask. After reacting for 15min, add the remaining mixed monomer A and 1 / 2 of the initiator solution B dropwise to the four-necked flask over 3-4h. After the dropwise addition is complete, keep the reaction at the temperature for 5h. Then add the remaining 1 / 4 of the initiator solution B and continue to keep the reaction at the temperature for 2h. After cooling to 45℃ (40-50℃ is acceptable), add the pH adjuster N,N-dimethylethanolamine to adjust the pH of the system to 8.5 (8-9 is acceptable). Stir the reaction for 0.5h to obtain water-soluble acrylic resin.

[0070] Example 3

[0071] This embodiment prepares a water-soluble acrylic resin, and the specific process is as follows:

[0072] (1) Weigh 30g of methyl methacrylate, 15g of butyl acrylate, 5g of hydroxyethyl acrylate, 5g of acrylic acid, 3g of polyether methacrylate and 2g of methoxy polyethylene glycol (550) acrylate and mix them evenly to obtain mixed monomer A.

[0073] (2) Weigh 0.6g of azobisisobutyronitrile and dissolve it in 5g of propylene glycol methyl ether to obtain initiator solution B;

[0074] (3) Add 15g of propylene glycol methyl ether and 20g of diethylene glycol butyl ether to a four-necked flask, start stirring (250rpm) and heat to 90℃. Add 1 / 3 of the mixed monomer A and 1 / 4 of the initiator solution B to the four-necked flask. After reacting for 15min, add the remaining mixture of mixed monomer A and 1 / 2 of the initiator solution B dropwise to the four-necked flask over 3-4h. After the dropwise addition is complete, keep the reaction at the temperature for 5h. Then add the remaining 1 / 4 of the initiator solution B and continue to keep the reaction at the temperature for 2h. After cooling to 45℃ (40-50℃ is acceptable), add the pH adjuster N,N-dimethylethanolamine to adjust the pH of the system to 8.5 (8-9 is acceptable). Stir the reaction for 0.5h to obtain water-soluble acrylic resin.

[0075] Example 4

[0076] This embodiment prepares a water-soluble acrylic resin, and the specific process is as follows:

[0077] (1) Weigh 20g of methyl methacrylate, 20g of butyl acrylate, 5g of hydroxyethyl acrylate, 5g of acrylic acid, 5g of methacryloyl oxyethyl phosphate, and 5g of methoxy polyethylene glycol (1000) acrylate and mix them evenly to obtain mixed monomer A.

[0078] (2) Weigh 0.45g of azobisisobutyronitrile and dissolve it in 5g of propylene glycol methyl ether to obtain initiator solution B;

[0079] (3) Add 15g of propylene glycol methyl ether and 20g of diethylene glycol butyl ether to a four-necked flask, start stirring (250rpm) and heat to 90℃. Add 1 / 3 of the mixed monomer A and 1 / 4 of the initiator solution B to the four-necked flask. After reacting for 15min, add the remaining mixture of mixed monomer A and 1 / 2 of the initiator solution B dropwise to the four-necked flask over 3-4h. After the dropwise addition is complete, keep the reaction at the temperature for 5h. Then add the remaining 1 / 4 of the initiator solution B and continue to keep the reaction at the temperature for 2h. After cooling to 45℃ (40-50℃ is acceptable), add the pH adjuster N,N-dimethylethanolamine to adjust the pH of the system to 8.5 (8-9 is acceptable). Stir the reaction for 0.5h to obtain water-soluble acrylic resin.

[0080] Example 5

[0081] This embodiment prepares an ink oil for photovoltaic glass glaze, and the specific process is as follows:

[0082] Under low-speed stirring (400 rpm), 2 g of polyamide wax was slowly added to 89 g of alcohol ether solvent and dispersed and stirred for 45 min (30-60 min is also acceptable). After it was completely dissolved, 6 g of water-soluble acrylic resin prepared in Example 1 was added to it and mixed evenly. Then, 2 g of dispersant TEGO750W and 1 g of leveling agent BYK380N were added and stirred thoroughly. After forming a uniform and transparent liquid, the ink oil for photovoltaic glass glaze was obtained.

[0083] Example 6

[0084] This embodiment prepares an ink oil for photovoltaic glass glaze, and the specific process is as follows:

[0085] Under low-speed stirring (400 rpm), 1 g of thickening and anti-settling agent modified polyurea solution was slowly added to 90 g of alcohol ether solvent and dispersed and stirred for 45 min (30-60 min is also acceptable). After complete dissolution, 8 g of water-soluble acrylic resin prepared in Example 2 was added to it and mixed evenly. Then, 0.5 g of dispersant TEGO750W and 0.5 g of leveling agent BYK380N were added and stirred thoroughly until a uniform and transparent liquid was formed. This is the ink oil for photovoltaic glass glaze.

[0086] Example 7

[0087] This embodiment prepares an ink oil for photovoltaic glass glaze, and the specific process is as follows:

[0088] Under low-speed stirring (400 rpm), 3 g of thickening and anti-settling agent ethyl cellulose was slowly added to 85 g of alcohol ether solvent. If necessary, the mixture was heated appropriately to 50°C (40-60°C is acceptable). The mixture was dispersed and stirred for 45 min (30-60 min is acceptable). After complete dissolution, 10 g of water-soluble acrylic resin prepared in Example 3 was added to the mixture. After mixing evenly, 1 g of dispersant TEGO 750W, 0.1 g of defoamer TEGO Foamex 830, and 0.9 g of leveling agent BYK 380N were added. The mixture was stirred thoroughly until a uniform and transparent liquid was formed, which is the ink oil for photovoltaic glass glaze.

[0089] Example 8

[0090] This embodiment prepares an ink oil for photovoltaic glass glaze, and the specific process is as follows:

[0091] Under low-speed stirring (400 rpm), 2 g of thickening and anti-settling agent ethyl cellulose was slowly added to 88 g of alcohol ether solvent. If necessary, the mixture was heated appropriately to 50°C (40-60°C is acceptable). The mixture was dispersed and stirred for 45 min (30-60 min is acceptable). After complete dissolution, 10 g of the water-soluble acrylic resin prepared in Example 4 was added to the mixture. After thorough stirring to form a uniform and transparent liquid, the ink for photovoltaic glass glaze was obtained.

[0092] Comparative Example 1

[0093] This comparative example prepared an organosilicon-modified water-soluble acrylic resin, and the specific process is as follows:

[0094] (1) Keep the reactor clean and dry. Add 40 parts of alcohol ether solvent by weight. Pour nitrogen into the reactor and keep it running. Pour cooling water into the condenser and heat the alcohol ether solvent to 140°C.

[0095] (2) Take another dispersion vessel and add, by weight, 10 parts glycidyl tert-carbonate, 5 parts hydroxyethyl acrylate, 3 parts methyl methacrylate, 5 parts acrylic acid, 10 parts isobornyl methacrylate, 25 parts butyl acrylate, 15 parts styrene, 5 parts organosilicon monomer, 2 parts molecular weight regulator (chain transfer agent), and 3.5 parts initiator; stir and mix evenly at a stirring speed of 300 r / min for 40 min; add the above mixed solution dropwise to the reaction vessel of step (1) for 6 h, and control the temperature at 140℃; after the dropwise addition is completed, keep the reaction at 140℃ for 2 h.

[0096] (3) Add 0.2 parts by weight of initiator to the reactor of step (1) and continue the reaction for 2 hours, with the temperature controlled at 140°C.

[0097] (4) Cool down to 80°C, add 40 parts by weight of alcohol ether solvent, stir and mix evenly, stir at 400 r / min for 30 min.

[0098] (5) Add 10% pH adjuster to adjust the pH value to 8.0, stir at 400 r / min for 20 min to obtain organosilicon modified water-soluble acrylic resin.

[0099] Comparative Example 2

[0100] This comparative example prepared an ink oil for photovoltaic glass glaze, and the specific process is as follows:

[0101] Under low-speed stirring (400 rpm), 2 g of thickening and anti-settling agent ethyl cellulose was slowly added to 88 g of alcohol ether solvent. If necessary, the mixture was heated appropriately to 50℃ (40-60℃ is acceptable). The mixture was dispersed and stirred for 45 min (30-60 min is acceptable). After complete dissolution, 10 g of the organosilicon-modified water-soluble acrylic resin prepared in Comparative Example 1 was added to the mixture. After thorough stirring to form a uniform and transparent liquid, the ink for photovoltaic glass glaze was obtained.

[0102] Comparative Example 3

[0103] This comparative example prepared a water-soluble acrylic resin, and the specific process is as follows:

[0104] (1) Weigh 30g of methyl methacrylate, 15g of styrene, 5g of hydroxyethyl acrylate, 5g of acrylic acid, 3g of polyether methacrylate and 2g of methoxy polyethylene glycol (550) acrylate and mix them evenly to obtain mixed monomer A.

[0105] (2) Weigh 0.6g of azobisisobutyronitrile and dissolve it in 5g of propylene glycol methyl ether to obtain initiator solution B;

[0106] (3) Add 15g of propylene glycol methyl ether and 20g of diethylene glycol butyl ether to a four-necked flask, start stirring (250rpm) and heat to 90℃. Add 1 / 3 of the mixed monomer A and 1 / 4 of the initiator solution B to the four-necked flask. After reacting for 15min, add the remaining mixture of mixed monomer A and 1 / 2 of the initiator solution B dropwise to the four-necked flask over 3-4h. After the dropwise addition is complete, keep the reaction at the temperature for 5h. Then add the remaining 1 / 4 of the initiator solution B and continue to keep the reaction at the temperature for 2h. After cooling to 45℃ (40-50℃ is acceptable), add the pH adjuster N,N-dimethylethanolamine to adjust the pH of the system to 8.5 (8-9 is acceptable). Stir the reaction for 0.5h to obtain water-soluble acrylic resin.

[0107] Comparative Example 4

[0108] This comparative example prepared an ink oil for photovoltaic glass glaze, and the specific process is as follows:

[0109] Under low-speed stirring (400 rpm), 2 g of thickening and anti-settling agent ethyl cellulose was slowly added to 88 g of alcohol ether solvent. If necessary, the mixture was heated appropriately to 50°C (40-60°C is acceptable). The mixture was dispersed and stirred for 45 min (30-60 min is acceptable). After complete dissolution, 10 g of the water-soluble acrylic resin prepared in Comparative Example 3 was added to the mixture. After thorough stirring to form a uniform and transparent liquid, the ink for photovoltaic glass glaze was obtained.

[0110] Comparative Example 5

[0111] This comparative example prepared a water-soluble acrylic resin, and the specific process is as follows:

[0112] (1) Weigh 30g of methyl methacrylate, 15g of butyl acrylate, 5g of hydroxyethyl acrylate, 5g of acrylic acid, and 2g of methoxy polyethylene glycol (550) acrylate and mix them evenly to obtain mixed monomer A.

[0113] (2) Weigh 0.6g of azobisisobutyronitrile and dissolve it in 5g of propylene glycol methyl ether to obtain initiator solution B;

[0114] (3) Add 15g of propylene glycol methyl ether and 20g of diethylene glycol butyl ether to a four-necked flask, start stirring (250rpm) and heat to 90℃. Add 1 / 3 of the mixed monomer A and 1 / 4 of the initiator solution B to the four-necked flask. After reacting for 15min, add the remaining mixture of mixed monomer A and 1 / 2 of the initiator solution B dropwise to the four-necked flask over 3-4h. After the dropwise addition is complete, keep the reaction at the temperature for 5h. Then add the remaining 1 / 4 of the initiator solution B and continue to keep the reaction at the temperature for 2h. After cooling to 45℃ (40-50℃ is acceptable), add the pH adjuster N,N-dimethylethanolamine to adjust the pH of the system to 8.5 (8-9 is acceptable). Stir the reaction for 0.5h to obtain water-soluble acrylic resin.

[0115] Comparative Example 6

[0116] This comparative example prepared an ink oil for photovoltaic glass glaze, and the specific process is as follows:

[0117] Under low-speed stirring (400 rpm), 2 g of thickening and anti-settling agent ethyl cellulose was slowly added to 88 g of alcohol ether solvent. If necessary, the mixture was heated appropriately to 50℃ (40-60℃ is acceptable). The mixture was dispersed and stirred for 45 min (30-60 min is acceptable). After complete dissolution, 10 g of water-soluble acrylic resin prepared in Comparative Example 5 was added to the mixture. After thorough stirring to form a uniform and transparent liquid, the ink for photovoltaic glass glaze was obtained.

[0118] Comparative Example 7

[0119] This comparative example prepared a water-soluble acrylic resin, and the specific process is as follows:

[0120] (1) Weigh 30g of methyl methacrylate, 15g of butyl acrylate, 5g of hydroxyethyl acrylate, 5g of acrylic acid, and 3g of polyether methacrylate and mix them evenly to obtain mixed monomer A;

[0121] (2) Weigh 0.6g of azobisisobutyronitrile and dissolve it in 5g of propylene glycol methyl ether to obtain initiator solution B;

[0122] (3) Add 15g of propylene glycol methyl ether and 20g of diethylene glycol butyl ether to a four-necked flask, start stirring (250rpm) and heat to 90℃. Add 1 / 3 of the mixed monomer A and 1 / 4 of the initiator solution B to the four-necked flask. After reacting for 15min, add the remaining mixture of mixed monomer A and 1 / 2 of the initiator solution B dropwise to the four-necked flask over 3-4h. After the dropwise addition is complete, keep the reaction at the temperature for 5h. Then add the remaining 1 / 4 of the initiator solution B and continue to keep the reaction at the temperature for 2h. After cooling to 45℃ (40-50℃ is acceptable), add the pH adjuster N,N-dimethylethanolamine to adjust the pH of the system to 8.5 (8-9 is acceptable). Stir the reaction for 0.5h to obtain water-soluble acrylic resin.

[0123] Comparative Example 8

[0124] This comparative example prepared an ink oil for photovoltaic glass glaze, and the specific process is as follows:

[0125] Under low-speed stirring (400 rpm), 2 g of thickening and anti-settling agent ethyl cellulose was slowly added to 88 g of alcohol ether solvent. If necessary, the mixture was heated appropriately to 50°C (40-60°C is acceptable). The mixture was dispersed and stirred for 45 min (30-60 min is acceptable). After complete dissolution, 10 g of the water-soluble acrylic resin prepared in Comparative Example 7 was added to the mixture. After thorough stirring to form a uniform and transparent liquid, the ink for photovoltaic glass glaze was obtained.

[0126] Test case

[0127] This experiment tested the residual carbon content of the photovoltaic glass glazes prepared in Examples 5-8 and Comparative Examples 2 and 4 after high-temperature sintering with ink.

[0128] Test method: (1) Mix the prepared photovoltaic glass glaze with ink oil and glass flux to form a paste. The amount of ink oil added is 30% of the glass flux. Screen print the paste onto the glass. After curing, temper the glass at a tempering temperature of 680~720℃ / 90s (700℃ / 90s in this test example) and observe the appearance of the glaze.

[0129] (2) The transmittance T value of the above-mentioned glazed glass was determined using the AOPTEKGST-3 air-floating tabletop spectral transmittance measurement system of Beijing AOPTEK Technology Co., Ltd., in accordance with the standard ISO9050-2003.

[0130] Test results as follows Figure 1 and 2 As shown in the figure, the photovoltaic glass glaze prepared using the ink and glass flux in Examples 5-8 exhibits high transparency and a light transmittance exceeding 80% after sintering. In contrast, the photovoltaic glass glaze prepared using the ink and glass flux in Comparative Examples 2 and 4 exhibits a brownish-yellow to blackish glaze with a light transmittance of less than 50% after sintering. This indicates that the ink used in the photovoltaic glass glaze prepared in the examples has a low carbonization temperature, resulting in less residue after high-temperature sintering and minimal impact on color. Conversely, the ink used in the photovoltaic glass glaze prepared in Comparative Examples 2 and 4 has a high carbonization temperature, resulting in more residue after high-temperature sintering and a greater impact on color.

[0131] The photovoltaic glass glazes prepared in Comparative Examples 6 and 8, after sintering with ink and glass flux, showed high transparency and did not turn yellow or black. However, when the powder was dispersed using the ink, the powder was not well wetted and dispersed, easily clumped together, and difficult to disperse. The prepared glazes had poor fluidity, and the printing process was prone to ink drying and clogging of the screen.

[0132] The embodiments of the present invention have been described in detail above with reference to the accompanying drawings. However, the present invention is not limited to the above embodiments, and various changes can be made within the scope of knowledge possessed by those skilled in the art without departing from the spirit of the present invention. Furthermore, the embodiments of the present invention and the features thereof can be combined with each other unless otherwise specified.

Claims

1. A type of ink for photovoltaic glass glaze, characterized in that, The ink for photovoltaic glass glaze comprises water-soluble acrylic resin, alcohol ether solvent, thickener and anti-settling agent, and additives; the water-soluble acrylic resin is prepared by the following method: (1) Mix 20-30 parts of methyl methacrylate, 10-20 parts of butyl acrylate, 5-10 parts of hydroxyethyl acrylate, 2-5 parts of acrylic acid, 1-5 parts of copolymer functional monomer, and 2-5 parts of methoxy polyethylene glycol acrylate to obtain a mixed solution. (2) The mixed solution obtained in step (1) and 0.002-0.1 parts of initiator are added in batches to 40-60 parts of alcohol ether solvent for reaction. The pH is then adjusted to 8-9 to obtain water-soluble acrylate. The copolymer functional monomers include phosphate ester functional monomers; The phosphate ester functional monomers include at least one of methacryloyloxyethyl phosphate, ethylene glycol methacrylate phosphate, alkyl acrylate phosphate, allyl polyether phosphate, and methacrylate polyether phosphate.

2. The ink for photovoltaic glass enamel according to claim 1, characterized in that, The methoxy polyethylene glycol acrylate includes at least one of methoxy polyethylene glycol (350) acrylate, methoxy polyethylene glycol (400) acrylate, methoxy polyethylene glycol (550) acrylate, and methoxy polyethylene glycol (1000) acrylate; and / or the alcohol ether solvent is at least one of propylene glycol methyl ether, propylene glycol butyl ether, diethylene glycol butyl ether, dipropylene glycol methyl ether, tripropylene glycol methyl ether, dipropylene glycol butyl ether, and tripropylene glycol butyl ether; and / or the initiator is at least one of azobisisobutyronitrile, azobisisobutyramidine hydrochloride, benzoyl peroxide, and tert-butyl peroxide.

3. The ink for photovoltaic glass enamel according to claim 1, characterized in that, The water-soluble acrylic resin has a solid content of 40-60%; and / or the water-soluble acrylic resin has a weight-average molecular weight of 5000-100000MW.

4. The ink for photovoltaic glass enamel according to claim 1, characterized in that, The thickening and anti-settling agent is one or more of polyamide wax, cellulose, and modified polyurea solution.

5. The ink for photovoltaic glass enamel according to claim 1, characterized in that, The additive is one or more of wetting and dispersing agents, defoamers, and leveling agents.

6. The ink for photovoltaic glass enamel according to claim 5, characterized in that, The wetting and dispersing agent is one or more of BYK-180, BYK-182, TEGO750W, TEGO755W, and TEGO760W.

7. The ink for photovoltaic glass enamel according to claim 5, characterized in that, The defoamer includes non-silicone defoamers.

8. The ink for photovoltaic glass enamel according to claim 5, characterized in that, The leveling agent includes non-silicone leveling agents.

9. A method for preparing an ink for photovoltaic glass glaze as described in any one of claims 1-8, characterized in that, The method includes the following steps: adding a thickening and anti-settling agent to an alcohol ether solvent, dissolving it, and then adding a water-soluble acrylic resin to obtain a mixed solution; adding an additive to the mixed solution, and mixing to obtain an ink for photovoltaic glass glaze.

10. The application of the photovoltaic glass enamel ink according to any one of claims 1-8 in the preparation of high reflectivity ink for photovoltaic glass.

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