A water-based ink oil and its preparation method and application

Abstract

The application discloses a kind of water-based ink oil and its preparation method and application, preparation raw material includes according to weight parts: phosphate modified acrylate resin 1~10 parts, thickening agent 0.5~5 parts, dispersing agent 1~2 parts and solvent 80~95 parts;The preparation raw material of phosphate modified acrylate resin includes: phosphate functional monomer, methoxyl polyethylene glycol acrylate, acrylic acid and acrylate;Phosphate functional monomer includes at least one of methyl methacrylate acyloxy ethyl phosphate, ethylene glycol methacrylate phosphate, alkyl acrylate phosphate, allyl polyether phosphate and methyl methacrylate polyether phosphate;The weight average molecular weight of phosphate modified acrylate resin is 5000~100000MW.The environmentally friendly water-based ink oil prepared by the phosphate modified acrylate resin of the application is only low in odor, green and environmentally friendly, has less ash and carbon residue after high-temperature sintering, and has little effect on glaze color.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of ink, and particularly relates to a water-based ink oil and a preparation method and application thereof. BACKGROUND

[0002] At present, the high-reflective ink for photovoltaic glass is generally prepared by mixing low-melting point glass powder, titanium white powder and ink oil, wherein the content of the powder is as high as 70% or more. The ink oil, also called doctor blade oil (connecting material), is an important component of printing ink. The rheological property, viscosity, drying property, film-forming property and printing property of the ink are dependent on the ink oil, and the ink oil is the key to the quality of the ink. The main components of the ink oil are various organic resins, high-boiling organic solvents and additives. In the glass screen printing ink formula, the role of the ink oil is mainly to mix the powdery low-melting point glass powder and titanium white powder into paste for screen printing, and the ink oil can also temporarily adhere the glass powder and titanium white powder to the surface of the smooth glass product by virtue of its viscosity, and the ink oil itself must be completely volatilized and burned during the high-temperature baking process. The sintering process of the high-reflective ink for photovoltaic glass is generally sintering at 680-750 DEG C for 2-6 min, and the softening point of the low-melting point glass powder used for the high-reflective ink for photovoltaic glass is generally between 450-600 DEG C. When the glass is tempered, the resin rapidly decomposes at high temperature, and the low-melting point glass powder melts and softens to replace the resin as the connecting material to form an enamel body, thereby playing a role of "secondary film formation" to make the ink change from organic bonding to inorganic bonding, and firmly bond with the glass. In order to obtain good sintering performance (high reflectivity and ink layer density) and acid resistance, the resin and the low-melting point glass powder need to have good matching, that is, to ensure that the resin is completely decomposed when the low-melting point glass powder begins to melt and flow. Therefore, the final decomposition temperature of the resin and the softening point of the low-melting point glass powder need to be close to each other; at the same time, the softening point and the 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 to form a dense surface layer during sintering, and the surface layer is crystallized to achieve good reflectivity and weather resistance. This requires that the decomposition temperature of the ink oil resin and the melting temperature of the selected low-melting point glass powder and the temperature of the tempering furnace have a matching problem. The resin cannot decompose too early, because if the resin decomposes too early, the ink layer is easy to powder and fall off because the glass powder has not been melted. The resin also cannot decompose too late, because if the resin decomposes too late, the organic matter cannot be completely decomposed because it is covered by the glass liquid formed by the melting of the glass powder, which will cause the color glaze to be carbonized and blackened. Moreover, for the ink with high powder content, the resin of the ink oil also needs to have excellent wetting and dispersing ability for the powder, and can quickly wet and penetrate the surface of the powder and quickly open the powder to improve the efficiency of the dispersion and grinding of the powder, so that the particle size of the dispersed powder is small, and the powder is prevented from agglomerating, otherwise the inorganic powder is easy to settle and stratify, thereby affecting the storage stability and printing adaptability of the ink.

[0003] In the prior art, the introduction of silicone can reduce the surface energy and increase the wettability of the resin to glass powder and titanium white powder, but the introduction of silicone and styrene can also cause the decomposition temperature of the resin to rise, which can easily cause the carbon residue of the white high-reflective glaze layer to be too high after sintering, and the color of the glaze layer to be too black; meanwhile, a large amount of production data shows that the introduction of silicone can easily cause "white fog" in the tempering furnace, that is, gaseous silicon dioxide formed by the gasification of silicone adheres to the upper cavity and conveying roller of the tempering furnace, which needs to be cleaned frequently, affecting the production efficiency.

[0004] In summary, it is a difficult problem for researchers in the field to develop a water-based ink oil with little carbon residue after high-temperature sintering. SUMMARY

[0005] The present application aims to at least solve one of the technical problems existing in the prior art. To this end, the present application proposes a water-based ink oil and its preparation method and application. The water-based ink oil of the present application is prepared from a phosphate-modified acrylate resin, so the water-based ink oil not only has low odor, is environmentally friendly, has good screen printing properties, does not block the screen plate, has no serrated ink overflow and other screen printing problems, has little ash after high-temperature sintering, has little carbon residue, and has little effect on the color of the glaze layer.

[0006] The second aspect of the present application proposes a preparation method of a water-based ink oil.

[0007] The third aspect of the present application also proposes a reflective glaze, and the preparation raw materials of the reflective glaze include the above-mentioned water-based ink oil.

[0008] The fourth aspect of the present application also proposes an application of the reflective glaze in photovoltaic glass.

[0009] According to the first aspect of the present application, a water-based ink oil is proposed, and the preparation raw materials include, by weight: 1-10 parts of phosphate-modified acrylate resin, 0.5-5 parts of thickening agent, 1-2 parts of dispersing agent, and 80-95 parts of solvent.

[0010] The preparation raw materials of the phosphate-modified acrylate resin include phosphate functional monomer, methoxy polyethylene glycol acrylate, acrylic acid, and acrylate;

[0011] The phosphate functional monomer includes at least one of methyl methacryloyloxyethyl phosphate, ethylene glycol methacrylate phosphate, alkyl acrylate phosphate, allyl polyether phosphate, and methacrylic acid polyether phosphate;

[0012] The weight average molecular weight of the phosphate-modified acrylate resin is 5000-100000 MW

[0013] According to the first aspect of the present application, at least the following beneficial effects are achieved:

[0014] The phosphate-modified acrylate resin of the present application is prepared by introducing phosphate functional monomers and methoxy polyethylene glycol acrylate into conventional acrylic acid / acrylate monomers to obtain a water-soluble acrylate resin with a weight average molecular weight of 5000-100000 MW. If the molecular weight is too low, the continuous film-forming property is poor. If the molecular weight is too high, the wetting and dispersing effect on powder is poor, and the decomposition temperature is too high. The environmentally friendly water-based ink oil has low odor, is green and environmentally friendly, and has good wetting and dispersing ability for powder materials such as glass powder and titanium dioxide. The photovoltaic glass ink prepared by using the ink oil has good storage stability, good screen printing property, no screen plate blocking, no screen printing problems such as sawtooth overflow, and less ash and carbon residue after high-temperature sintering, which has little effect on the color of the glaze layer. At the same time, the process adaptability of the photovoltaic glass ink prepared by using the ink oil is good, the requirements for the temperature and humidity environment of the screen printing room are low, and the screen plate can be cleaned with water, which reduces the comprehensive cost of preparing the glaze layer of the photovoltaic backplane glass.

[0015] In some embodiments of the present application, the thickening agent includes at least one of hydroxypropyl methyl cellulose, cellulose acetate butyrate, and carboxymethyl cellulose acetate butyrate.

[0016] In some embodiments of the present application, the dispersant includes at least one of BYK-180, BYK-182, TEGO 750W, TEGO 755W, and TEGO 760W.

[0017] In some embodiments of the present application, the solvent of the water-based ink oil includes at least one of diethylene glycol butyl ether, dipropylene glycol methyl ether, tripropylene glycol methyl ether, dipropylene glycol butyl ether, tripropylene glycol butyl ether, diethylene glycol tert-butyl ether, RY305, RY306, RY307, RY308, and RY505.

[0018] The above solvent is a low-carbon environmentally friendly high-boiling point solvent without a benzene ring and not having a benzene ring itself. It has a covalent ether bond with lipophilicity and an alcohol hydroxyl group with hydrophilicity in chemical structure, so that the solvent has the characteristics of low surface tension, high boiling point, slow evaporation, low toxicity, low odor, good solubility for resin, and good hydrophilicity, can improve ink leveling, eliminate pinholes, small particles, and bubbles in the paint film, and can also adjust the drying speed of the ink, which is beneficial to the adaptability of screen printing, is not easy to block the screen plate, and the screen plate can be cleaned with water.

[0019] In some embodiments of the present application, the raw materials for preparing the water-based ink oil further include a defoaming agent and a leveling agent.

[0020] In some embodiments of the present application, the defoaming agent includes a non-silicon defoaming agent.

[0021] In some embodiments of the present application, the non-silicon defoaming agent includes at least one of BYK 1790, BYK-A501, TEGO Foamex 830, TEGO 936 and TEGO 920.

[0022] In some embodiments of the present application, the leveling agent includes a water-oil universal non-silicon leveling agent.

[0023] In some embodiments of the present application, the water-oil universal non-silicon leveling agent includes at least one of BYK 358N, BYK 380N and BYK 381.

[0024] In some embodiments of the present application, the raw materials for preparing the phosphate-modified acrylate resin include 1-5 parts of phosphate functional monomer, 2-5 parts of methoxy polyethylene glycol acrylate, 2-5 parts of acrylic acid and 35-60 parts of acrylate by weight.

[0025] In some embodiments of the present application, 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.

[0026] The methoxy polyethylene glycol acrylate can increase the solubility of the resin in the dispersion medium due to a large number of ether bonds in the molecular chain, and can stabilize the powder particles through the steric hindrance effect due to the long polyether segment.

[0027] In some embodiments of the present application, the acrylate includes at least one of methyl methacrylate, butyl acrylate and hydroxyethyl acrylate.

[0028] In some embodiments of the present application, the raw materials for preparing the phosphate-modified acrylate resin further include an alcohol-ether solvent.

[0029] In some embodiments of the present application, the alcohol-ether solvent includes at least one of 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.

[0030] In some embodiments of the present application, the raw materials for preparing the phosphate-modified acrylate resin further include an initiator and a pH adjuster.

[0031] In some embodiments of the present application, the initiator includes at least one of azobisdimethylcyanamide, azobisdimethylamidinium hydrochloride, benzoyl peroxide and tert-butyl peroxybenzoate.

[0032] In some embodiments of the present application, the pH regulator comprises at least one of ammonia, N, N dimethyl ethanolamine and 2-amino-2-methyl-1-propanol.

[0033] In some embodiments of the present application, the raw materials for preparing the phosphate-modified acrylate resin comprise 1-5 parts of phosphate functional monomer, 2-5 parts of methoxy polyethylene glycol acrylate, 2-5 parts of acrylic acid, 20-30 parts of methyl methacrylate, 10-20 parts of butyl acrylate, 5-10 parts of hydroxyethyl acrylate and 40-60 parts of alcohol ether solvent, 0.1-5 parts of pH regulator, by weight.

[0034] In some embodiments of the present application, the initiator accounts for 0.2-2% of the total weight of the monomers.

[0035] In some embodiments of the present application, the method for preparing the phosphate-modified acrylate resin comprises mixing the raw materials for preparing the phosphate-modified acrylate resin.

[0036] In some embodiments of the present application, the temperature of the mixing is 70-100°C.

[0037] In some preferred embodiments of the present application, the method for preparing the modified phosphate-modified acrylate resin comprises: alcohol ether solvent is added into a four-necked flask at 70-100°C, about 1 / 3 of the mixed monomers (methyl methacrylate, butyl acrylate, hydroxyethyl acrylate, acrylic acid, copolymerization functional monomer mixture), 1 / 4 of the initiator are taken, after 15 min of reaction, the mixture of the remaining mixed monomers and 1 / 2 of the initiator is added dropwise into the four-necked flask within 3-4 h, after the dropwise addition is completed, the reaction is kept for 3-6 h, then the remaining 1 / 4 of the initiator is added, and the reaction is kept for 1-2 h, after the temperature is lowered to 40-50°C, the pH regulator is added, the pH of the system is adjusted to 8-9, and the reaction is stirred for 0.5 h, to obtain the water-soluble acrylate resin.

[0038] The copolymerization functional monomer mixture is phosphate functional monomer and methoxy polyethylene glycol acrylate.

[0039] According to the second aspect of the present application, a method for preparing water-based ink oil is provided, which comprises mixing the raw materials for preparing the water-based ink oil.

[0040] In some embodiments of the present application, the method for preparing the water-based ink oil comprises mixing the thickening agent and the solvent, adding the phosphate-modified acrylate resin, uniformly mixing, and then adding the dispersant, defoaming agent, leveling agent and neutralizing agent.

[0041] According to the third aspect of the present application, a reflective glaze is provided, and the raw materials for preparing the reflective glaze comprise the water-based ink oil.

[0042] In some embodiments of the present application, the preparation raw materials of the reflective glaze further include sodium aluminum silicate and titanium white powder.

[0043] In some embodiments of the present application, the sodium aluminum silicate includes Sipernat 820A of Degussa.

[0044] The sodium aluminum silicate in the present application has high whiteness, can replace part of the titanium white powder to improve the hiding power and whiteness of the glaze layer, thereby improving the reflectivity of the white glaze layer, and has auxiliary thickening and thixotropy, which can improve the defects such as overflow, sawtooth and paste in the silk printing process of the glaze, and the sodium aluminum silicate has lower cost than the titanium white powder, and the replacement of part of the titanium white powder can realize the effects of improving whiteness, improving reflectivity and reducing cost.

[0045] In some embodiments of the present application, the preparation raw materials of the reflective glaze further include glass flux, high-temperature anti-cracking powder and diluent.

[0046] In some embodiments of the present application, the preparation raw materials of the reflective glaze include 20-30 parts of environmentally friendly water-based ink adjusting oil, 3-18 parts of titanium white powder, 12-41.5 parts of sodium aluminum silicate, 55-70 parts of glass flux and 0-10 parts of high-temperature anti-cracking powder by weight.

[0047] In some embodiments of the present application, the titanium white powder includes rutile titanium white powder.

[0048] The above-mentioned addition amount can ensure the weather resistance of the white high-reflective glaze layer.

[0049] The above-mentioned titanium white powder is rutile titanium white powder prepared by chlorination method and is inorganic coated with silicon oxide and aluminum oxide. The prepared titanium white powder has extremely low impurity content, and the inorganic coating with silicon oxide and aluminum oxide can block the lattice defects caused by titanium dioxide under ultraviolet irradiation, shield the surface light activation points, and improve the PID resistance.

[0050] In some embodiments of the present application, the glass flux includes lead-free cadmium environmentally friendly low-melting point glass powder.

[0051] In some embodiments of the present application, the glass flux includes one of D245, N250 and N255.

[0052] The glass flux in the present application is lead-free cadmium environmentally friendly low-melting point glass powder, the particle size is preferably 5-10 μm, the complete melting temperature is preferably 600-670 ℃, the white high-reflective glaze is completely melted in a short time in the range of 680-720 ℃ tempering temperature, and the melting flow performance is better, so that the titanium white powder has better coating, and the high adhesion and weather resistance of the glaze layer are ensured.

[0053] In some embodiments of the present application, the high-temperature anti-cracking powder comprises inorganic ultra-fine powder.

[0054] In some embodiments of the present application, the inorganic ultra-fine powder comprises GT18 high-temperature anti-cracking powder.

[0055] In some embodiments of the present application, the inorganic ultra-fine powder can cause phase transition of material structure shape at temperatures of 220℃ and 350℃ respectively, and the volume relatively increases, which can improve the shrinkage stress impact of high-temperature liquid phase material caused by solidification due to temperature drop, balance the material process mechanics and prevent shrinkage cracking, thereby improving the impact resistance of white high-reflective glazing glass. For example, GT18 high-temperature anti-cracking powder of Ami Micro-nano Co., Ltd.

[0056] In some embodiments of the present application, the preparation method of the reflective glaze comprises mixing the water-based ink oil, the titanium white powder, the sodium aluminum silicate, the glass flux and the high-temperature anti-cracking powder.

[0057] In some embodiments of the present application, the fineness of the reflective glaze is <10 μm.

[0058] According to a fourth aspect of the present application, the reflective glaze is applied in photovoltaic glass. DETAILED DESCRIPTION

[0059] The concept and technical effects of the present application will be described below in combination with embodiments, so as to fully understand the purpose, features and effects of the present application. Obviously, the described embodiments are only some of the embodiments of the present application, but not all the embodiments. Based on the embodiments of the present application, other embodiments obtained by those skilled in the art without creative labor are within the scope of protection of the present application.

[0060] Embodiment 1

[0061] In this embodiment, a phosphate-modified acrylate resin and an environmentally-friendly water-based ink oil are prepared.

[0062] The preparation steps of the phosphate-modified acrylate resin are as follows:

[0063] S1. 25 g of methyl methacrylate, 10 g of butyl acrylate, 10 g of hydroxyethyl acrylate, 4 g of acrylic acid, 2 g of allyl polyether phosphate and 4 g of methoxy polyethylene glycol (400) acrylate are weighed and uniformly mixed to obtain a mixed monomer A;

[0064] S2. 0.22 g of azobis isobutyronitrile is dissolved in 5 g of propylene glycol methyl ether to obtain an initiator solution B;

[0065] S3. In a four-necked flask, 15 g of propylene glycol methyl ether and 25 g of diethylene glycol butyl ether were added, and stirring was started to warm up to 90°C. One-third of the mixed monomer A and one-fourth of the initiator solution B were added to the four-necked flask, and after 15 min of reaction, the mixture of the remaining mixed monomer A and one-half of the initiator solution B was added dropwise to the four-necked flask within 3-4 h. After the dropwise addition was completed, the reaction was maintained for 5 h, then the remaining one-fourth of the initiator solution B was added, and the reaction was maintained for another 2 h. After the temperature was lowered to 40-50°C, the pH regulator N, N-dimethyl ethanolamine was added to adjust the pH of the system to 8-9, and the reaction was maintained for 0.5 h under stirring to obtain the water-soluble acrylic resin.

[0066] The preparation steps of the environmentally friendly water-based ink oil are as follows:

[0067] S4. Under low-speed stirring, 2 g of thickening anti-settling agent carboxymethyl cellulose butyric acid CMCAB641-0.2 (Eastman) was slowly added to 89 g of solvent, and the temperature was heated to 40-60°C. After 30-60 min of dispersion stirring, the water-soluble acrylic resin 6 g was added, and after being mixed uniformly, 2 g of dispersant TEGO750W and 1 g of leveling agent BYK380N were added. After the uniform transparent liquid was fully stirred, an appropriate amount of neutralizer AMP95 was added to obtain the environmentally friendly water-based ink oil.

[0068] Preparation of the water-based white high-reflectance glaze:

[0069] S5. The above-mentioned environmentally friendly water-based ink oil 30 g was added to a dispersion cylinder, and a mechanical stirrer was started at a stirring speed of 500-1500 rpm.

[0070] S6. 36 g of titanium white and 4 g of sodium aluminum silicate salt were sequentially added to the dispersion cylinder for high-speed dispersion at 500-1500 rpm for 10-90 min to obtain a uniform and fine white slurry.

[0071] S7. Then, 60 g of glass flux and 5 g of high-temperature anti-cracking powder were sequentially added to the white slurry, and high-speed dispersion was continued at 500-1500 rpm for 10-90 min. Then, the viscosity was adjusted to about 60000-100000 mPa s using a diluent as needed.

[0072] S8. Finally, the above-mentioned white ink was poured into a three-roll mill to grind the ink, and the fineness of the ink was detected to be less than 10 μm to obtain the water-based white high-reflectance glaze.

[0073] Example 2

[0074] In this example, a phosphate-modified acrylate resin and an environmentally friendly water-based ink oil were prepared.

[0075] The preparation steps of the phosphate-modified acrylate resin are as follows:

[0076] S1. Take 20 g of methyl methacrylate, 10 g of butyl acrylate, 8 g of hydroxyethyl acrylate, 4 g of acrylic acid, 4 g of ethylene glycol methacrylate phosphate, and 4 g of methoxy polyethylene glycol (350) acrylate, and mix them uniformly to obtain a mixed monomer A;

[0077] S2. Take 0.5 g of azobis isobutyronitrile and dissolve it in 5 g of propylene glycol methyl ether to obtain an initiator solution B;

[0078] S3. In a four-necked flask, add 20 g of propylene glycol methyl ether and 25 g of diethylene glycol butyl ether, start stirring, and warm up to 90°C. Take 1 / 3 of the mixed monomer A and 1 / 4 of the initiator solution B, and add them to the four-necked flask. After 15 min of reaction, add the mixture of the remaining mixed monomer A and 1 / 2 of the initiator solution B dropwise into the four-necked flask within 3-4 h. After the dropwise addition is completed, keep the reaction for 5 h. Then, add the remaining 1 / 4 of the initiator solution B, and continue to keep the reaction for 2 h. After the temperature is lowered to 40-50°C, add a pH regulator N, N dimethyl ethanolamine to adjust the pH of the system to 8-9. Stir for 0.5 h, and then a water-soluble acrylic resin is obtained.

[0079] The preparation steps of the environmentally friendly water-based ink oil are as follows:

[0080] S4. Under the condition of low-speed stirring, slowly add 1 g of thickening and anti-settling agent carboxymethyl cellulose CMCAB641-0.5 (Eastman) into 90 g of clean and environmentally friendly solvent. If necessary, properly heat, the heating temperature is 40-60°C, and the dispersion stirring is performed for 30-60 min. After all are dissolved, take 8 g of the above water-soluble acrylic resin, add it, mix uniformly, add 0.5 g of dispersant TEGO750W and 0.5 g of leveling agent BYK380N, fully stir, form a uniform and transparent liquid, and then add an appropriate amount of neutralizer AMP95 to obtain the environmentally friendly water-based ink oil.

[0081] Preparation of water-based white high-reflective glaze:

[0082] S5. Add 30 g of the above environmentally friendly water-based ink oil into a dispersion cylinder, and start the mechanical stirrer with a stirring speed of 500-1500 rpm;

[0083] S6. Add 32 g of titanium white and 8 g of sodium aluminum silicate salt into the dispersion cylinder in sequence, and continue to disperse at a high speed of 500-1500 rpm for 10-90 min to obtain a uniform and fine white slurry;

[0084] S7. Add 60 g of glass flux and 8 g of high-temperature anti-cracking powder into the white slurry in sequence, continue to disperse at a high speed of 500-1500 rpm for 10-90 min, and then adjust the viscosity to about 60000-100000 mPa s as needed by using a diluent;

[0085] S8. Finally, pour the white ink into a three-roll mill to grind the ink, and detect the fineness of the ink, so that the fineness is <10 μm, and then the water-based white high-reflective glaze is obtained.

[0086] Example 3

[0087] In this example, a phosphate-modified acrylate resin and an environmentally friendly water-based ink vehicle are prepared.

[0088] The preparation steps of the phosphate-modified acrylate resin are as follows:

[0089] S1. Weigh 30 g of methyl methacrylate, 15 g of butyl acrylate, 5 g of hydroxyethyl acrylate, 5 g of acrylic acid, 3 g of polyether phosphate methacrylate, and 2 g of methoxy polyethylene glycol (550) acrylate, and mix them uniformly to obtain a mixed monomer A;

[0090] S2. Weigh 0.6 g of azobis isobutyronitrile, and dissolve it in 5 g of propylene glycol methyl ether to obtain an initiator solution B;

[0091] S3. In a four-necked flask, add 15 g of propylene glycol methyl ether and 20 g of diethylene glycol butyl ether, and start stirring and heating to 90°C. Add 1 / 3 of the mixed monomer A and 1 / 4 of the initiator solution B into the four-necked flask, and react for 15 min. Then, drop the mixture of the remaining mixed monomer A and 1 / 2 of the initiator solution B into the four-necked flask within 3-4 h. After the dropping is completed, keep the reaction for 5 h. Then, add the remaining 1 / 4 of the initiator solution B, and continue to keep the reaction for 2 h. When the temperature is lowered to 40-50°C, add a pH regulator N, N-dimethyl ethanolamine to adjust the pH of the system to 8-9, and stir for 0.5 h to obtain a water-soluble acrylate resin.

[0092] The preparation steps of the environmentally friendly water-based ink vehicle are as follows:

[0093] S4. Under the condition of low-speed stirring, slowly add 3 g of a thickening and anti-settling agent hydroxypropyl methyl cellulose into 85 g of a clean and environmentally friendly solvent, and appropriately heat if necessary. The heating temperature is 40-60°C, and the dispersion and stirring time is 30-60 min. After the complete dissolution, add 10 g of the water-soluble acrylate resin into the mixture, mix uniformly, and then add 1 g of a dispersant TEGO 750W, 0.1 g of an antifoaming agent TEGO Foamex 830, and 0.9 g of a leveling agent BYK 380N. After the formation of a uniform and transparent liquid, add an appropriate amount of a neutralizing agent AMP 95 to obtain the environmentally friendly water-based ink vehicle.

[0094] Preparation of the water-based white high-reflective glaze:

[0095] S5. Add 30 g of the above-mentioned environmentally friendly water-based ink vehicle into a dispersion cylinder, and start the mechanical stirrer with a stirring speed of 500-1500 rpm;

[0096] S6. 28 g of titanium white powder and 12 g of sodium aluminum silicate salt were sequentially added into a dispersion cylinder and high-speed dispersed at 500-1500 rpm for 10-90 min to obtain a uniform and fine white slurry;

[0097] S7. 60 g of glass flux and 10 g of high-temperature anti-cracking powder were sequentially added into the white slurry, and high-speed dispersed at 500-1500 rpm for 10-90 min, and then the viscosity was adjusted to about 60000-100000 mPas using a diluent as needed;

[0098] S8. Finally, the above white ink was poured into a three-roll mill to grind the ink, and the fineness of the ink was detected to be less than 10 μm, thereby obtaining the water-based white high-reflective glaze.

[0099] Example 4

[0100] In this example, a phosphate-modified acrylate resin and an environmentally friendly water-based ink were prepared.

[0101] The preparation steps of the phosphate-modified acrylate resin are as follows:

[0102] S1. 20 g of methyl methacrylate, 20 g of butyl acrylate, 5 g of hydroxyethyl acrylate, 5 g of acrylic acid, 5 g of methacrylic acid acyloxyethyl phosphate, and 5 g of methoxy polyethylene glycol (1000) acrylate were mixed to obtain a mixed monomer A;

[0103] S2. 0.45 g of azobis isobutyronitrile was dissolved in 5 g of propylene glycol methyl ether to obtain an initiator solution B;

[0104] S3. In a four-necked flask, 15 g of propylene glycol methyl ether and 20 g of diethylene glycol butyl ether were added, and stirring was started to heat to 90°C. One third of the mixed monomer A and one fourth of the initiator solution B were added to the four-necked flask, and reacted for 15 min. Then, the remaining mixed monomer A and one half of the initiator solution B were added dropwise to the four-necked flask within 3-4 h. After the dropwise addition was completed, the reaction was maintained for 5 h. Then, the remaining one fourth of the initiator solution B was added, and the reaction was maintained for 2 h. After the temperature was lowered to 40-50°C, a pH regulator N, N dimethyl ethanolamine was added to adjust the pH of the system to 8-9. The stirring reaction was maintained for 0.5 h, thereby obtaining a water-soluble acrylate resin.

[0105] The preparation steps of the environmentally friendly water-based ink are as follows:

[0106] S4. Under low-speed stirring, 2 g of a thickening and anti-settling agent cellulose acetate butyrate CAB553-0.4 was slowly added into 88 g of a clean and environmentally friendly solvent. If necessary, appropriate heating was performed at a temperature of 40-60°C, and the dispersion was stirred for 30-60 min until all were dissolved. Then, 10 g of the above water-soluble acrylate resin was added, and a uniform and transparent liquid was formed after sufficient stirring. Thus, an environmentally friendly water-based ink was obtained.

[0107] Preparation of water-based white high-reflective glaze:

[0108] S5. Add 30 g of the above environmentally friendly water-based ink oil to the dispersion cylinder, turn on the mechanical stirrer, and stir at a speed of 500-1500 rpm;

[0109] S6. Add 24 g of titanium dioxide and 16 g of sodium aluminum silicate salt to the dispersion cylinder in turn, and continue to disperse at a high speed of 500-1500 rpm for 10-90 min to obtain a uniform and fine white slurry;

[0110] S7. Add 60 g of glass flux and 2 g of high-temperature anti-cracking powder to the white slurry in turn, continue to disperse at a high speed of 500-1500 rpm for 10-90 min, and then adjust the viscosity to about 60,000-100,000 mPa s as needed using a diluent;

[0111] S8. Finally, pour the above white ink into a three-roll mill to grind the ink, detect the fineness of the ink, and make the fineness <10 μm, to obtain a water-based white high-reflective glaze.

[0112] Comparative Example 1

[0113] This comparative example prepared an organosilicon-modified water-soluble acrylic resin and an environmentally friendly water-based ink oil, and the specific steps were as follows:

[0114] S1. Keep the reaction kettle clean and dry, add 40 parts of alcohol ether solvent by weight, introduce nitrogen into the reaction kettle and keep it, introduce cooling water into the condenser, and heat the alcohol ether solvent to 140℃;

[0115] S2. Take another dispersion kettle, add 10 parts of glycidyl ester, 5 parts of hydroxyethyl acrylate, 3 parts of methyl methacrylate, 5 parts of acrylic acid, 10 parts of isobornyl methacrylate, 25 parts of butyl acrylate, 15 parts of styrene, 5 parts of organosilicon monomer, 2 parts of molecular weight regulator (chain transfer agent), and 3.5 parts of initiator in turn by weight, stir and mix uniformly, the stirring speed is 300 r / min, and the stirring time is 40 min; add the above mixed solution to the reaction kettle of step (1) dropwise, the dropping time is 6 h, and the temperature is controlled at 140℃; after the dropping is completed, keep the temperature at 140℃ for 2 h;

[0116] S3. Add 0.2 parts of initiator to the reaction kettle of step (1) by weight, continue to react for 2 h, and control the temperature at 140℃;

[0117] S4. Cool down to 80℃, add 40 parts of alcohol ether solvent by weight, stir and mix uniformly, the stirring speed is 400 r / min, and the stirring time is 30 min;

[0118] S5. Drop 10% mass concentration of pH regulator, adjust pH value to 8.0, stirring speed is 400 r / min, stirring time is 20 min, to obtain silicone modified water-soluble acrylic resin.

[0119] The preparation steps of the environment-friendly water-based ink oil are as follows:

[0120] S6. Under the condition of low-speed stirring, 1 g of thickening anti-settling agent hydroxypropyl methyl cellulose is slowly added into 85 g of clean environment-friendly solvent, and appropriate heating is performed if necessary, heating temperature is 40-60℃, dispersion stirring is performed for 30-60 min, after complete dissolution, 10 g of the above-mentioned silicone modified water-soluble acrylic resin is added, after uniform mixing, 2 g of dispersant TEGO 750W, 0.1 g of defoaming agent TEGO Foamex 830, 1.9 g of leveling agent BYK 380N are added, after sufficient stirring, a uniform transparent liquid is formed, and then a proper amount of neutralizer AMP 95 is added, to obtain the environment-friendly water-based ink oil.

[0121] Preparation of water-based white high-reflective glaze:

[0122] S7. 30 g of the above-mentioned environment-friendly water-based ink oil is added into a dispersion cylinder, and a mechanical stirrer is started, stirring speed is 500-1500 rpm;

[0123] S8. 28 g of titanium white and 12 g of sodium aluminum silicate salt are sequentially added into the dispersion cylinder, and high-speed dispersion is continuously performed at 500-1500 rpm for 10-90 min, to obtain a uniform and fine white slurry;

[0124] S9. 60 g of glass flux and 10 g of high-temperature anti-cracking powder are sequentially added into the white slurry, and high-speed dispersion is continuously performed at 500-1500 rpm for 10-90 min, and then a diluent is used to adjust the viscosity to about 60000-100000 mPas;

[0125] S10. Finally, the above-mentioned white ink is poured into a three-roll mill to grind the ink, and the fineness of the ink is detected, so that the fineness is less than 10 μm, to obtain the water-based white high-reflective glaze.

[0126] Comparative Example 2

[0127] In the present comparative example, a silicone modified water-soluble acrylic resin and an environment-friendly water-based ink oil are prepared, and the specific steps are as follows:

[0128] S1. 30 g of methyl methacrylate, 15 g of styrene, 5 g of hydroxyethyl acrylate, 5 g of acrylic acid, 3 g of methacrylic acid polyether phosphate, and 2 g of methoxy polyethylene glycol (550) acrylate are uniformly mixed to obtain a mixed monomer A;

[0129] S2. 0.6 g of azobis isobutyronitrile is dissolved in 5 g of propylene glycol methyl ether to obtain an initiator solution B;

[0130] S3. In a four-necked flask, 15 g of propylene glycol methyl ether and 20 g of diethylene glycol butyl ether were added, and stirring was started to warm to 90°C. One-third of the mixed monomer A and one-fourth of the initiator solution B were added to the four-necked flask, and after 15 min, the mixture of the remaining mixed monomer A and one-half of the initiator solution B was added dropwise to the four-necked flask within 3-4 h. After the dropwise addition was completed, the reaction was maintained for 5 h, then the remaining one-fourth of the initiator solution B was added, and the reaction was maintained for another 2 h. After the temperature was lowered to 40-50°C, the pH regulator N, N-dimethyl ethanolamine was added to adjust the pH of the system to 8-9, and the reaction was maintained for 0.5 h. Thus, a water-soluble acrylic resin was obtained.

[0131] The preparation steps of the environmentally friendly water-based ink oil are as follows:

[0132] S4. Under low-speed stirring, 1 g of thickening anti-settling agent hydroxypropyl methyl cellulose was slowly added to 85 g of clean environmentally friendly solvent, and if necessary, appropriate heating was added. The heating temperature was 40-60°C, and the dispersion stirring was performed for 30-60 min. After complete dissolution, 10 g of the above-mentioned silicone-modified water-soluble acrylic resin was added, and after uniform mixing, 2 g of dispersant TEGO 750W, 0.1 g of defoaming agent TEGO Foamex 830, and 1.9 g of leveling agent BYK 380N were added. After sufficient stirring to form a uniform transparent liquid, an appropriate amount of neutralizing agent AMP95 was added. Thus, the environmentally friendly water-based ink oil was obtained.

[0133] Preparation of water-based white high-reflective glaze:

[0134] S5. 30 g of the above-mentioned environmentally friendly water-based ink oil was added to a dispersion cylinder, and a mechanical stirrer was started with a stirring speed of 500-1500 rpm.

[0135] S6. 40 g of titanium white powder was sequentially added to the dispersion cylinder and was continuously dispersed at a high speed of 500-1500 rpm for 10-90 min to obtain a uniform and fine white slurry.

[0136] S7. Then, 60 g of glass flux and 2 g of high-temperature anti-cracking powder were sequentially added to the white slurry, and continuous high-speed dispersion was performed at 500-1500 rpm for 10-90 min. Then, the viscosity was adjusted to about 60000-100000 mPas using a diluent as needed.

[0137] S8. Finally, the above-mentioned white ink was poured into a three-roll mill to grind the ink, and the fineness of the ink was detected to be less than 10 μm. Thus, a water-based white high-reflective glaze was obtained.

[0138] Comparative Example 3

[0139] In this comparative example, a silicone-modified water-soluble acrylic resin and an environmentally friendly water-based ink oil were prepared, and the specific steps were as follows:

[0140] S1. Take 30 g of methyl methacrylate, 15 g of butyl acrylate, 5 g of hydroxyethyl acrylate, 5 g of acrylic acid, 2 g of methoxy polyethylene glycol (550) acrylate, and mix them evenly to obtain a mixed monomer A;

[0141] S2. Take 0.6 g of azobis isobutyronitrile and dissolve it in 5 g of propylene glycol methyl ether to obtain an initiator solution B;

[0142] S3. In a four-necked flask, add 15 g of propylene glycol methyl ether and 20 g of diethylene glycol butyl ether, start stirring and heat to 90°C, take 1 / 3 of the mixed monomer A and 1 / 4 of the initiator solution B and add them to the four-necked flask, after 15 min of reaction, add the mixture of the remaining mixed monomer A and 1 / 2 of the initiator solution B dropwise into the four-necked flask within 3-4 h, after the dropwise addition is completed, keep the reaction for 5 h, then add the remaining 1 / 4 of the initiator solution B, continue to keep the reaction for 2 h, after cooling to 40-50°C, add the pH regulator N, N dimethyl ethanolamine to adjust the pH of the system to 8-9, stir for 0.5 h, and then the water-soluble acrylic resin is obtained.

[0143] The preparation steps of the environmentally friendly water-based ink oil are as follows:

[0144] S4. Under low-speed stirring conditions, slowly add 1 g of thickening anti-settling agent hydroxypropyl methyl cellulose to 85 g of clean and environmentally friendly solvent, if necessary, appropriate heating, heating temperature 40-60°C, dispersion stirring for 30-60 min, after complete dissolution, take 10 g of the above-mentioned silicone modified water-soluble acrylic resin and add it, mix evenly, then add 2 g of dispersant TEGO 750W, 0.1 g of defoaming agent TEGO Foamex 830, 1.9 g of leveling agent BYK380N, fully stir, form a uniform transparent liquid, then add an appropriate amount of neutralizing agent AMP95, and the environmentally friendly water-based ink oil is obtained.

[0145] Preparation of water-based white high-reflective glaze:

[0146] S5. Add 30 g of the above-mentioned environmentally friendly water-based ink oil to the dispersion cylinder, start the mechanical stirrer, and the stirring speed is 500-1500 rpm;

[0147] S6. Add 28 g of titanium white and 12 g of sodium aluminum silicate salt to the dispersion cylinder in turn and continue to disperse at a high speed of 500-1500 rpm for 10-90 min to obtain a uniform and delicate white slurry;

[0148] S7. Add 60 g of glass flux to the white slurry, continue to disperse at a high speed of 500-1500 rpm for 10-90 min, then adjust the viscosity to about 60000-100000 mpa s as needed with a diluent;

[0149] S8. Finally, pour the white ink described above into a three-roll mill to grind the ink, detect the fineness of the ink, and make the fineness <10 μm, to obtain the water-based white high-reflectance glaze.

[0150] Comparative Example 4

[0151] This comparative example prepared an organic silicon modified water-soluble acrylic resin and an environmentally friendly water-based ink oil, and the specific steps were as follows:

[0152] S1. Weigh 30 g of methyl methacrylate, 15 g of butyl acrylate, 5 g of hydroxyethyl acrylate, 5 g of acrylic acid, and 3 g of methacrylic acid polyether phosphate, and mix them evenly to obtain a mixed monomer A;

[0153] S2. Weigh 0.6 g of azobis isobutyronitrile and dissolve it in 5 g of propylene glycol methyl ether to obtain an initiator solution B;

[0154] S3. In a four-necked flask, add 15 g of propylene glycol methyl ether and 20 g of diethylene glycol butyl ether, start stirring, and heat to 90°C. Take 1 / 3 of the mixed monomer A and 1 / 4 of the initiator solution B, and add them to the four-necked flask. After 15 min of reaction, add the remaining mixed monomer A and 1 / 2 of the initiator solution B dropwise to the four-necked flask within 3-4 h. After the dropwise addition is completed, keep the reaction for 5 h, then add the remaining 1 / 4 of the initiator solution B, and continue to keep the reaction for 2 h. When the temperature is lowered to 40-50°C, add the pH regulator N, N-dimethyl ethanolamine to adjust the pH of the system to 8-9, and stir for 0.5 h. Thus, a water-soluble acrylic resin is obtained.

[0155] The preparation steps of the environmentally friendly water-based ink oil are as follows:

[0156] S4. Under low-speed stirring conditions, slowly add 1 g of thickening and anti-settling agent hydroxypropyl methyl cellulose to 85 g of odorless environmentally friendly solvent. If necessary, appropriately heat to a temperature of 40-60°C, and disperse and stir for 30-60 min. After complete dissolution, add 10 g of the above-mentioned organic silicon modified water-soluble acrylic resin, mix evenly, then add 2 g of dispersant TEGO 750W, 0.1 g of defoaming agent TEGO Foamex 830, and 1.9 g of leveling agent BYK 380N. After sufficient stirring to form a uniform transparent liquid, add an appropriate amount of neutralizing agent AMP 95, and thus an environmentally friendly water-based ink oil is obtained.

[0157] Preparation of the water-based white high-reflectance glaze:

[0158] S5. Add 30 g of the above-mentioned environmentally friendly water-based ink oil to a dispersion cylinder, and start the mechanical stirrer at a speed of 500-1500 rpm;

[0159] S6. Add 40 g of titanium white powder to the dispersion cylinder, and continue to disperse at a high speed of 500-1500 rpm for 10-90 min to obtain a uniform and fine white slurry.

[0160] S7. Again 60g glass flux is added into the white slurry, continue to high speed dispersion at 500-1500rpm for 10-90min, then adjust the viscosity with diluent to about 60000-100000mpas as needed;

[0161] S8. Finally, pour the above white ink into three-roll mill to grind the ink, detect the fineness of the ink, and make the fineness <10μm, to obtain the water-based white high reflective glaze.

[0162] The above has made the detailed description to the embodiment of the present application, but the present application is not limited to the above-mentioned embodiment, within the knowledge range possessed by the ordinary skilled in the art, various changes can be made without departing from the gist of the present application. In addition, the embodiments of the present application and the features in the embodiments can be combined with each other without conflict.

Claims

1. A reflective glaze characterized in that, The preparation raw materials of the reflective glaze include a water-based ink vehicle; The preparation raw materials of the water-based ink vehicle are, by weight parts, 1-10 parts of a phosphate-modified acrylate resin, 0.5-5 parts of a thickening agent, 1-2 parts of a dispersing agent, and 80-95 parts of a solvent. The preparation raw materials of the phosphate-modified acrylate resin are a phosphate functional monomer, methoxyl polyethylene glycol acrylate, acrylic acid, and acrylate. The phosphate functional monomer is at least one of methyl methacryloyloxyethyl phosphate, ethylene glycol methacrylate phosphate, alkyl acrylate phosphate, allyl polyether phosphate, and methacrylic acid polyether phosphate. The weight average molecular weight of the phosphate-modified acrylate resin is 5000-100000 MW. The preparation raw materials of the reflective glaze further include sodium aluminum silicate and titanium white.

2. The reflective glaze of claim 1, wherein, The preparation raw materials of the phosphate-modified acrylate resin include, by weight parts, 1-5 parts of the phosphate functional monomer, 2-5 parts of the methoxyl polyethylene glycol acrylate, 2-5 parts of the acrylic acid, and 35-60 parts of the acrylate.

3. The reflective glaze of claim 1, wherein, The preparation raw materials of the phosphate-modified acrylate resin further include an alcohol ether solvent; the alcohol ether solvent includes at least one of diethylene glycol butyl ether, dipropylene glycol methyl ether, tripropylene glycol methyl ether, dipropylene glycol butyl ether, tripropylene glycol butyl ether, and diethylene glycol tertiary butyl ether.

4. The reflective glaze of claim 1, wherein, The preparation raw materials of the phosphate-modified acrylate resin further include an initiator and a pH adjuster.

5. The reflective glaze of claim 1, wherein, The preparation raw materials of the water-based ink vehicle further include a defoaming agent and a leveling agent.

6. A reflective glaze according to claim 1 wherein, The preparation method of the water-based ink vehicle includes mixing the preparation raw materials of the water-based ink vehicle.

7. The reflective glaze of claim 6, wherein, The temperature of the mixing is 40-60°C.

8. Use of the reflective glaze according to any one of claims 1-7 in photovoltaic glass.