CN117210058A - Water-based ink-regulating oil and preparation method and application thereof - Google Patents

Water-based ink-regulating oil and preparation method and application thereof Download PDF

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Publication number
CN117210058A
CN117210058A CN202311064755.3A CN202311064755A CN117210058A CN 117210058 A CN117210058 A CN 117210058A CN 202311064755 A CN202311064755 A CN 202311064755A CN 117210058 A CN117210058 A CN 117210058A
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phosphate
parts
acrylate
water
resin
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Chinese (zh)
Inventor
周志文
王科
蔡敬
向黎明
陈志鸿
何进
唐高山
黎达成
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CSG Holding Co Ltd
Dongguan CSG Solar Glass Co Ltd
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CSG Holding Co Ltd
Dongguan CSG Solar Glass Co Ltd
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Abstract

The invention discloses water-based ink-regulating oil and a preparation method and application thereof, wherein the preparation raw materials comprise the following components in parts by weight: 1 to 10 parts of phosphate modified acrylic resin, 0.5 to 5 parts of thickener, 1 to 2 parts of dispersant and 80 to 95 parts of solvent; the preparation raw materials of the phosphate modified acrylic resin comprise: phosphate functional monomers, methoxypolyethylene glycol acrylate, acrylic acid and acrylate; the phosphate functional monomer comprises at least one of methacrylic acid acyloxyethyl 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 acrylic resin is 5000-100000 MW. The environment-friendly water-based ink varnish prepared from the phosphate modified acrylate resin has low smell, is environment-friendly, has little ash content after high-temperature sintering, has little carbon residue, and has little influence on the color of a glaze layer.

Description

Water-based ink-regulating oil and preparation method and application thereof
Technical Field
The invention belongs to the technical field of ink, and particularly relates to water-based ink-regulating oil, and a preparation method and application thereof.
Background
The existing photovoltaic glass high-reflection ink is generally prepared from low-melting-point glass powder, titanium dioxide, ink-regulating oil and the like, wherein the content of the powder is up to more than 70%. The ink-regulating oil, also called as scraping plate oil (binder), is an important component of printing ink, and the rheological property, viscosity, drying property, film forming property, printing property and the like of the ink depend on the ink-regulating oil, and is the key of the quality of the ink. The main components of the glass screen printing ink are various organic resins, high boiling point organic solvents and auxiliary agents, and the glass screen printing ink mainly has the functions of mixing powdery low-melting glass powder, titanium pigment and other pigment fillers into paste so as to facilitate screen printing, and the glass powder and the titanium pigment can be temporarily adhered to the surface of a smooth glass product by means of the viscosity of the glass powder and the titanium pigment, and the glass powder and the titanium pigment must be completely volatilized and burnt in the high-temperature decoration firing (firing) process. The sintering process of the high-reflection printing ink for the photovoltaic glass is generally carried out at 680-750 ℃ for 2-6 min, the softening point of the low-melting glass powder for the high-reflection printing ink for the photovoltaic glass is generally between 450-600 ℃, the resin is rapidly decomposed at high temperature during glass tempering, and meanwhile, the low-melting glass powder is melted and softened to replace the resin as a binder to form an enamel body, so that the printing ink is converted from organic bonding to inorganic bonding and firmly bonded with the glass. In order to obtain good sintering properties (high reflection and ink layer compactness) and acid resistance, it is desirable that the resin and the low melting glass frit have good matching properties, i.e., to ensure that the low melting glass frit starts to melt flow when the resin decomposition is completed. Therefore, it is required that the final decomposition temperature of the resin and the softening point of the low melting glass frit are not greatly different; meanwhile, the softening point and crystallization temperature of the low-melting-point glass powder are required to be lower than the sintering temperature, so that the ink can be fully melted, flowed and spread into a compact surface layer during sintering, and the surface layer is crystallized to achieve better reflectivity and weather resistance. The problem of matching between the decomposition temperature of the varnish resin and the melting temperature of the selected low-melting-point glass powder and the temperature of a tempering furnace is required, the varnish cannot be decomposed prematurely, the ink layer is easy to pulverize and fall off due to the fact that the glass powder is not melted in the early decomposition process, the varnish cannot be decomposed too late, organic matters cannot be decomposed completely due to the fact that glass liquid melted by the glass powder covers and wraps the varnish in the late decomposition process, and the colored glaze is coked and blackened. In addition, for the ink with high powder content, the ink-preparing oil resin is also required to have excellent wetting and dispersing ability on powder, so that the surface of the powder is rapidly wetted and wrapped and the powder is quickly opened after penetrating into the powder, the powder dispersing and grinding efficiency is improved, the powder dispersing particle size is small, meanwhile, the agglomeration of the powder can be prevented, and the inorganic powder is easy to settle and delaminate, so that the storage stability and printing adaptability of the ink are affected.
In the prior art, the introduction of the organic silicon can reduce the surface energy and increase the wettability of resin to glass powder and titanium pigment, but the introduction of the organic silicon and styrene can also cause the decomposition temperature of the resin to be increased, so that the white high-reflection glaze layer is easy to cause higher carbon residue after sintering, and the color of the glaze layer is blacker; meanwhile, mass production data show that the introduction of the organic silicon easily causes 'white fog' in the toughening furnace, namely, the organic silicon is gasified to form fumed silica which is adhered to the upper cavity of the toughening furnace and the conveying roller, and the furnace needs to be shut down frequently for cleaning, so that the production efficiency is affected.
In summary, developing an aqueous ink-transfer oil with less residual carbon after high-temperature sintering is a difficult problem that researchers in the field need to explore.
Disclosure of Invention
The present invention aims to solve at least one of the technical problems in the prior art described above. Therefore, the invention provides the water-based ink-transfer oil, and the preparation method and application thereof, and the water-based ink-transfer oil is prepared from the phosphate modified acrylic ester resin, so that the water-based ink-transfer oil has low smell, is environment-friendly, has good screen printability, does not block a screen plate, has no screen printing problems such as sawtooth ink overflow and the like, has less ash content after high-temperature sintering, has less carbon residue, and has small influence on the color of a glaze layer.
The second aspect of the invention provides a preparation method of the water-based ink-regulating oil.
The third aspect of the invention also provides a reflective glaze, and the preparation raw materials of the reflective glaze comprise the water-based varnish.
The fourth aspect of the invention also provides an application of the reflective glaze in photovoltaic glass.
According to a first aspect of the invention, an aqueous varnish is provided, which comprises the following raw materials in parts by weight: 1 to 10 parts of phosphate modified acrylic resin, 0.5 to 5 parts of thickener, 1 to 2 parts of dispersant and 80 to 95 parts of solvent;
the preparation raw materials of the phosphate modified acrylic ester resin comprise: phosphate functional monomers, methoxypolyethylene glycol acrylate, acrylic acid and acrylate;
the phosphate functional monomer comprises at least one of methacrylic acid acyloxyethyl 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 acrylic resin is 5000-100000 MW
The first aspect according to the invention has at least the following advantages:
the phosphate modified acrylic resin is prepared by introducing phosphate functional monomers, methoxy polyethylene glycol acrylic ester and conventional acrylic acid/acrylic ester monomers, and has the advantages of low molecular weight, poor continuous film forming property, high molecular weight, poor wetting and dispersing effects on powder and high decomposition temperature, and the weight average molecular weight of the water soluble acrylic resin is 5000-100000 MW. The environment-friendly water-based ink-regulating oil is low in smell, environment-friendly, good in wetting and dispersing capacity for powder materials such as glass powder and titanium dioxide, stable in storage of the prepared photovoltaic glass ink, good in screen printing performance, free of screen blocking, free of screen printing problems such as sawtooth ink overflow and the like, less in ash content after high-temperature sintering, less in carbon residue, and small in influence on the color of a glaze layer. Meanwhile, the photovoltaic glass ink prepared by the environment-friendly water-based ink-regulating oil has good process adaptability, has lower requirements on temperature and humidity environments between silk-screen printing, can be cleaned by water, and reduces the comprehensive cost for preparing the glass glaze layer of the photovoltaic backboard.
In some embodiments of the invention, the thickener comprises at least one of hydroxypropyl methylcellulose, cellulose acetate butyrate and carboxymethyl cellulose acetate butyrate.
In some embodiments of the invention, the dispersant includes at least one of BYK-180, BYK-182, TEGO750W, TEGO755W, and TEGO 760W.
In some embodiments of the invention, the solvent of the aqueous ink-transfer 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 t-butyl ether, RY305, RY306, RY307, RY308, RY505, and the like.
The solvent is a low-carbon environment-friendly high-boiling point solvent which does not contain benzene rings and does not contain benzene rings, and has lipophilic covalent ether bonds and hydrophilic alcoholic hydroxyl groups on chemical structures, so that the solvent has the characteristics of low surface tension, high boiling point, slow volatilization, low toxicity, low odor, good solubility to resin and good hydrophilicity, can improve ink leveling, eliminate pinholes, small particles and bubbles of a paint film, can also adjust ink drying speed, is favorable for screen printing adaptability, is not easy to block a screen printing plate, and can be cleaned by water.
In some embodiments of the invention, the aqueous varnish preparation raw material further comprises an antifoaming agent and a leveling agent.
In some embodiments of the invention, the defoamer comprises a non-silicon based defoamer.
In some embodiments of the invention, the non-silicon based defoamer includes at least one of BYK1790, BYK-A501, TEGO Foamex 830, TEGO 936, and TEGO 920.
In some embodiments of the invention, the leveling agent comprises a water-oil universal non-silicone leveling agent.
In some embodiments of the present invention, the water-oil universal non-silicone leveling agent includes at least one of BYK358N, BYK N and BYK 381.
In some embodiments of the present invention, the preparation raw materials of the phosphate modified acrylate resin include 1 to 5 parts by weight of phosphate functional monomer, 2 to 5 parts by weight of methoxypolyethylene glycol acrylate, 2 to 5 parts by weight of acrylic acid and 35 to 60 parts by weight of acrylate.
In some embodiments of the invention, the methoxypolyethylene glycol acrylate comprises at least one of methoxypolyethylene glycol (350) acrylate, methoxypolyethylene glycol (400) acrylate, methoxypolyethylene glycol (550) acrylate, and methoxypolyethylene glycol (1000) acrylate.
The methoxy polyethylene glycol acrylate has great amount of ether bond in the molecular chain, so that the resin has raised solubility in the dispersing medium, and the polyether segment is relatively long, so as to stabilize the powder particle via steric effect.
In some embodiments of the invention, the acrylate comprises at least one of methyl methacrylate, butyl acrylate, and hydroxyethyl acrylate.
In some embodiments of the invention, the phosphate modified acrylate resin is prepared from a starting material that further includes an alcohol ether solvent.
In some embodiments of the invention, the alcohol ether solvent comprises 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 t-butyl ether.
In some embodiments of the present invention, the preparation raw materials of the phosphate modified acrylate resin further comprise an initiator and a pH regulator.
In some embodiments of the invention, the initiator comprises at least one of azobisisobutyronitrile, azobisisobutylamidine hydrochloride, benzoyl peroxide, and t-butyl peroxybenzoate.
In some embodiments of the invention, the pH adjuster comprises at least one of ammonia, N-dimethylethanolamine, and 2-amino-2-methyl-1-propanol.
In some embodiments of the invention, the preparation raw materials of the phosphate modified acrylate resin comprise, by weight, 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, 40-60 parts of alcohol ether solvent and 0.1-5 parts of pH regulator.
In some embodiments of the invention, the initiator comprises 0.2 to 2% by weight of the total monomer weight.
In some embodiments of the present invention, the method for preparing a phosphate modified acrylate resin includes: and mixing the preparation raw materials of the phosphate modified acrylate resin.
In some embodiments of the invention, the temperature of the mixing is 70-100 ℃.
In some preferred embodiments of the present invention, the method for preparing the modified phosphate modified acrylate resin comprises: taking about 1/3 of mixed monomer (methyl methacrylate, butyl acrylate, hydroxyethyl acrylate, acrylic acid and a copolymerization function monomer mixture) of an alcohol ether solvent at 70-100 ℃, adding 1/4 of initiator into a four-neck flask, reacting for 15min, dropwise adding the mixture of the rest mixed monomer and 1/2 of initiator into the four-neck flask within 3-4 h, preserving heat for reacting for 3-6 h after dropwise adding, adding the rest 1/4 of initiator, continuously preserving heat for reacting for 1-2 h, cooling to 40-50 ℃, adding a pH regulator, regulating the pH of the system to 8-9, and stirring for reacting for 0.5h to obtain the water-soluble acrylic resin.
The mixture of the copolymerization functional monomers is phosphate functional monomers and methoxy polyethylene glycol acrylate.
According to a second aspect of the present invention, a method for preparing an aqueous varnish is provided, comprising mixing the preparation raw materials of the aqueous varnish.
In some embodiments of the present invention, the method of preparing the aqueous varnish includes mixing the thickener and the solvent, adding the phosphate modified acrylate resin, mixing uniformly, and adding the dispersant, the defoamer, the leveling agent and the neutralizer.
The third aspect of the invention provides a reflective glaze, wherein the preparation raw materials of the reflective glaze comprise the aqueous varnish.
In some embodiments of the present invention, the reflective glaze material further comprises sodium aluminum silicate salt and titanium pigment.
In some embodiments of the invention, the sodium aluminum silicate salt comprises Sipernat 820A of desipramine.
The sodium aluminum silicate salt has high whiteness, can replace part of titanium dioxide to improve the covering power and whiteness of a glaze layer, thereby improving the reflectivity of the white glaze layer, has auxiliary thickening and thixotropic effects, can improve the defects of ink overflow, saw teeth, paste plates and the like in the silk screen printing process of the glaze, has lower cost than the titanium dioxide, and has the effects of improving the whiteness, improving the reflectivity and reducing the cost by replacing part of the titanium dioxide.
In some embodiments of the invention, the reflective glaze is prepared from raw materials further comprising a glass flux, high temperature crack resistance powder, and a diluent.
In some embodiments of the invention, the reflective glaze is prepared from the following raw materials, by weight, 20-30 parts of environment-friendly water-based ink-transfer oil, 3-18 parts of titanium dioxide, 12-41.5 parts of aluminum silicate sodium salt, 55-70 parts of glass flux and 0-10 parts of high-temperature anti-cracking powder.
In some embodiments of the invention, the titanium dioxide comprises rutile titanium dioxide.
The weather resistance of the white high-reflection glaze layer can be ensured under the addition amount.
The titanium dioxide is rutile titanium dioxide prepared by a chlorination method, and silica and alumina are used for inorganic coating treatment. The titanium dioxide prepared by the method has extremely low impurity content, and silicon oxide and aluminum oxide are used for coating treatment, so that lattice defects caused by titanium dioxide under the ultraviolet irradiation condition can be blocked, light activation points on the surface of the titanium dioxide are shielded, and the PID resistance is improved.
In some embodiments of the invention, the glass flux comprises a lead-free cadmium-free environmentally friendly low melting glass frit.
In some embodiments of the invention, the glass fusing agent comprises one of D245, N250, and N255.
The glass flux is lead-free cadmium environment-friendly low-melting-point glass powder, the grain size is preferably 5-10 mu m, the complete melting temperature is preferably 600-670 ℃, the white high-reflection glaze is enabled to be completely melted within a tempering temperature range of 680-720 ℃ in a short time, the melting flow property is better, the titanium pigment can be better coated, and the high adhesive force and the weather resistance of the glaze layer are further ensured.
In some embodiments of the invention, the high temperature crack resistant powder comprises an inorganic ultra-fine powder.
In some embodiments of the invention, the inorganic-based ultrafine powder comprises GT18 high temperature crack resistant powder.
In some embodiments of the invention, the inorganic superfine powder can generate phase change in the structural shape of the material at 220 ℃ and 350 ℃ respectively, the volume is relatively increased, the shrinkage stress impact caused by cooling and solidifying the high-temperature liquid phase material can be improved, the material process mechanics is balanced to prevent shrinkage cracking, and the shock resistance of the white high-reflection glazed glass is improved. Such as An Miwei nm, inc. GT18 high temperature crack resistant powder.
In some embodiments of the present invention, the method of preparing the reflective frit includes: mixing the water-based ink-regulating oil, the titanium pigment, the sodium aluminum silicate, the glass flux and the high-temperature anti-cracking powder.
In some embodiments of the invention, the reflective frit has a fineness of < 10 μm.
According to a fourth aspect of the invention, the use of said reflective glazing in photovoltaic glass is proposed.
Detailed Description
The conception and the technical effects produced by the present invention will be clearly and completely described in conjunction with the embodiments below to fully understand the objects, features and effects of the present invention. It is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments, and that other embodiments obtained by those skilled in the art without inventive effort are within the scope of the present invention based on the embodiments of the present invention.
Example 1
The phosphate modified acrylic resin and the environment-friendly water-based varnish are prepared in the embodiment.
The preparation method of the phosphate modified acrylic resin comprises the following steps:
s1, weighing 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) acrylic ester, and uniformly mixing to obtain a mixed monomer A;
s2, weighing 0.22g of azodiisobutyl cyanide and dissolving in 5g of propylene glycol methyl ether to obtain an initiator solution B;
s3, adding 15g of propylene glycol methyl ether and 25g of diethylene glycol butyl ether into a four-necked flask, starting stirring and heating to 90 ℃, adding 1/3 of mixed monomer A and 1/4 of initiator solution B into the four-necked flask, reacting for 15min, dropwise adding the mixture of the residual mixed monomer A and 1/2 of initiator solution B into the four-necked flask within 3-4 h, preserving heat and reacting for 5h after dropwise adding, adding the residual 1/4 of initiator solution B, continuing to preserving heat and reacting for 2h, cooling to 40-50 ℃, adding pH regulator N, N-dimethylethanolamine, regulating the pH of the system to 8-9, and stirring and reacting for 0.5h to obtain the water-soluble acrylic resin.
The preparation method of the environment-friendly water-based varnish comprises the following steps:
s4, slowly adding 2g of thickening anti-settling agent carboxymethyl cellulose acetate butyrate CMCAB641-0.2 (Isman) into 89g of solvent under the condition of low-speed stirring, heating at 40-60 ℃, dispersing and stirring for 30-60 min, taking 6g of water-soluble acrylic resin after complete dissolution, adding 2g of dispersing agent TEGO750W and 1g of flatting agent BYK380N after uniform mixing, and adding a proper amount of neutralizing agent AMP95 after uniform transparent liquid is formed, thus obtaining the environment-friendly water-based ink-regulating oil.
Preparation of aqueous white high-reflection glaze:
s5, adding 30g of the environment-friendly water-based varnish into a dispersion cylinder, and starting a mechanical stirrer, wherein the stirring speed is 500-1500 rpm;
s6, sequentially adding 36g of titanium dioxide and 4g of aluminum silicate sodium salt into a dispersing cylinder, and continuing to disperse at a high speed of 500-1500 rpm for 10-90 min to prepare uniform and fine white slurry;
s7, sequentially adding 60g of glass flux and 5g of high-temperature anti-cracking powder into the white slurry, continuing to disperse at a high speed of 500-1500 rpm for 10-90 min, and then adjusting the viscosity to about 60000-100000 mpas by using a diluent according to the requirement;
s8, finally pouring the white ink into a three-roller grinder for ink binding, and detecting the fineness of the ink to ensure that the fineness is less than 10 mu m, thus obtaining the water-based white high-reflection glaze.
Example 2
The phosphate modified acrylic resin and the environment-friendly water-based varnish are prepared in the embodiment.
The preparation method of the phosphate modified acrylic resin comprises the following steps:
s1, weighing and uniformly mixing 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) acrylic ester to obtain a mixed monomer A;
s2, weighing 0.5g of azodiisobutyl cyanide and dissolving in 5g of propylene glycol methyl ether to obtain an initiator solution B;
s3, adding 20g of propylene glycol methyl ether and 25g of diethylene glycol butyl ether into the four-necked flask, starting stirring and heating to 90 ℃, adding 1/3 of mixed monomer A and 1/4 of initiator solution B into the four-necked flask, reacting for 15min, dropwise adding the mixture of the residual mixed monomer A and 1/2 of initiator solution B into the four-necked flask within 3-4 h, preserving heat and reacting for 5h after dropwise adding, adding the residual 1/4 of initiator solution B, continuing to preserving heat and reacting for 2h, cooling to 40-50 ℃, adding pH regulator N, N-dimethylethanolamine, regulating the pH of the system to 8-9, and stirring and reacting for 0.5h to obtain the water-soluble acrylic resin.
The preparation method of the environment-friendly water-based varnish comprises the following steps:
s4, slowly adding 1g of thickening anti-settling agent carboxymethyl cellulose acetate butyrate CMCAB641-0.5 (Isman) into 90g of odor-free environment-friendly solvent under the condition of low-speed stirring, properly heating if necessary, dispersing and stirring for 30-60 min at the temperature of 40-60 ℃, taking 8g of water-soluble acrylic resin, adding 8g of dispersing agent TEGO750W and 0.5g of flatting agent BYK380N after completely dissolving, fully stirring to form uniform transparent liquid, and adding a proper amount of neutralizing agent AMP95 to obtain the environment-friendly water-based varnish.
Preparation of aqueous white high-reflection glaze:
s5, adding 30g of the environment-friendly water-based varnish into a dispersion cylinder, and starting a mechanical stirrer, wherein the stirring speed is 500-1500 rpm;
s6, sequentially adding 32g of titanium dioxide and 8g of aluminum silicate sodium salt into a dispersing cylinder, and continuing to disperse at a high speed of 500-1500 rpm for 10-90 min to prepare uniform and fine white slurry;
s7, sequentially adding 60g of glass flux and 8g of high-temperature anti-cracking powder into the white slurry, continuing to disperse at a high speed of 500-1500 rpm for 10-90 min, and then adjusting the viscosity to about 60000-100000 mpas by using a diluent according to the requirement;
s8, finally pouring the white ink into a three-roller grinder for ink binding, and detecting the fineness of the ink to ensure that the fineness is less than 10 mu m, thus obtaining the water-based white high-reflection glaze.
Example 3
The phosphate modified acrylic resin and the environment-friendly water-based varnish are prepared in the embodiment.
The preparation method of the phosphate modified acrylic resin comprises the following steps:
s1, weighing 30g of methyl methacrylate, 15g of butyl acrylate, 5g of hydroxyethyl acrylate, 5g of acrylic acid, 3g of polyether phosphate methacrylate and 2g of methoxy polyethylene glycol (550) acrylic ester, and uniformly mixing to obtain a mixed monomer A;
s2, weighing 0.6g of azodiisobutyl cyanide and dissolving in 5g of propylene glycol methyl ether to obtain an initiator solution B;
s3, adding 15g of propylene glycol methyl ether and 20g of diethylene glycol butyl ether into a four-neck flask, starting stirring and heating to 90 ℃, adding 1/3 of mixed monomer A and 1/4 of initiator solution B into the four-neck flask, reacting for 15min, dropwise adding the mixture of the residual mixed monomer A and 1/2 of initiator solution B into the four-neck flask within 3-4 h, preserving heat and reacting for 5h after dropwise adding, adding the residual 1/4 of initiator solution B, continuing to preserving heat and reacting for 2h, cooling to 40-50 ℃, adding pH regulator N, N-dimethylethanolamine, regulating the pH of the system to 8-9, and stirring and reacting for 0.5h to obtain the water-soluble acrylic resin.
The preparation method of the environment-friendly water-based varnish comprises the following steps:
s4, slowly adding 3g of thickening anti-settling agent hydroxypropyl methylcellulose into 85g of odor-free environment-friendly solvent under the condition of low-speed stirring, heating appropriately if necessary, dispersing and stirring for 30-60 min at the temperature of 40-60 ℃, adding 10g of water-soluble acrylic resin into the mixture after the mixture is completely dissolved, uniformly mixing, adding 1g of dispersing agent TEGO750W,0.1g of defoaming agent TEGO Foamex 830 and 0.9g of flatting agent BYK380N, fully stirring to form uniform transparent liquid, and adding a proper amount of neutralizing agent AMP95 to obtain the environment-friendly water-based ink regulating oil.
Preparation of aqueous white high-reflection glaze:
s5, adding 30g of the environment-friendly water-based varnish into a dispersion cylinder, and starting a mechanical stirrer, wherein the stirring speed is 500-1500 rpm;
s6, sequentially adding 28g of titanium dioxide and 12g of aluminum silicate sodium salt into a dispersing cylinder, and continuing to disperse at a high speed of 500-1500 rpm for 10-90 min to prepare uniform and fine white slurry;
s7, sequentially adding 60g of glass flux and 10g of high-temperature anti-cracking powder into the white slurry, continuing to disperse at a high speed of 500-1500 rpm for 10-90 min, and then adjusting the viscosity to about 60000-100000 mpas by using a diluent according to the requirement;
s8, finally pouring the white ink into a three-roller grinder for ink binding, and detecting the fineness of the ink to ensure that the fineness is less than 10 mu m, thus obtaining the water-based white high-reflection glaze.
Example 4
The phosphate modified acrylic resin and the environment-friendly water-based varnish are prepared in the embodiment.
The preparation method of the phosphate modified acrylic resin comprises the following steps:
s1, weighing and uniformly mixing 20g of methyl methacrylate, 20g of butyl acrylate, 5g of hydroxyethyl acrylate, 5g of acrylic acid, 5g of acyloxy ethyl phosphate methacrylate and 5g of methoxy polyethylene glycol (1000) acrylic ester to obtain a mixed monomer A;
s2, weighing 0.45g of azodiisobutyl cyanide and dissolving in 5g of propylene glycol methyl ether to obtain an initiator solution B;
s3, adding 15g of propylene glycol methyl ether and 20g of diethylene glycol butyl ether into a four-neck flask, starting stirring and heating to 90 ℃, adding 1/3 of mixed monomer A and 1/4 of initiator solution B into the four-neck flask, reacting for 15min, dropwise adding the mixture of the residual mixed monomer A and 1/2 of initiator solution B into the four-neck flask within 3-4 h, preserving heat and reacting for 5h after dropwise adding, adding the residual 1/4 of initiator solution B, continuing to preserving heat and reacting for 2h, cooling to 40-50 ℃, adding pH regulator N, N-dimethylethanolamine, regulating the pH of the system to 8-9, and stirring and reacting for 0.5h to obtain the water-soluble acrylic resin.
The preparation method of the environment-friendly water-based varnish comprises the following steps:
s4, slowly adding 2g of thickening anti-settling agent cellulose acetate butyrate CAB553-0.4 into 88g of odor-removing environment-friendly solvent under the condition of low-speed stirring, heating properly when necessary, dispersing and stirring for 30-60 min at the temperature of 40-60 ℃, adding 10g of water-soluble acrylic resin into the mixture after the mixture is completely dissolved, and fully stirring the mixture to form uniform transparent liquid, thus obtaining the environment-friendly water-based ink-transfer oil.
Preparation of aqueous white high-reflection glaze:
s5, adding 30g of the environment-friendly water-based varnish into a dispersion cylinder, and starting a mechanical stirrer, wherein the stirring speed is 500-1500 rpm;
s6, sequentially adding 24g of titanium dioxide and 16g of sodium aluminum silicate into a dispersing cylinder, and continuing to disperse at a high speed of 500-1500 rpm for 10-90 min to prepare uniform and fine white slurry;
s7, sequentially adding 60g of glass flux and 2g of high-temperature anti-cracking powder into the white slurry, continuing to disperse at a high speed of 500-1500 rpm for 10-90 min, and then adjusting the viscosity to about 60000-100000 mpas by using a diluent according to the requirement;
s8, finally pouring the white ink into a three-roller grinder for ink binding, and detecting the fineness of the ink to ensure that the fineness is less than 10 mu m, thus obtaining the water-based white high-reflection glaze.
Comparative example 1
The comparative example prepares an organosilicon modified water-soluble acrylic resin and an environment-friendly water-based varnish, which comprises the following specific steps:
s1, keeping a reaction kettle clean and anhydrous, adding 40 parts of alcohol ether solvent according to parts by weight, introducing nitrogen into the reaction kettle, keeping the reaction kettle, introducing cooling water into a condensing tube, and heating the alcohol ether solvent to 140 ℃;
s2, taking a dispersing kettle in addition, and sequentially adding 10 parts of tertiary 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 organic silicon monomer, 2 parts of molecular weight regulator (chain transfer agent) and 3.5 parts of initiator according to parts by weight; stirring and mixing uniformly, wherein the stirring rotating speed is 300r/min, and the stirring time is 40min; dripping the mixed solution into the reaction kettle in the step (1) for 6 hours, and controlling the temperature at 140 ℃; after the dripping is finished, preserving heat and reacting for 2 hours, and controlling the temperature at 140 ℃;
s3, adding 0.2 part of initiator into the reaction kettle in the step (1) according to parts by weight, and continuously reacting for 2 hours, wherein the temperature is controlled at 140 ℃;
s4, cooling to 80 ℃, adding 40 parts of alcohol ether solvent according to parts by weight, stirring and mixing uniformly, wherein the stirring speed is 400r/min, and the stirring time is 30min;
s5, dropwise adding a pH regulator with the mass concentration of 10%, adjusting the pH value to 8.0, stirring at the speed of 400r/min and for 20min to obtain the organosilicon modified water-soluble acrylic resin.
The preparation method of the environment-friendly water-based varnish comprises the following steps:
s6, slowly adding 1g of thickening anti-settling agent hydroxypropyl methyl cellulose into 85g of odor-free environment-friendly solvent under the condition of low-speed stirring, heating appropriately if necessary, dispersing and stirring for 30-60 min at the temperature of 40-60 ℃, adding 10g of the organosilicon modified water-soluble acrylic resin into the mixture after the organosilicon modified water-soluble acrylic resin is completely dissolved, uniformly mixing, adding 2g of dispersing agent TEGO750W,0.1g of defoaming agent TEGO Foamex 830 and 1.9g of flatting agent BYK380N, fully stirring to form uniform transparent liquid, and adding a proper amount of neutralizing agent AMP95 to obtain the environment-friendly water-based ink-regulating oil.
Preparation of aqueous white high-reflection glaze:
s7, adding 30g of the environment-friendly water-based varnish into a dispersion cylinder, and starting a mechanical stirrer at a stirring speed of 500-1500 rpm;
s8, sequentially adding 28g of titanium dioxide and 12g of aluminum silicate sodium salt into a dispersing cylinder, and continuing to disperse at a high speed of 500-1500 rpm for 10-90 min to prepare uniform and fine white slurry;
s9, sequentially adding 60g of glass flux and 10g of high-temperature anti-cracking powder into the white slurry, continuing to disperse at a high speed of 500-1500 rpm for 10-90 min, and then adjusting the viscosity to about 60000-100000 mpas by using a diluent according to the requirement;
s10, finally pouring the white ink into a three-roller grinder for ink pricking, and detecting the fineness of the ink to ensure that the fineness is less than 10 mu m, thus obtaining the water-based white high-reflection glaze.
Comparative example 2
The comparative example prepares an organosilicon modified water-soluble acrylic resin and an environment-friendly water-based varnish, which comprises the following specific steps:
s1, weighing 30g of methyl methacrylate, 15g of styrene, 5g of hydroxyethyl acrylate, 5g of acrylic acid, 3g of polyether phosphate methacrylate and 2g of methoxy polyethylene glycol (550) acrylic ester, and uniformly mixing to obtain a mixed monomer A;
s2, weighing 0.6g of azodiisobutyl cyanide and dissolving in 5g of propylene glycol methyl ether to obtain an initiator solution B;
s3, adding 15g of propylene glycol methyl ether and 20g of diethylene glycol butyl ether into a four-neck flask, starting stirring and heating to 90 ℃, adding 1/3 of mixed monomer A and 1/4 of initiator solution B into the four-neck flask, reacting for 15min, dropwise adding the mixture of the residual mixed monomer A and 1/2 of initiator solution B into the four-neck flask within 3-4 h, preserving heat and reacting for 5h after dropwise adding, adding the residual 1/4 of initiator solution B, continuing to preserving heat and reacting for 2h, cooling to 40-50 ℃, adding pH regulator N, N-dimethylethanolamine, regulating the pH of the system to 8-9, and stirring and reacting for 0.5h to obtain the water-soluble acrylic resin.
The preparation method of the environment-friendly water-based varnish comprises the following steps:
s4, slowly adding 1g of thickening anti-settling agent hydroxypropyl methyl cellulose into 85g of odor-free environment-friendly solvent under the condition of low-speed stirring, heating appropriately if necessary, dispersing and stirring for 30-60 min at the temperature of 40-60 ℃, adding 10g of the organosilicon modified water-soluble acrylic resin into the mixture after the organosilicon modified water-soluble acrylic resin is completely dissolved, uniformly mixing, adding 2g of dispersing agent TEGO750W,0.1g of defoaming agent TEGO Foamex 830 and 1.9g of flatting agent BYK380N, fully stirring to form uniform transparent liquid, and adding a proper amount of neutralizing agent AMP95 to obtain the environment-friendly water-based ink-regulating oil.
Preparation of aqueous white high-reflection glaze:
s5, adding 30g of the environment-friendly water-based varnish into a dispersion cylinder, and starting a mechanical stirrer, wherein the stirring speed is 500-1500 rpm;
s6, sequentially adding 40g of titanium dioxide into a dispersing cylinder, and continuing to disperse at a high speed of 500-1500 rpm for 10-90 min to prepare uniform and fine white slurry;
s7, sequentially adding 60g of glass flux and 2g of high-temperature anti-cracking powder into the white slurry, continuing to disperse at a high speed of 500-1500 rpm for 10-90 min, and then adjusting the viscosity to about 60000-100000 mpas by using a diluent according to the requirement;
s8, finally pouring the white ink into a three-roller grinder for ink binding, and detecting the fineness of the ink to ensure that the fineness is less than 10 mu m, thus obtaining the water-based white high-reflection glaze.
Comparative example 3
The comparative example prepares an organosilicon modified water-soluble acrylic resin and an environment-friendly water-based varnish, which comprises the following specific steps:
s1, weighing 30g of methyl methacrylate, 15g of butyl acrylate, 5g of hydroxyethyl acrylate, 5g of acrylic acid and 2g of methoxy polyethylene glycol (550) acrylic ester, and uniformly mixing to obtain a mixed monomer A;
s2, weighing 0.6g of azodiisobutyl cyanide and dissolving in 5g of propylene glycol methyl ether to obtain an initiator solution B;
s3, adding 15g of propylene glycol methyl ether and 20g of diethylene glycol butyl ether into a four-neck flask, starting stirring and heating to 90 ℃, adding 1/3 of mixed monomer A and 1/4 of initiator solution B into the four-neck flask, reacting for 15min, dropwise adding the mixture of the residual mixed monomer A and 1/2 of initiator solution B into the four-neck flask within 3-4 h, preserving heat and reacting for 5h after dropwise adding, adding the residual 1/4 of initiator solution B, continuing to preserving heat and reacting for 2h, cooling to 40-50 ℃, adding pH regulator N, N-dimethylethanolamine, regulating the pH of the system to 8-9, and stirring and reacting for 0.5h to obtain the water-soluble acrylic resin.
The preparation method of the environment-friendly water-based varnish comprises the following steps:
s4, slowly adding 1g of thickening anti-settling agent hydroxypropyl methyl cellulose into 85g of odor-free environment-friendly solvent under the condition of low-speed stirring, heating appropriately if necessary, dispersing and stirring for 30-60 min at the temperature of 40-60 ℃, adding 10g of the organosilicon modified water-soluble acrylic resin into the mixture after the organosilicon modified water-soluble acrylic resin is completely dissolved, uniformly mixing, adding 2g of dispersing agent TEGO750W,0.1g of defoaming agent TEGO Foamex 830 and 1.9g of flatting agent BYK380N, fully stirring to form uniform transparent liquid, and adding a proper amount of neutralizing agent AMP95 to obtain the environment-friendly water-based ink-regulating oil.
Preparation of aqueous white high-reflection glaze:
s5, adding 30g of the environment-friendly water-based varnish into a dispersion cylinder, and starting a mechanical stirrer, wherein the stirring speed is 500-1500 rpm;
s6, sequentially adding 28g of titanium dioxide and 12g of aluminum silicate sodium salt into a dispersing cylinder, and continuing to disperse at a high speed of 500-1500 rpm for 10-90 min to prepare uniform and fine white slurry;
s7, adding 60g of glass flux into the white slurry, continuing to disperse at a high speed of 500-1500 rpm for 10-90 min, and then adjusting the viscosity to about 60000-100000 mpas by using a diluent according to the requirement;
s8, finally pouring the white ink into a three-roller grinder for ink binding, and detecting the fineness of the ink to ensure that the fineness is less than 10 mu m, thus obtaining the water-based white high-reflection glaze.
Comparative example 4
The comparative example prepares an organosilicon modified water-soluble acrylic resin and an environment-friendly water-based varnish, which comprises the following specific steps:
s1, weighing 30g of methyl methacrylate, 15g of butyl acrylate, 5g of hydroxyethyl acrylate, 5g of acrylic acid and 3g of polyether phosphate methacrylate, and uniformly mixing to obtain a mixed monomer A;
s2, weighing 0.6g of azodiisobutyl cyanide and dissolving in 5g of propylene glycol methyl ether to obtain an initiator solution B;
s3, adding 15g of propylene glycol methyl ether and 20g of diethylene glycol butyl ether into a four-neck flask, starting stirring and heating to 90 ℃, adding 1/3 of mixed monomer A and 1/4 of initiator solution B into the four-neck flask, reacting for 15min, dropwise adding the mixture of the residual mixed monomer A and 1/2 of initiator solution B into the four-neck flask within 3-4 h, preserving heat and reacting for 5h after dropwise adding, adding the residual 1/4 of initiator solution B, continuing to preserving heat and reacting for 2h, cooling to 40-50 ℃, adding pH regulator N, N-dimethylethanolamine, regulating the pH of the system to 8-9, and stirring and reacting for 0.5h to obtain the water-soluble acrylic resin.
The preparation method of the environment-friendly water-based varnish comprises the following steps:
s4, slowly adding 1g of thickening anti-settling agent hydroxypropyl methyl cellulose into 85g of odor-free environment-friendly solvent under the condition of low-speed stirring, heating appropriately if necessary, dispersing and stirring for 30-60 min at the temperature of 40-60 ℃, adding 10g of the organosilicon modified water-soluble acrylic resin into the mixture after the organosilicon modified water-soluble acrylic resin is completely dissolved, uniformly mixing, adding 2g of dispersing agent TEGO750W,0.1g of defoaming agent TEGO Foamex 830 and 1.9g of flatting agent BYK380N, fully stirring to form uniform transparent liquid, and adding a proper amount of neutralizing agent AMP95 to obtain the environment-friendly water-based ink-regulating oil.
Preparation of aqueous white high-reflection glaze:
s5, adding 30g of the environment-friendly water-based varnish into a dispersion cylinder, and starting a mechanical stirrer, wherein the stirring speed is 500-1500 rpm;
s6, adding 40g of titanium dioxide into a dispersion cylinder, and continuing to disperse at a high speed of 500-1500 rpm for 10-90 min to prepare uniform and fine white slurry;
s7, adding 60g of glass flux into the white slurry, continuing to disperse at a high speed of 500-1500 rpm for 10-90 min, and then adjusting the viscosity to about 60000-100000 mpas by using a diluent according to the requirement;
s8, finally pouring the white ink into a three-roller grinder for ink binding, and detecting the fineness of the ink to ensure that the fineness is less than 10 mu m, thus obtaining the water-based white high-reflection glaze.
While the embodiments of the present invention have been described in detail, the present invention is not limited to the above embodiments, and various changes can be made without departing from the spirit of the present invention within the knowledge of those skilled in the art. Furthermore, embodiments of the invention and features of the embodiments may be combined with each other without conflict.

Claims (10)

1. The water-based varnish is characterized by comprising the following raw materials in parts by weight: 1 to 10 parts of phosphate modified acrylic resin, 0.5 to 5 parts of thickener, 1 to 2 parts of dispersant and 80 to 95 parts of solvent;
the preparation raw materials of the phosphate modified acrylic ester resin comprise: phosphate functional monomers, methoxypolyethylene glycol acrylate, acrylic acid and acrylate;
the phosphate functional monomer comprises at least one of methacrylic acid acyloxyethyl 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 acrylic resin is 5000-100000 MW.
2. The aqueous varnish as claimed in claim 1, wherein the phosphate modified acrylate resin is prepared from (by weight parts) phosphate functional monomer 1-5, methoxypolyethylene glycol acrylate 2-5, acrylic acid 2-5 and acrylate 35-60.
3. The aqueous varnish of claim 1, wherein the phosphate modified acrylate resin is prepared from a raw material further comprising an alcohol ether solvent; preferably, the alcohol ether solvent comprises 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.
4. The phosphate modified acrylate resin of claim 1 wherein the phosphate modified acrylate resin is prepared from a raw material further comprising an initiator and a pH adjuster.
5. The aqueous varnish according to claim 1, wherein the raw materials for preparing the aqueous varnish further comprise an antifoaming agent and a leveling agent.
6. A method of preparing an aqueous varnish as claimed in any one of claims 1 to 5, comprising mixing the preparation materials of the aqueous varnish.
7. The method for producing an aqueous varnish according to claim 6, wherein the mixing temperature is 40 to 60 ℃.
8. A reflective glaze, characterized in that the reflective glaze is prepared from the aqueous varnish according to any one of claims 1 to 5.
9. The reflective glaze according to claim 8, wherein the reflective glaze is further prepared from aluminum silicate sodium salt and titanium pigment.
10. Use of the reflective glazing of claim 8 or 9 in photovoltaic glass.
CN202311064755.3A 2023-08-22 2023-08-22 Water-based ink-regulating oil and preparation method and application thereof Pending CN117210058A (en)

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