CN115612347A - Environment-friendly water-based varnish for photovoltaic glass glaze, preparation method of varnish and water-based white glaze - Google Patents
Environment-friendly water-based varnish for photovoltaic glass glaze, preparation method of varnish and water-based white glaze Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C09D11/107—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from unsaturated acids or derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
Abstract
The invention discloses a preparation method of environment-friendly water-based varnish for photovoltaic glass glaze, which comprises the following steps: under the condition of stirring, uniformly mixing an alcohol ether solvent, the organic silicon modified water-soluble acrylic resin and the rheological anti-settling agent, heating to 80-90 ℃, cooling to 40-50 ℃ after the organic silicon modified water-soluble acrylic resin and the rheological anti-settling agent are completely dissolved, adding a dispersing agent into the system, and uniformly mixing to obtain the environment-friendly water-based ink-regulating oil for the photovoltaic glass glaze. Compared with the mode of synthesizing silica sol in advance or polymerizing acrylic resin in advance, the method for preparing the organosilicon modified water-soluble acrylic resin by the homogeneous one-step method has the advantages that the process is simplified, organosilicon monomers and other raw materials are uniformly mixed in advance and then are dripped into an alcohol ether solvent for reaction, double bonds are cracked and polymerized synchronously with acrylic acid (ester) monomers and styrene, and the organosilicon monomers are uniform and better. And the organic silicon can reduce the surface energy and has better wettability to the glass powder and the titanium dioxide.
Description
The application is a divisional application of an invention patent application with the application date of 2021, 6 months and 25 days, the application number of 2021107127802 and the invention name of "an environment-friendly water-based varnish for photovoltaic glass glaze and a preparation method thereof".
Technical Field
The invention relates to the technical field of photovoltaic modules, in particular to environment-friendly water-based ink adjusting oil for photovoltaic glass glaze, a preparation method of the water-based ink adjusting oil and application of the water-based ink adjusting oil in photovoltaic backboard glass glaze.
Background
The double-glass photovoltaic module consists of front plate glass, back plate glass, solar cells and the like, wherein the cells are connected in series and in parallel by leads and collected to a lead terminal to form the photovoltaic cell module, and the double-glass photovoltaic module is particularly suitable for relatively harsh climatic environments, such as photovoltaic power stations in areas with high humidity. For effectively promoting dual glass assembly efficiency, except using white packaging material such as EVA and POE, still can coat photovoltaic glass frit on backplate glass.
The photovoltaic glass glaze comprises glass powder, titanium dioxide, ink mixing oil and the like, wherein polymer resin in the ink mixing oil is used as an adhesive, a glaze system is loaded on the back plate glass during silk printing, and good adhesive force is provided after the back plate glass is thermally cured (180-220 ℃). The varnish affects the adaptability, screen printing performance and glaze storage performance of glass powder, titanium dioxide and the like.
In the prior technical scheme, most of the ink mixing oil used for the photovoltaic glass glaze has large smell and is not environment-friendly, the adhesion force between the ink mixing oil and a glass substrate after thermal curing (180-220 ℃) is poor, and the like, and the ink mixing oil needs to be cleaned by using a solvent, has high comprehensive use cost and higher content of volatile VOCs, and has great harm to human beings and the environment.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide an improved preparation method of water-based varnish, wherein the organic silicon modified water-soluble acrylic resin is prepared by a homogeneous one-step method, has better wettability on glass powder and titanium dioxide, further increases the compatibility of the whole system, and improves the dispersion and grinding efficiency of the prepared white glaze.
The invention adopts the following technical scheme:
the environment-friendly water-based ink mixing oil for the photovoltaic glass glaze comprises the following raw material components in parts by weight: 60-80 parts of alcohol ether solvent, 20-40 parts of organic silicon modified water-soluble acrylic resin, 1-5 parts of rheological anti-settling agent and 1-5 parts of dispersing agent; the organic silicon modified water-soluble acrylic resin is prepared by a homogeneous one-step method, the solid content of the organic silicon modified water-soluble acrylic resin is 55 +/-1%, and the viscosity is 10000 +/-2000 mpa · s (25 +/-1 ℃). The organic silicon modified water-soluble acrylic resin with the viscosity range is used for preparing water-based varnish with moderate viscosity on the basis of ensuring the number of effective adherends, and is added with functional fillers such as glass powder, titanium dioxide and the like in a quantitative range to prepare the glaze, so that the integral viscosity of a glaze system is ensured.
According to some preferred embodiments of the present invention, the silicone-modified water-soluble acrylic resin comprises the following raw material components in parts by weight:
according to some preferred embodiments of the present invention, the silicone-modified water-soluble acrylic resin is prepared by:
mixing an acrylic monomer and/or an acrylate monomer, styrene, an organic silicon monomer, a molecular weight regulator and a part of initiator, uniformly mixing, dropwise adding into a part of alcohol ether solvent with the temperature of 140-150 ℃, controlling the dropwise adding time to be 6-8h, and carrying out heat preservation reaction for 1-2h after the dropwise adding is finished; adding the rest of initiator into the system, and continuing to react for 1-2h; cooling to 70-80 deg.C, adding the rest alcohol ether solvent, and mixing; and regulating the pH value of a system to be 8-9 by using an organic amine neutralizer to obtain the organic silicon modified water-soluble acrylic resin.
According to some preferred embodiments of the invention, the part of the alcohol ether solvent accounts for 40-60% of the total amount of the alcohol ether solvent in the organosilicon modified water-soluble acrylic resin raw material; the part of the initiator accounts for 80-95% of the total amount of the initiator in the raw material of the organosilicon modified water-soluble acrylic resin. The alcohol ether solvent is added in two times, and the purpose is to reduce the heating time in the synthetic process of the organic silicon modified water-soluble acrylic resin, and simultaneously reduce the cooling time and the usage amount of cooling water, thereby reducing the energy consumption in the production process. The initiator is added for two times, and the purpose is that the initiator supplemented for the second time is initiated at 140-150 ℃, and the residual monomer is polymerized again, so that the conversion rate of the organosilicon modified water-soluble acrylic resin is improved.
The preparation method has the following two advantages:
(1) Acrylic acid monomer and/or acrylate monomer, styrene, organic silicon monomer, molecular weight regulator, partial initiator and the like are uniformly mixed and dripped into a reaction kettle under the condition of homogeneous phase, molecular chains are increased through the fracture and polymerization of double bonds of acrylic acid (ester), styrene, vinyl and the like in the whole process, and the polymerization molecular weight is controlled through the molecular weight regulator (chain transfer agent), so that the viscosity of the organic silicon modified water-soluble acrylic resin obtained by the homogeneous one-step method is relatively low. Compared with the mode of synthesizing silica sol in advance or polymerizing acrylic resin in advance, the method has the advantages that the process is simplified, the organic silicon monomer and other raw materials are uniformly mixed in advance, then the mixture is dripped into an alcohol ether solvent to react, double bond fracture and polymerization are carried out synchronously with the acrylic acid (ester) monomer and the styrene, and the uniformity of the organic silicon monomer is better. And the organosilicon can reduce the surface energy, has better wettability to glass powder and titanium dioxide, and then increases the compatibility of the whole glaze system, and improves the dispersion and grinding efficiency of the prepared white glaze.
(2) The temperature of the system is reduced to 70-80 ℃, and the residual alcohol ether solvent is added to continue to be stirred and mixed evenly. By adopting the method, the heating time in the synthetic process of the organic silicon modified water-based acrylic resin can be reduced, and the cooling time and the use amount of cooling water are reduced, so that the energy consumption in the production process is reduced.
According to some preferred embodiment aspects of the present invention, the acrylic acid (ester) monomer is an acrylic acid monomer and/or an acrylate ester monomer. The acrylic monomer is acrylic acid; the acrylate monomer is one or more of tertiary carbonic acid glycidyl ester, hydroxyethyl acrylate, methyl methacrylate, isobornyl methacrylate and butyl acrylate; the organic silicon monomer is vinyl triethoxysilane and/or 3- (methacryloyloxy) propyl trimethoxysilane.
According to some preferred embodiments of the invention, the molecular weight regulator (chain transfer agent) is a 2, 4-diphenyl-4-methyl-1-pentenylmethylstyrene linear dimer; the initiator is di-tert-butyl peroxide and/or di-tert-amyl peroxide; the pH regulator is an organic amine neutralizer, and the organic amine neutralizer is dimethylethanolamine and/or 2-amino-2-methyl-1-propanol.
According to some preferred embodiment aspects of the invention, the alcohol ether solvent in the environment-friendly water-based varnish for photovoltaic glass glazes and/or the alcohol ether solvent in the organosilicon modified water-soluble acrylic resin is selected from one or more of diethylene glycol butyl ether, dipropylene glycol methyl ether, tripropylene glycol methyl ether, dipropylene glycol butyl ether and tripropylene glycol butyl ether.
According to some preferred embodiment aspects of the present invention, the rheological anti-settling agent in the eco-friendly aqueous varnish for photovoltaic glass glazes is one or more of fumed silica, organic bentonite, a modified polyurea solution and ethyl cellulose.
According to some preferred embodiment aspects of the invention, the dispersant in the environment-friendly aqueous varnish for photovoltaic glass glazes is an aqueous high molecular polymer, such as TEGO 755W.
The invention also provides a preparation method of the environment-friendly water-based varnish for the photovoltaic glass glaze, which comprises the following steps:
(1) The preparation of the organic silicon modified water-soluble acrylic resin comprises the following steps:
mixing an acrylic monomer and/or an acrylate monomer, styrene, an organic silicon monomer, a molecular weight regulator and a part of initiator, uniformly mixing, dropwise adding into a part of alcohol ether solvent with the temperature of 140-150 ℃, controlling the dropwise adding time to be 6-8h, and carrying out heat preservation reaction for 1-2h after the dropwise adding is finished; adding the rest initiator into the system, and continuing to react for 1-2h; cooling to 70-80 deg.C, adding the rest alcohol ether solvent, and mixing; adjusting the pH value of a system to be 8-9 by using a pH regulator to obtain the organic silicon modified water-soluble acrylic resin;
(2) Preparing the environment-friendly water-based varnish for the photovoltaic glass glaze:
under the condition of stirring, uniformly mixing an alcohol ether solvent, the organic silicon modified water-soluble acrylic resin and the rheological anti-settling agent, heating to 80-90 ℃, cooling to 40-50 ℃ after the organic silicon modified water-soluble acrylic resin and the rheological anti-settling agent are completely dissolved, adding a dispersing agent into the system, and uniformly mixing to obtain the environment-friendly water-based ink-regulating oil for the photovoltaic glass glaze.
The solid content of the environment-friendly water-based ink-regulating oil for photovoltaic glass glaze prepared by the preparation method is 3 +/-1%; the viscosity is 100-500 mpa.s (25 + -1 deg.C).
In some embodiments of the present invention, the method specifically includes the following steps:
(1) Preparing organic silicon modified water-soluble acrylic resin:
(a) Keeping the reaction kettle clean and anhydrous, adding 20-40 parts by weight of alcohol ether solvent, introducing nitrogen into the reaction kettle, keeping the reaction kettle, introducing cooling water into a condensation pipe, and heating the alcohol ether solvent to 140-150 ℃.
(b) Taking another dispersion kettle, and sequentially adding 10-15 parts of tertiary carbonic acid glycidyl ester, 5-10 parts of hydroxyethyl acrylate, 1-5 parts of methyl methacrylate, 3-6 parts of acrylic acid, 5-10 parts of isobornyl methacrylate, 25-35 parts of butyl acrylate, 10-20 parts of styrene, 5-10 parts of organosilicon monomer, 1-2 parts of molecular weight regulator (chain transfer agent) and 2-5 parts of initiator according to parts by weight; stirring and mixing uniformly, wherein the stirring speed is 200-300r/min, and the stirring time is 30-40min; dropwise adding the mixed solution (a homogeneous system formed by a mixed monomer, a molecular weight regulator (chain transfer agent) and an initiator) into the reaction kettle in the step (a), wherein the dropwise adding time is 6-8h, and the temperature is controlled at 140-150 ℃; after the dropwise addition, the reaction is carried out for 1 to 2 hours under the condition of heat preservation, and the temperature is controlled to be 140 to 150 ℃.
(c) Adding 0.1-0.3 part of initiator into the reaction kettle in the step (a) according to the weight part, and continuing to react for 1-2 hours, wherein the temperature is controlled at 140-150 ℃.
(d) Cooling to 70-80 deg.C, adding 20-40 parts by weight of alcohol ether solvent, stirring at 400-500r/min for 20-30min.
(e) And (3) dropwise adding 10-15% of pH regulator with mass concentration, adjusting the pH value to 8.0-9.0, stirring at the rotating speed of 400-500r/min for 20-30min, and thus obtaining the organic silicon modified water-soluble acrylic resin.
(2) Preparing the environment-friendly water-based varnish for the photovoltaic glass glaze:
under the stirring condition, 60-80 parts by weight of alcohol ether solvent, 20-40 parts by weight of organic silicon modified water-soluble acrylic resin and 1-5 parts by weight of rheological anti-settling agent are sequentially put into a stirring kettle, stirred to be uniform, the stirring speed is 200-300r/min, stirring is kept, the temperature is raised to 80-90 ℃, and the temperature is reduced and cooled after complete dissolution. And keeping stirring and cooling to 40-50 ℃, putting 1-5 parts of dispersing agent into a stirring kettle, and stirring uniformly for 20-30min to obtain the environment-friendly water-based varnish for photovoltaic glass glaze.
The invention also provides application of the environment-friendly water-based varnish for photovoltaic glass glaze in water-based environment-friendly white glaze for photovoltaic back plate glass. The water-based environment-friendly white glaze comprises glass powder, titanium dioxide, ink mixing oil and the like, wherein polymer resin (organic silicon modified water-soluble acrylic resin) in the ink mixing oil is used as an adhesive, a glaze system is loaded on back plate glass during silk printing, and good adhesive force is provided after thermocuring (180-220 ℃). The organic silicon modified water-soluble acrylic resin used in the environment-friendly water-based varnish for photovoltaic glass glaze has good wettability on glass powder and titanium dioxide, so that the compatibility of the whole system is increased, and the dispersion and grinding efficiency of the prepared white glaze is improved.
Due to the adoption of the technical scheme, compared with the prior art, the invention has the following advantages: compared with the mode of pre-synthesizing silica sol or pre-polymerizing acrylic resin, the process is simplified, the organosilicon monomer and other raw materials are uniformly mixed in advance, then the mixture is dripped into an alcohol ether solvent for reaction, double bond fracture and polymerization are synchronously carried out with acrylic acid (ester) monomer and styrene, and the uniformity of the organosilicon monomer is better. And the organosilicon can reduce the surface energy, has better wettability to glass powder and titanium dioxide, further increases the compatibility of the whole system, and improves the dispersion and grinding efficiency of the prepared white glaze. And at the later stage of synthesis of the organic silicon modified water-soluble acrylic resin, reducing the temperature of the system to 70-80 ℃, adding the residual alcohol ether solvent, and continuously stirring and uniformly mixing. By adopting the method, the heating time in the synthetic process of the organic silicon modified water-based acrylic resin can be reduced, and the cooling time and the use amount of cooling water are reduced, so that the energy consumption in the production process is reduced.
Detailed Description
In order to make those skilled in the art better understand the technical solution of the present invention, the following will clearly and completely describe the technical solution in conjunction with the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, shall fall within the protection scope of the present invention.
Example 1
The preparation method of the environment-friendly water-based varnish for the photovoltaic glass glaze in the embodiment comprises the following steps:
(1) Preparing organic silicon modified water-soluble acrylic resin:
(a) Keeping the reaction kettle clean and anhydrous, adding 40 parts by weight of alcohol ether solvent, introducing nitrogen into the reaction kettle and keeping the nitrogen, introducing cooling water into a condensation pipe, and heating the alcohol ether solvent to 140 ℃.
(b) Taking another dispersion kettle, and sequentially adding 10 parts of tertiary carbonic acid 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 speed is 300r/min, and the stirring time is 40min; dropwise adding the mixed solution into the reaction kettle in the step (a), wherein the dropwise adding time is 6 hours, and the temperature is controlled at 140 ℃; after the dropwise addition, the reaction is carried out for 2 hours under the condition of heat preservation, and the temperature is controlled at 140 ℃.
(c) Adding 0.2 part of initiator by weight into the reaction kettle in the step (a), and continuing to react for 2 hours, wherein the temperature is controlled at 140 ℃.
(d) Cooling to 80 ℃, adding 40 parts by weight of alcohol ether solvent, and uniformly stirring and mixing at the stirring speed of 400r/min for 30min.
(e) And (3) dropwise adding a pH regulator with the mass concentration of 10%, adjusting the pH value to 8.0, stirring at the rotating speed of 400r/min for 20min, and thus obtaining the organic silicon modified water-soluble acrylic resin.
(2) Preparing the environment-friendly water-based varnish for the photovoltaic glass glaze:
under the stirring condition, 60 parts of alcohol ether solvent, 32.5 parts of organic silicon modified water-soluble acrylic resin and 5 parts of rheological anti-settling agent are sequentially put into a stirring kettle in parts by weight, stirred uniformly at the stirring speed of 300r/min, kept stirred, heated to 90 ℃, cooled after being completely dissolved. And keeping stirring and cooling to 50 ℃, putting 2.5 parts of dispersing agent into a stirring kettle, and stirring uniformly for 20min to obtain the environment-friendly water-based ink mixing oil for the photovoltaic glass glaze.
Example 2
The preparation method of the environment-friendly water-based varnish for the photovoltaic glass glaze in the embodiment comprises the following steps:
(1) Preparing organic silicon modified water-soluble acrylic resin:
(a) Keeping the reaction kettle clean and anhydrous, adding 40 parts by weight of alcohol ether solvent, introducing nitrogen into the reaction kettle and keeping the nitrogen, introducing cooling water into a condensation pipe, and heating the alcohol ether solvent to 150 ℃.
(b) Taking another dispersion kettle, and sequentially adding 15 parts of tertiary carbonic acid glycidyl ester, 5 parts of hydroxyethyl acrylate, 5 parts of methyl methacrylate, 5 parts of acrylic acid, 5 parts of isobornyl methacrylate, 35 parts of butyl acrylate, 15 parts of styrene, 5 parts of organic silicon monomer, 1.5 parts of molecular weight regulator (chain transfer agent) and 4 parts of initiator according to parts by weight; stirring and mixing uniformly, wherein the stirring speed is 300r/min, and the stirring time is 30min; dropwise adding the mixed solution into the reaction kettle in the step (a), wherein the dropwise adding time is 6 hours, and the temperature is controlled at 150 ℃; after the dropwise addition, the temperature is kept for 2 hours, and the temperature is controlled at 150 ℃.
(c) Adding 0.3 part of initiator by weight into the reaction kettle in the step (a), and continuing to react for 2 hours, wherein the temperature is controlled at 150 ℃.
(d) And cooling to 70 ℃, adding 40 parts by weight of alcohol ether solvent, and uniformly stirring and mixing at the stirring speed of 400r/min for 30min.
(e) And (3) dropwise adding a pH regulator with the mass concentration of 15%, adjusting the pH value to 9.0, stirring at the rotating speed of 400r/min for 30min, and thus obtaining the organic silicon modified water-soluble acrylic resin.
(2) Preparing the environment-friendly water-based varnish for the photovoltaic glass glaze:
under the stirring condition, according to the weight portion, 70 portions of alcohol ether solvent, 25 portions of organic silicon modified water-soluble acrylic resin and 3 portions of rheological anti-settling agent are sequentially put into a stirring kettle, stirred to be uniform, the stirring speed is 300r/min, the stirring is kept, the temperature is raised to 85 ℃, and the temperature is reduced and the cooling is carried out after the complete dissolution. And keeping stirring and cooling to 50 ℃, putting 2 parts of dispersing agent into a stirring kettle, and stirring uniformly for 25min to obtain the environment-friendly water-based ink mixing oil for the photovoltaic glass glaze.
Example 3
The preparation method of the environment-friendly water-based varnish for the photovoltaic glass glaze in the embodiment comprises the following steps:
(1) Polymerization preparation of organosilicon modified water-soluble acrylic resin:
(a) Keeping the reaction kettle clean and anhydrous, adding 40 parts by weight of alcohol ether solvent, introducing nitrogen into the reaction kettle and keeping the nitrogen, introducing cooling water into a condensation pipe, and heating the alcohol ether solvent to 145 ℃.
(b) Taking another dispersion kettle, and sequentially adding 12 parts of tertiary carbonic acid glycidyl ester, 10 parts of hydroxyethyl acrylate, 5 parts of methyl methacrylate, 3 parts of acrylic acid, 10 parts of isobornyl methacrylate, 30 parts of butyl acrylate, 10 parts of styrene, 8 parts of organic silicon monomer, 2 parts of molecular weight regulator (chain transfer agent) and 5 parts of initiator according to parts by weight; stirring and mixing uniformly, wherein the stirring speed is 300r/min, and the stirring time is 30min; dropwise adding the mixed solution into the reaction kettle in the step (a), wherein the dropwise adding time is 8h, and the temperature is controlled at 145 ℃; after the dropwise addition, the reaction is carried out for 2 hours under the condition of heat preservation, and the temperature is controlled to be 145 ℃.
(c) Adding 0.3 part of initiator into the reaction kettle of the step (a) by weight part, and continuing to react for 1 hour, wherein the temperature is controlled at 145 ℃.
(d) And cooling to 75 ℃, adding 30 parts by weight of alcohol ether solvent, and uniformly stirring and mixing at the stirring speed of 400r/min for 30min.
(e) Dropwise adding a pH regulator with the mass concentration of 15%, adjusting the pH value to 8.5, stirring at the rotating speed of 400r/min for 30min, and thus obtaining the organic silicon modified water-soluble acrylic resin.
(2) Preparing the environment-friendly water-based varnish for the photovoltaic glass glaze:
under the stirring condition, 65 parts of alcohol ether solvent, 25 parts of organic silicon modified water-soluble acrylic resin and 5 parts of rheological anti-settling agent are sequentially put into a stirring kettle in parts by weight, stirred uniformly at the stirring speed of 300r/min, kept stirred, heated to 90 ℃, cooled after being completely dissolved. And keeping stirring and cooling to 40 ℃, putting 5 parts of dispersing agent into a stirring kettle, and stirring uniformly for 30min to obtain the environment-friendly water-based ink mixing oil for the photovoltaic glass glaze.
Comparative example 1
When the organic silicon modified water-soluble acrylic resin in the comparative example is prepared, the organic silicon modified water-soluble acrylic resin is prepared by a method of pre-polymerizing the water-soluble acrylic resin and supplementing organic silicon monomers and residual alcohol ether solvents after the completion, and the method specifically comprises the following steps:
(1) Polymerization preparation of organosilicon modified water-soluble acrylic resin:
(a) Keeping the reaction kettle clean and anhydrous, adding 40 parts by weight of alcohol ether solvent, introducing nitrogen into the reaction kettle and keeping the nitrogen, introducing cooling water into a condensation pipe, and heating the alcohol ether solvent to 140 ℃.
(b) Taking another dispersion kettle, and sequentially adding 10 parts of tertiary carboxylic acid 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, 2 parts of a molecular weight regulator (chain transfer agent) and 3.5 parts of an initiator according to parts by weight; stirring and mixing uniformly, wherein the stirring speed is 300r/min, and the stirring time is 40min; dropwise adding the mixed solution into the reaction kettle in the step (a), wherein the dropwise adding time is 6 hours, and the temperature is controlled at 140 ℃; after the dropwise addition, the temperature is kept for 2 hours, and the temperature is controlled at 140 ℃.
(c) Adding 0.2 part by weight of initiator into the reaction kettle in the step (a), and continuing to react for 2 hours, wherein the temperature is controlled at 140 ℃.
(d) And (3) cooling to 80 ℃, adding 5 parts of organic silicon monomer and 40 parts of alcohol ether solvent by weight, and stirring and mixing uniformly, wherein the stirring speed is 400r/min, and the stirring time is 30min.
(e) And (3) dropwise adding a pH regulator with the mass concentration of 10%, adjusting the pH value to 8.0, stirring at the rotating speed of 400r/min for 20min, and thus obtaining the organic silicon modified water-soluble acrylic resin.
(2) Preparing the environment-friendly water-based varnish for the photovoltaic glass glaze:
under the stirring condition, 60 parts of alcohol ether solvent, 32.5 parts of organic silicon modified water-soluble acrylic resin and 5 parts of rheological anti-settling agent are sequentially put into a stirring kettle in parts by weight, stirred to be uniform, the stirring speed is 300r/min, stirring is kept, the temperature is raised to 90 ℃, and the temperature is reduced and the cooling is carried out after the alcohol ether solvent, the organic silicon modified water-soluble acrylic resin and the rheological anti-settling agent are completely dissolved. And keeping stirring and cooling to 50 ℃, putting 2.5 parts of dispersing agent into a stirring kettle, and stirring uniformly for 20min to obtain the environment-friendly water-based varnish for photovoltaic glass glaze.
Example 4
The environment-friendly water-based varnish for photovoltaic glass glaze materials prepared in examples 1 to 3 and comparative example 1 was prepared to obtain a water-based white glaze material according to the following method: putting the ink mixing oil into a container, starting stirring at the rotating speed of 800-1000r/min, sequentially putting the low-melting-point glass powder and the titanium dioxide into the container, and stirring until the mixture is uniform and free of agglomeration for 90-120min; regulating the rotating speed to 400-600r/min, sequentially putting the flatting agent and the defoaming agent into a container, and stirring uniformly for 20-30min. And then the water-based white glaze is obtained by three-roller milling.
The test results of the aqueous white glaze prepared by correspondingly applying the environment-friendly aqueous varnish to the photovoltaic glass glazes in the examples 1 to 3 and the comparative example 1 on the photovoltaic assembly back plate glass after curing or toughening are shown in table 1.
TABLE 1 test indexes described in examples 1 to 3 and comparative example 1
The results in Table 1 show that the screen printing properties, the adhesion to photovoltaic glass after thermal curing and the adhesion in examples 1 to 3 are superior to those of comparative example 1. Compared with the method of pre-synthesizing silica sol or pre-polymerizing acrylic resin, the method in examples 1-3 has simplified process, uniformly pre-mixing the organosilicon monomer and other raw materials, dropwise adding the mixture into the alcohol ether solvent for reaction, and synchronously performing double bond fracture and polymerization with the acrylic acid (ester) monomer and styrene, wherein the organosilicon monomer has better uniformity. And the organosilicon can reduce the surface energy, has better wettability to glass powder and titanium dioxide, and then increases the compatibility of the whole glaze system, and promotes the dispersion and grinding efficiency of the prepared white glaze.
The above embodiments are merely illustrative of the technical concept and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the content of the present invention and implement the invention, and not to limit the scope of the invention, and all equivalent changes or modifications made according to the spirit of the present invention should be covered by the scope of the present invention.
Claims (10)
1. The preparation method of the environment-friendly water-based varnish for the photovoltaic glass glaze is characterized by comprising the following steps:
(1) Preparing organic silicon modified water-soluble acrylic resin:
mixing an acrylic monomer and/or an acrylate monomer, styrene, an organic silicon monomer, a molecular weight regulator and a part of initiator, dropwise adding the mixture into a part of alcohol ether solvent with the temperature of 140-150 ℃ after uniform mixing, and carrying out heat preservation reaction for 1-2h after dropwise adding; adding the rest initiator into the system, and continuing to react for 1-2h; cooling to 70-80 deg.C, adding the rest alcohol ether solvent, and mixing; adjusting the pH value of the system to 8-9 to obtain the organic silicon modified water-soluble acrylic resin;
(2) Preparing the environment-friendly water-based varnish for the photovoltaic glass glaze:
under the condition of stirring, uniformly mixing an alcohol ether solvent, the organic silicon modified water-soluble acrylic resin and the rheological anti-settling agent, heating to 80-90 ℃, cooling to 40-50 ℃ after the organic silicon modified water-soluble acrylic resin and the rheological anti-settling agent are completely dissolved, adding a dispersing agent into the system, and uniformly mixing to obtain the environment-friendly water-based ink-regulating oil for the photovoltaic glass glaze.
2. The preparation method according to claim 1, wherein the environment-friendly aqueous varnish for photovoltaic glass glazes comprises, by weight, 60-80 parts of an alcohol ether solvent, 20-40 parts of an organosilicon modified water-soluble acrylic resin, 1-5 parts of a rheological anti-settling agent and 1-5 parts of a dispersant.
3. The preparation method according to claim 1, wherein the prepared environment-friendly water-based varnish for photovoltaic glass glaze has a solid content of 3 +/-1%; the viscosity is 100-500 mPa.s (25 +/-1 ℃).
4. The preparation method of claim 1, wherein the partial alcohol ether solvent accounts for 40-60% of the total mass of the alcohol ether solvent in the raw material of the organosilicon modified water-soluble acrylic resin; the part of the initiator accounts for 80-95% of the total amount of the initiator in the raw material of the organosilicon modified water-soluble acrylic resin.
5. The preparation method according to claim 1, wherein the dropping time is 6-8h, and the temperature of the system is controlled to 140-150 ℃ during the dropping.
6. The method according to claim 1, wherein nitrogen gas is introduced into the system and maintained during the preparation of the silicone-modified water-soluble acrylic resin.
7. The preparation method according to claim 1, wherein the organosilicon modified water-soluble acrylic resin comprises the following raw material components in parts by weight:
8. the preparation method according to claim 1, wherein the alcohol ether solvent in the environment-friendly aqueous varnish for photovoltaic glass glaze and/or the alcohol ether solvent in the organosilicon-modified water-soluble acrylic resin is selected from one or more of diethylene glycol butyl ether, dipropylene glycol methyl ether, tripropylene glycol methyl ether, dipropylene glycol butyl ether and tripropylene glycol butyl ether.
9. An environment-friendly aqueous varnish for photovoltaic glass glazes prepared by the preparation method according to any one of claims 1 to 8.
10. An environment-friendly water-based white glaze for photovoltaic glass glaze, which is characterized in that the environment-friendly water-based ink mixing oil for photovoltaic glass glaze prepared by the preparation method of any one of claims 1 to 8 is put into a container, stirring is started, low-melting glass powder and titanium dioxide are sequentially put into the container, stirring is carried out until the mixture is uniform and no agglomeration exists, a leveling agent and a defoaming agent are sequentially put into the container, stirring is carried out until the mixture is uniform, and rolling and grinding are carried out to obtain the water-based white glaze.
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| CN113998891B (en) * | 2021-12-15 | 2023-10-20 | 安徽工程大学 | Low-titanium high-reflection glaze and preparation method thereof, and high-reflection photovoltaic backboard glass and preparation method thereof |
| CN114958075B (en) * | 2022-06-06 | 2023-05-12 | 东莞南玻太阳能玻璃有限公司 | Water-based reflective ink, preparation method thereof and application thereof in photovoltaic glass |
| CN115073002B (en) * | 2022-06-30 | 2023-07-07 | 吴江南玻玻璃有限公司 | Combined glaze suitable for laminated glaze plating and preparation method and application thereof |
| CN116239312A (en) * | 2023-03-17 | 2023-06-09 | 江西盛富莱光学科技股份有限公司 | Environment-friendly high-reflection ink coating for photovoltaic glass and preparation method thereof |
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