CN113603362B - Water-based environment-friendly white glaze with high adhesion and weather resistance for photovoltaic back plate glass and preparation method thereof - Google Patents
Water-based environment-friendly white glaze with high adhesion and weather resistance for photovoltaic back plate glass and preparation method thereof Download PDFInfo
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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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- 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
- C03C1/02—Pretreated ingredients
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- 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
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/006—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character
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- 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
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- 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
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Abstract
The invention discloses a high-adhesion high-weather-resistance water-based environment-friendly white glaze for photovoltaic back plate glass, which consists of ink adjusting oil, a dispersing agent, low-melting-point glass powder, titanium dioxide, a flatting agent and a defoaming agent, can be used for preparing a high-adhesion high-weather-resistance glaze layer of the photovoltaic back plate glass, is applied to a photovoltaic assembly, has the reflectivity of more than 78 percent and the adhesion of 0 level, and has the reflectivity attenuation rate average value of less than 1 percent in weather resistance tests (ultraviolet resistance and PCT aging resistance).
Description
Technical Field
The invention relates to the technical field of photovoltaic modules and glass glazes, in particular to a water-based environment-friendly white glaze with high adhesion and high weather resistance for photovoltaic back plate glass, a preparation method of the water-based environment-friendly white glaze and application of the water-based environment-friendly white glaze in photovoltaic module glass.
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's efficiency, except using white encapsulating material such as EVA and POE, still can pass through on the silk screen printing technology coating photovoltaic backplate glass white frit, can reflect the light that sees through the battery piece clearance to the battery piece surface through the glaze layer and be recycled, and then promote photovoltaic assembly's conversion efficiency.
However, the existing white glaze has some problems to be solved, such as adhesion force can not reach grade 1 (generally grade 2); the reflectivity attenuation rate in weather resistance tests (ultraviolet resistance and PCT aging resistance) is large, and the glass is not suitable for photovoltaic glass.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide the water-based environment-friendly white glaze with high adhesion and high weather resistance for the photovoltaic back plate glass, and the water-based environment-friendly white glaze has excellent adhesion and weather resistance when being applied to the photovoltaic glass.
The invention adopts the following technical scheme:
the water-based environment-friendly white glaze with high adhesive force and high weather resistance for the photovoltaic back plate glass comprises the following raw material components in parts by weight:
the ink adjusting oil comprises organic silicon modified water-soluble acrylic resin, and the organic silicon modified water-soluble acrylic resin is prepared by a homogeneous one-step method; the low-melting-point glass powder is a lead-free cadmium low-melting-point Bi-Zn-B system.
The organic silicon monomer in the raw material components of the organic silicon modified water-soluble acrylic resin used for the varnish has better wettability on low-melting-point glass powder and titanium dioxide coated by silicon oxide and aluminum oxide, so that the compatibility of the whole system is increased, and the dispersion and grinding efficiency of the prepared white glaze is improved.
According to some preferred embodiments of the invention, the varnish 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 and 1-5 parts of rheological anti-settling agent; the raw material components of the organic silicon modified water-soluble acrylic resin comprise 5-10 parts of organic silicon monomer.
According to some preferred embodiment aspects of the invention, the alcohol ether solvent in the varnish 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 embodiments of the present invention, the silicone-modified water-soluble acrylic resin has a viscosity of 10000 ± 2000mpa · s (25 ± 1 ℃); the solid content of the organic silicon modified water-soluble acrylic resin is 50-60%. The organic silicon modified water-soluble acrylic resin with the viscosity range is prepared into water-based varnish with moderate viscosity on the basis of ensuring the number of effective adhesives, and the integral viscosity of a glaze system is ensured after functional fillers such as glass powder, titanium dioxide and the like in a quantitative range are added.
According to some preferred embodiments of the invention, the rheological anti-settling agent is selected from one or more of fumed silica, organobentonite, and modified polyurea solution.
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 at 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 adjusting the pH value of the system to 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 present invention, the part of the 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 partial initiator accounts for 80-95% of the total mass of the initiators in the raw materials 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 bonds are cracked and polymerized synchronously with the acrylic monomer and/or acrylate monomer and 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, further increases the compatibility of the whole 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.
In some embodiments of the present invention, the polymerization preparation of the silicone-modified water-soluble acrylic resin specifically comprises the following steps:
(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 of alcohol ether solvent, stirring at 400-500r/min for 20-30min.
(e) Stirring and dripping 10-15% of pH regulator, adjusting pH value to 8.0-9.0, stirring at 400-500r/min for 20-30min.
According to some preferred embodiment aspects of the present invention, the alcohol ether solvent in the silicone-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 invention, 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. The organosilicon monomer and other raw materials are mixed uniformly in advance, and then the mixture is dripped into an alcohol ether solvent to react, and the double bonds are cracked and polymerized synchronously with an acrylic monomer and/or an acrylate monomer and styrene, so that the organosilicon monomer has better uniformity. 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 water-based environment-friendly white glaze.
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 embodiments of the invention, the dispersant is an aqueous high molecular polymer, such as TEGO 755W, a winning creation.
According to some preferred embodiments of the present invention, the low melting point glass frit has a softening temperature of 400 to 500 ℃, preferably 450 ℃, and a total melting temperature of 500 to 550 ℃, preferably 520 ℃, so that it is aqueousThe environment-friendly white glaze is completely melted in a short time within the tempering temperature range of 600-720 ℃, thereby ensuring the high adhesive force of the glaze layer. The linear expansion coefficient of the sheet glass is generally 85 x 10 -7 The low-melting-point glass powder has a linear expansion coefficient of 75-80 to 10 and/or more than one hundred thousand atoms (30-300℃) -7 The temperature is 30-300 ℃, the coefficient of linear expansion of the glaze layer is lower than that of the base glass, the shrinkage of the glaze layer is smaller than that of the base in the cooling process, the glaze layer is automatically deformed under the self-shrinkage effect and also under the compression effect given by the shrinkage of the base, and the permanent compression stress is generated due to the compression elastic deformation, so that the adhesion of the glaze layer is improved.
According to some preferred embodiments of the invention, the titanium dioxide is prepared by a chlorination method, the titanium dioxide prepared by the method has extremely low impurity content, and the silicon oxide and the aluminum oxide are used for coating, so that lattice defects caused by the titanium dioxide under the ultraviolet irradiation condition can be blocked, light activation points on the surface of the titanium dioxide are shielded, and the weather resistance and the chemical stability of the titanium dioxide are improved.
According to some preferred embodiments of the present invention, the raw material composition of the aqueous environment-friendly white glaze further comprises 0.5 to 1.0 part of a leveling agent and 0.5 to 1.0 part of an antifoaming agent. In some embodiments, the leveling agent is a polyether siloxane copolymer; preferably, the defoamer is a polyether modified polydimethylsiloxane interpolymer.
The invention also provides a preparation method of the water-based environment-friendly white glaze with high adhesion and weather resistance for the photovoltaic back plate glass, which comprises the following steps:
(1) Preparing ink mixing oil: under the stirring condition, sequentially putting the alcohol ether solvent, the organic silicon modified water-soluble acrylic resin and the rheological anti-settling agent into a stirring kettle according to the parts by weight, and stirring the mixture until the mixture is uniform to obtain the varnish. The stirring speed is 400-600r/min, and the stirring time is 40-60min.
(2) Preparing water-based environment-friendly white glaze: putting the ink regulating oil into a container according to the weight part, starting stirring, and controlling the rotating speed to be 400-600r/min; putting the dispersing agent into a container, and stirring uniformly for 20-30 min; regulating the rotating speed to 800-1000r/min, sequentially putting the low-melting-point glass powder and the titanium dioxide into a 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 grinding by a three-roll machine (three-roll grinding), wherein the fineness is less than 10 mu m, and obtaining the water-based environment-friendly white glaze.
Due to the adoption of the technical scheme, compared with the prior art, the invention has the following advantages: the water-based environment-friendly white glaze with high adhesion and high weather resistance for the photovoltaic back plate glass is prepared by selecting the low-melting-point glass powder with the softening temperature of 400-500 ℃ and the full-melting temperature of 500-550 ℃, so that the water-based environment-friendly white glaze is completely melted in a short time within the tempering temperature range of 600-720 ℃, and the high adhesion of a glaze layer is further ensured. The coefficient of expansion of the sheet glass is generally 85 x 10 -7 The low-melting point glass powder has a linear expansion coefficient of 75-80 x 10 at a temperature of 30-300 DEG C -7 The temperature is 30-300 ℃, the coefficient of linear expansion of the glaze layer is lower than that of the base glass, the shrinkage of the glaze layer in the cooling process is smaller than that of the base, the glaze layer is automatically deformed under the self-shrinkage action and is also subjected to the compression action given by the shrinkage of the base, and the permanent compression stress is generated due to the compression elastic deformation, so that the adhesion of the glaze layer is improved. The titanium dioxide is prepared by a chlorination method, the content of impurities in the titanium dioxide prepared by the method is extremely low, and the silicon oxide and the aluminum oxide are used for coating, so that the lattice defect of the titanium dioxide caused under the ultraviolet irradiation condition can be blocked, the photoactivation point on the surface of the titanium dioxide is shielded, and the weather resistance and the chemical stability of the titanium dioxide are improved.
Detailed Description
In order to make those skilled in the art better understand the technical solutions of the present invention, the technical solutions will be clearly and completely described below with reference to 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 of the 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 of the water-based environment-friendly white glaze with high adhesion and weather resistance for the photovoltaic back plate glass 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, keeping the reaction kettle, 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) And (3) 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 water-based varnish:
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, and are stirred uniformly at the stirring speed of 400r/min for 60min to obtain the water-based ink-regulating oil.
(3) Preparation of water-based environment-friendly white glaze
The water-based environment-friendly white glaze comprises the following raw material components in parts by weight:
putting the ink adjusting oil into a container according to the parts by weight, and stirring at the rotating speed of 400r/min; putting the dispersing agent into a container, and stirring uniformly for 20min; regulating the rotating speed to 1000r/min, sequentially putting the low-melting-point glass powder and the titanium dioxide into a container according to the parts by weight, and stirring until the mixture is uniform and free of agglomeration for 900min; regulating the rotating speed to 400r/min, sequentially putting the flatting agent and the defoaming agent into a container, and stirring uniformly for 30min. And then the water-based environment-friendly white glaze is obtained by three-roller milling to obtain the fineness of less than 10 mu m.
Example 2
The preparation of the water-based environment-friendly white glaze for the photovoltaic back plate glass with high adhesion and high weather resistance 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 150 ℃.
(b) Taking another dispersion kettle, and sequentially adding 15 parts of tertiary carboxylic 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 organosilicon 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 reaction is carried out for 2 hours under the condition of heat preservation, and the temperature is controlled at 150 ℃.
(c) Adding 0.3 part of initiator into the reaction kettle in the step (a) by weight part, and continuing to react for 2 hours at the temperature of 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 water-based varnish:
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 and stirred uniformly, the stirring speed is 400r/min, and the stirring time is 50min, so that the water-based ink-adjusting oil is obtained.
(3) Preparation of water-based environment-friendly white glaze
The white glaze comprises the following raw materials in parts by weight:
putting the ink adjusting oil into a container according to the parts by weight, and stirring at the rotating speed of 600r/min; putting the dispersing agent into a container, and stirring uniformly for 20min; regulating the rotating speed to 800r/min, sequentially putting the low-melting-point glass powder and the titanium dioxide into a container according to the weight parts, and stirring until the mixture is uniform and free of agglomeration for 120min; regulating the rotating speed to 400r/min, sequentially putting the flatting agent and the defoaming agent into a container, and stirring uniformly for 20min. And then the water-based environment-friendly white glaze is obtained by three-roller milling to obtain the fineness of less than 10 mu m.
Example 3
The preparation of the water-based environment-friendly white glaze for the photovoltaic back plate glass with high adhesion and high weather resistance in the embodiment comprises the following steps:
(1) Polymerization preparation of 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 145 ℃.
(b) Taking another dispersion kettle, and sequentially adding 12 parts of tertiary carboxylic 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 organosilicon 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 by weight into the reaction kettle in the step (a), and continuing the reaction for 1 hour, wherein the temperature is controlled at 145 ℃.
(d) Cooling to 75 ℃, adding 30 parts by weight of alcohol ether solvent, and uniformly stirring and mixing, wherein the stirring speed is 400r/min, and the stirring time is 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 water-based varnish:
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, and are stirred uniformly at the stirring speed of 400r/min for 50min to obtain the water-based ink-regulating oil.
(3) Preparation of water-based environment-friendly white glaze
The white glaze comprises the following raw materials in parts by weight:
putting the ink adjusting oil into a container according to the parts by weight, and stirring at the rotating speed of 400r/min; putting the dispersing agent into a container according to the weight parts, and stirring the dispersing agent uniformly for 25min; regulating the rotating speed to 1000r/min, sequentially putting the low-melting-point glass powder and the titanium dioxide into a container, and stirring until the mixture is uniform and free of agglomeration for 100min; adjusting the rotating speed to 400r/min, sequentially putting the flatting agent and the defoaming agent into a container, and stirring the mixture until the mixture is uniform, wherein the stirring time is 20min. And then the water-based environment-friendly white glaze is obtained by three-roller milling to obtain the fineness of less than 10 mu m.
Comparative example 1
The preparation of the white glaze in this comparative example differs from the previous examples mainly in that the titanium dioxide in this comparative example was prepared by the sulfuric acid method and was not coated with silica and alumina. The preparation of the white glaze in this comparative example comprises the following steps:
(1) Polymerization preparation of 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 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 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 water-based varnish:
under the stirring condition, sequentially putting 60 parts by weight of alcohol ether solvent, 32.5 parts by weight of organic silicon modified water-soluble acrylic resin and 5 parts by weight of rheological anti-settling agent into a stirring kettle, and stirring uniformly at the stirring speed of 400r/min for 60min to obtain the water-based varnish.
(3) Preparation of water-based environment-friendly white glaze
The water-based environment-friendly white glaze comprises the following raw material components in parts by weight:
according to the weight parts, the ink regulating oil is put into a container, and stirring is started, wherein the rotating speed is 400r/min; putting the dispersing agent into a container, and stirring uniformly for 20min; regulating the rotating speed to 1000r/min, sequentially putting the low-melting-point glass powder and titanium dioxide in a container according to the parts by weight, wherein the titanium dioxide is prepared by a sulfuric acid method, is not subjected to coating treatment of silicon peroxide and alumina, and is stirred until the mixture is uniform and free of agglomeration, and the stirring time is 900min; regulating the rotating speed to 400r/min, sequentially putting the flatting agent and the defoaming agent into a container, and stirring uniformly for 30min. And then the water-based environment-friendly white glaze is obtained by three-roller milling to obtain the fineness of less than 10 mu m.
Comparative example 2
The main difference between the preparation of the white glaze in this comparative example and the previous examples is that the low melting point glass frit used in this comparative example has a softening temperature of 480 ℃, a total melting temperature of 550 ℃ and a coefficient of linear expansion of 110 to 115 x 10 at 30 to 300 ℃ -7 and/K. The preparation of the white glaze in this comparative example comprises the following steps:
(1) Polymerization preparation of 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 water-based varnish:
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, and are stirred uniformly at the stirring speed of 400r/min for 60min to obtain the water-based ink-regulating oil.
(3) Preparation of water-based environment-friendly white glaze
The water-based environment-friendly white glaze comprises the following raw material components in parts by weight:
putting the ink adjusting oil into a container according to the parts by weight, and stirring at the rotating speed of 400r/min; dispersing agentPutting into a container, and stirring for 20min; regulating the rotating speed to 1000r/min, and sequentially putting the low-melting-point glass powder and the titanium dioxide into a container according to the parts by weight, wherein the softening temperature of the low-melting-point glass powder is 480 ℃, the total melting temperature is 550 ℃, and the linear expansion coefficient of the low-melting-point glass powder is 110-115 x 10 at the temperature of 30-300 DEG C -7 and/K is used. Stirring for 900min until the mixture is uniform and has no agglomeration; regulating the rotating speed to 400r/min, sequentially putting the flatting agent and the defoaming agent into a container, and stirring uniformly for 30min. And then the water-based environment-friendly white glaze is obtained by three-roller milling to obtain the fineness of less than 10 mu m.
Example 4
The aqueous environmentally friendly white glaze in examples 1 to 3 and comparative example 1 was applied to photovoltaic module glass and cured for testing, and the results are shown in table 1.
TABLE 1 test results
The results in Table 1 show that the UV resistance and the PCT aging resistance of examples 1 to 3 are superior to those of comparative example 1, and the short side part of the glass of comparative example 2 has cracks and the adhesion is grade 1. In the embodiment, the softening temperature of the low-melting-point glass powder is 400-500 ℃, the full-melting temperature is 500-550 ℃, so that the water-based environment-friendly white glaze is completely melted in a short time within the tempering temperature range of 600-720 ℃, and the high adhesive force of the glaze layer is further ensured. The coefficient of expansion of the sheet glass is generally 85 x 10 -7 The low-melting point glass powder has a linear expansion coefficient of 75-80 x 10 at a temperature of 30-300 DEG C -7 The temperature is 30-300 ℃, the coefficient of linear expansion of the glaze layer is lower than that of the base glass, the shrinkage of the glaze layer in the cooling process is smaller than that of the base, the glaze layer is automatically deformed under the self-shrinkage action and is also subjected to the compression action given by the shrinkage of the base, and the permanent compression stress is generated due to the compression elastic deformation, so that the adhesion of the glaze layer is improved. The titanium dioxide is prepared by a chlorination method, the content of impurities in the titanium dioxide prepared by the method is extremely low, and the silicon oxide and the aluminum oxide are used for coating, so that the lattice defect of the titanium dioxide caused under the ultraviolet irradiation condition can be blocked, and the surface of the titanium dioxide is shieldedPhotoactivation sites on the faces, which improve their weatherability and chemical stability.
The water-based environment-friendly white glaze with high adhesion and high weather resistance for the photovoltaic back plate glass can be used for a glaze layer with high adhesion and high weather resistance for the photovoltaic back plate glass, the reflectivity is more than 78%, the adhesion reaches 0 level, and the mean values of the reflectivity attenuation rates of weather resistance tests (ultraviolet resistance and PCT aging resistance) are less than 1%.
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 (5)
1. The water-based environment-friendly white glaze with high adhesive force and high weather resistance for the photovoltaic back plate glass is characterized by comprising the following raw material components in parts by weight:
The ink mixing oil comprises organic silicon modified water-soluble acrylic resin, and the organic silicon modified water-soluble acrylic resin is prepared by a homogeneous one-step method; the low-melting-point glass powder is a lead-free cadmium low-melting-point Bi-Zn-B system;
the ink mixing oil comprises the following raw material components in parts by weight: 60-80 parts of an alcohol ether solvent, 20-40 parts of organic silicon modified water-soluble acrylic resin and 1-5 parts of a rheological anti-settling agent; the raw material components of the organic silicon modified water-soluble acrylic resin comprise 5-10 parts of organic silicon monomer;
the organic silicon modified water-soluble acrylic resin is prepared by the following method:
mixing an acrylic monomer and/or an acrylate monomer, styrene, an organic silicon monomer, a molecular weight regulator and part of an initiator, dropwise adding the mixture into part of an alcohol ether solvent at 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 a system to be 8-9 by using a pH regulator to obtain the organic silicon modified water-soluble acrylic resin; the pH regulator is an organic amine neutralizer;
the organic silicon modified water-soluble acrylic resin comprises the following raw material components in parts by weight:
The softening temperature of the low-melting-point glass powder is 400-500 ℃, the total melting temperature is 500-550 ℃, and the linear expansion coefficient of the low-melting-point glass powder is 75-80 x 10 at 30-300 DEG C -7 /K；
The titanium dioxide is prepared by a chlorination method, and silicon oxide and aluminum oxide are used for carrying out compact inorganic coating surface treatment.
2. The water-based environment-friendly white glaze for photovoltaic back plate glass with high adhesion and weather resistance as claimed in claim 1, wherein the viscosity of the organosilicon-modified water-soluble acrylic resin is 10000 ± 2000 mpa-s at 25 ± 1 ℃; the solid content of the organic silicon modified water-soluble acrylic resin is 50-60%.
3. The water-based environment-friendly white glaze for photovoltaic back plate glass with high adhesion and high weather resistance as claimed in claim 1, wherein the raw material components of the white glaze further comprise 0.5-1.0 part of leveling agent and 0.5-1.0 part of defoaming agent.
4. The preparation method of the water-based environment-friendly white glaze for the high-adhesion high-weather-resistance photovoltaic back plate glass as described in any one of claims 1 to 3, which comprises the following steps:
(1) Preparing varnish: uniformly mixing an alcohol ether solvent, organic silicon modified water-soluble acrylic resin and a rheological anti-settling agent to obtain varnish;
(2) Preparing water-based environment-friendly white glaze: mixing the ink mixing oil and the dispersing agent uniformly, adding the low-melting-point glass powder and the titanium dioxide under stirring, adding the leveling agent and the defoaming agent after dispersing uniformly, mixing uniformly, and grinding by a three-roll machine to obtain the white glaze.
5. The application of the water-based environment-friendly white glaze with high adhesion and high weather resistance for the photovoltaic back plate glass as described in any one of claims 1 to 3 in the photovoltaic back plate glass.
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| CN114014545B (en) * | 2021-12-15 | 2023-11-07 | 安徽工程大学 | Water-based glaze as well as preparation method and application thereof |
| CN114853352B (en) * | 2022-05-13 | 2023-08-25 | 江苏秀强玻璃工艺股份有限公司 | Construction process of high-temperature-resistant and acid-resistant high-temperature uv texture |
| CN114956570B (en) * | 2022-05-27 | 2023-08-11 | 黄山市晶特美新材料有限公司 | White reflection-increasing glass slurry for crystalline silicon component and preparation method thereof |
| 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 |
| CN115010382B (en) * | 2022-07-12 | 2024-02-06 | 吴江南玻玻璃有限公司 | Combined material suitable for photovoltaic glass and preparation method and application thereof |
| CN115772004A (en) * | 2022-12-19 | 2023-03-10 | 东莞南玻太阳能玻璃有限公司 | Photovoltaic glaze, photovoltaic back plate glass, preparation method of photovoltaic back plate glass and double-glass photovoltaic module |
| CN116265534A (en) * | 2023-01-06 | 2023-06-20 | 宸光(常州)新材料科技有限公司 | Water-based high-reflection ink for photovoltaic backboard glass and preparation method thereof |
| CN116730629A (en) * | 2023-05-25 | 2023-09-12 | 华南理工大学 | Low-melting-point glass powder for high-temperature-resistant high-humidity photovoltaic glass slurry, and preparation method and application thereof |
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