CN115612347B - Environment-friendly water-based ink-transfer oil for photovoltaic glass glaze, preparation method of environment-friendly water-based ink-transfer oil and water-based white glaze - Google Patents
Environment-friendly water-based ink-transfer oil for photovoltaic glass glaze, preparation method of environment-friendly water-based ink-transfer oil and water-based white glaze Download PDFInfo
- Publication number
- CN115612347B CN115612347B CN202211374408.6A CN202211374408A CN115612347B CN 115612347 B CN115612347 B CN 115612347B CN 202211374408 A CN202211374408 A CN 202211374408A CN 115612347 B CN115612347 B CN 115612347B
- Authority
- CN
- China
- Prior art keywords
- water
- parts
- acrylic resin
- environment
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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 stirring condition, uniformly mixing an alcohol ether solvent, an organosilicon modified water-soluble acrylic resin and a rheological anti-settling agent, heating to 80-90 ℃, cooling to 40-50 ℃ after the organosilicon modified water-soluble acrylic resin and the rheological anti-settling agent are completely dissolved, adding a dispersing agent into a system, and uniformly mixing to obtain the environment-friendly water-based ink-transfer oil for the photovoltaic glass glaze. Compared with the mode of synthesizing silica sol in advance or polymerizing acrylic resin in advance, the preparation method has the advantages that the process is simplified, the organosilicon monomer and other raw materials are mixed uniformly in advance and then added into alcohol ether solvent in a dropwise manner for reaction, and the organosilicon monomer is better in uniformity when the organosilicon monomer is subjected to double bond breaking and polymerization synchronously with acrylic acid (ester) monomer and styrene. And the organosilicon can reduce the surface energy, and has better wettability to glass powder and titanium pigment.
Description
The application is a divisional application of an invention patent application with the application date of 2021, 6 and 25, the application number of 2021107127802 and the invention name of '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-transfer oil for photovoltaic glass glaze, a preparation method of the water-based ink-transfer oil and application of the water-based ink-transfer 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 parallel through wires and are converged at the lead ends to form the photovoltaic cell module, and the double-glass photovoltaic module is particularly suitable for photovoltaic power stations in relatively harsh climatic environments, such as areas with higher humidity. In order to effectively improve the efficiency of the double-glass assembly, besides using EVA, POE and other white packaging materials, the photovoltaic glass glaze can be coated on the back plate glass.
The photovoltaic glass glaze consists of glass powder, titanium pigment, varnish and other parts, wherein the polymer resin in the varnish is used as an adhesive, and the glaze system is borne on the back plate glass during silk screen printing, and provides good adhesive force after thermal curing (180-220 ℃). The ink-setting oil affects the mutual adaptability of glass powder, titanium pigment and the like, the screen printing property and the storage property of glaze.
In the prior art, most of ink-setting oil used for the photovoltaic glass glaze has large smell, is not environment-friendly, has poor adhesion with a glass substrate after heat curing (180-220 ℃), needs to be cleaned by using a solvent, has high comprehensive cost, has higher volatile VOCs content, 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 organosilicon modified water-soluble acrylic resin is prepared by a homogeneous one-step method, 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 preparing white glaze.
The invention adopts the following technical scheme:
the environment-friendly water-based ink varnish 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 organosilicon modified water-soluble acrylic resin, 1-5 parts of rheological anti-settling agent and 1-5 parts of dispersing agent; the organosilicon modified water-soluble acrylic resin is prepared by a homogeneous phase one-step method, the solid content of the organosilicon modified water-soluble acrylic resin is 55+/-1%, and the viscosity is 10000+/-2000 mpa.s (25+/-1 ℃). The organosilicon modified water-soluble acrylic resin with the viscosity range is prepared into water-based varnish with moderate viscosity on the basis of ensuring the quantity of effective binders, and the glaze is prepared by adding functional fillers such as glass powder, titanium pigment and the like with a quantitative range, so that the overall 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 acrylic acid monomer and/or acrylic ester monomer, styrene, organic silicon monomer, molecular weight regulator and partial initiator, dripping into partial alcohol ether solvent at 140-150deg.C for 6-8 hr, and maintaining the temperature for 1-2 hr; adding the rest initiator into the system, and continuing the reaction for 1-2h; cooling to 70-80deg.C, continuously adding the rest alcohol ether solvent, and mixing; and regulating the pH value of the system to 8-9 by using an organic amine neutralizer to obtain the organosilicon modified water-soluble acrylic resin.
According to some preferred embodiments of the present invention, the partial alcohol ether solvent accounts for 40-60% of the total amount of alcohol ether solvent in the silicone-modified water-soluble acrylic resin raw material; the partial initiator accounts for 80-95% of the total amount of the initiator in the organosilicon modified water-soluble acrylic resin raw material. The alcohol ether solvent is added twice, so that the heating time in the synthesis process of the organosilicon modified water-soluble acrylic resin is reduced, and the cooling time and the cooling water consumption are reduced, thereby reducing the energy consumption in the production process. The initiator is added in two times, and the aim is to initiate the secondary additional initiator at 140-150 ℃ and to re-polymerize the residual monomer, thereby improving the conversion rate of the organosilicon modified water-soluble acrylic resin.
The preparation method has the following two advantages:
(1) The preparation method comprises the steps of firstly uniformly mixing an acrylic acid monomer and/or an acrylic ester monomer, styrene, an organosilicon monomer, a molecular weight regulator, a part of initiator and the like, dropwise adding the mixture into a reaction kettle under a homogeneous condition, increasing molecular chains in the whole process through breaking and polymerization of double bonds such as acrylic acid (ester), styrene, vinyl and the like, and controlling the polymerization molecular weight through the molecular weight regulator (chain transfer agent) at the same time, so that the viscosity of the organosilicon modified water-soluble acrylic resin obtained by a homogeneous one-step method is relatively low. Compared with the mode of pre-synthesizing silica sol or pre-polymerizing acrylic resin, the method has the advantages that the process is simplified, the organosilicon monomer and other raw materials are pre-mixed uniformly, then the mixture is dripped into an alcohol ether solvent for reaction, the double bond breaking and polymerization are synchronously carried out with the acrylic acid (ester) monomer and the styrene, and the organosilicon monomer is better at the same time. And the organosilicon can reduce the surface energy, has better wettability to glass powder and titanium pigment, further increases the compatibility of the whole glaze system, and improves the dispersion and grinding efficiency of preparing white glaze.
(2) The temperature of the system is reduced to 70-80 ℃, and then the rest alcohol ether solvent is added for continuous stirring and even mixing. By the method, the heating time in the synthesis process of the organosilicon modified water-based acrylic resin can be reduced, and meanwhile, the cooling time and the using amount of cooling water are reduced, so that the energy consumption in the production process is reduced.
According to some preferred embodiments of the invention, the acrylic monomer is an acrylic monomer and/or an acrylate monomer. The acrylic acid monomer is acrylic acid; the acrylic ester monomer is one or more of glycidyl versatate, hydroxyethyl acrylate, methyl methacrylate, isobornyl methacrylate and butyl acrylate; the organosilicon monomer is vinyl triethoxysilane and/or 3- (methacryloyloxy) propyl trimethoxysilane.
According to some preferred embodiments of the present invention, the molecular weight regulator (chain transfer agent) is a 2, 4-diphenyl-4-methyl-1-pentenyl methyl styrene 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 present invention, the alcohol ether solvent in the environmentally friendly aqueous varnish for photovoltaic glass frit and/or 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 embodiments of the present invention, the rheology anti-settling agent in the environmentally friendly aqueous varnish for photovoltaic glass frit is one or more of fumed silica, organobentonite, modified polyurea solution and ethylcellulose.
According to some preferred embodiments of the invention, the dispersant in the environmentally friendly aqueous varnish for photovoltaic glass frit is an aqueous 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 organosilicon modified water-soluble acrylic resin comprises the following steps:
mixing acrylic acid monomer and/or acrylic ester monomer, styrene, organic silicon monomer, molecular weight regulator and partial initiator, dripping into partial alcohol ether solvent at 140-150deg.C for 6-8 hr, and maintaining the temperature for 1-2 hr; adding the rest initiator into the system, and continuing the reaction for 1-2h; cooling to 70-80deg.C, adding the rest alcohol ether solvent, and mixing; regulating the pH value of the system to 8-9 by a pH regulator to obtain the organosilicon modified water-soluble acrylic resin;
(2) Preparation of environment-friendly water-based ink varnish for photovoltaic glass glaze:
under the stirring condition, uniformly mixing an alcohol ether solvent, an organosilicon modified water-soluble acrylic resin and a rheological anti-settling agent, heating to 80-90 ℃, cooling to 40-50 ℃ after the organosilicon modified water-soluble acrylic resin and the rheological anti-settling agent are completely dissolved, adding a dispersing agent into a system, and uniformly mixing to obtain the environment-friendly water-based ink-transfer oil for the photovoltaic glass glaze.
The solid content of the environment-friendly water-based ink-regulating oil for the photovoltaic glass glaze prepared by the preparation method is 3+/-1%; the viscosity is 100-500 mpa.s (25+ -1deg.C).
In some embodiments of the present invention, the method specifically comprises the following steps:
(1) Preparation of organosilicon 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, introducing cooling water into a condensing tube, and heating the alcohol ether solvent to 140-150 ℃.
(b) Taking a dispersing kettle, and sequentially adding 10-15 parts of tertiary 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 an organosilicon monomer, 1-2 parts of a molecular weight regulator (chain transfer agent) and 2-5 parts of an initiator according to parts by weight; stirring and mixing uniformly, wherein the stirring rotation speed is 200-300r/min, and the stirring time is 30-40min; dripping the mixed solution (a homogeneous system formed by mixing monomers, a molecular weight regulator (chain transfer agent) and an initiator) into the reaction kettle in the step (a) for 6-8h, wherein the temperature is controlled at 140-150 ℃; after the dripping is finished, the reaction is carried out for 1 to 2 hours at the temperature of 140 to 150 ℃.
(c) Adding 0.1-0.3 part of initiator into the reaction kettle in the step (a) according to the weight parts, and continuously reacting for 1-2h, wherein the temperature is controlled at 140-150 ℃.
(d) Cooling to 70-80 ℃, adding 20-40 parts of alcohol ether solvent according to parts by weight, stirring and mixing uniformly, wherein the stirring speed is 400-500r/min, and the stirring time is 20-30min.
(e) And (3) dropwise adding a pH regulator with the mass concentration of 10-15%, adjusting the pH value to 8.0-9.0, stirring at the stirring speed of 400-500r/min and stirring for 20-30min to obtain the organosilicon modified water-soluble acrylic resin.
(2) The preparation of the environment-friendly water-based varnish for the photovoltaic glass glaze comprises the following steps:
under the stirring condition, sequentially adding 60-80 parts of alcohol ether solvent, 20-40 parts of organosilicon modified water-soluble acrylic resin and 1-5 parts of rheological anti-settling agent into a stirring kettle according to parts by weight, stirring until the stirring speed is 200-300r/min, keeping stirring, heating to 80-90 ℃, and cooling after complete dissolution. Stirring and cooling to 40-50 ℃, putting 1-5 parts of dispersing agent into a stirring kettle, stirring uniformly for 20-30min, and obtaining the environment-friendly water-based ink-regulating oil for the photovoltaic glass glaze.
The invention also provides application of the environment-friendly water-based ink-regulating oil for the photovoltaic glass glaze in the water-based environment-friendly white glaze for the photovoltaic backboard glass. The aqueous environment-friendly white glaze consists of glass powder, titanium pigment, varnish and the like, wherein high molecular resin (organosilicon modified water-soluble acrylic resin) in the varnish is used as an adhesive, a bearing glaze system is arranged on backboard glass during silk screen printing, and good adhesive force is provided after thermal curing (180-220 ℃). The organosilicon modified water-soluble acrylic resin used in the environment-friendly water-based varnish for the photovoltaic glass glaze has better wettability to glass powder and titanium pigment, so that the compatibility of the whole system is increased, and the dispersion and grinding efficiency of preparing the white glaze is improved.
Due to the adoption of the technical scheme, compared with the prior art, the invention has the following advantages: the preparation method of the environment-friendly water-based ink-transfer oil for the photovoltaic glass glaze adopts the organic silicon modified water-soluble acrylic resin prepared by a homogeneous one-step method, compared with the mode of pre-synthesizing silica sol or pre-polymerizing acrylic resin, the preparation method has the advantages that the process is simplified, organic silicon monomers and other raw materials are uniformly mixed in advance and then are dripped into an alcohol ether solvent for reaction, and double bond breaking and polymerization are synchronously carried out with acrylic acid (ester) monomers and styrene, so that the uniformity of the organic silicon monomers is better. And the organosilicon can reduce the surface energy, has better wettability to glass powder and titanium pigment, further increases the compatibility of the whole system, and improves the dispersion and grinding efficiency of preparing the white glaze. And (3) in the later stage of synthesis of the organosilicon modified water-soluble acrylic resin, the temperature of the system is reduced to 70-80 ℃, and then the rest alcohol ether solvent is added for continuous stirring and uniform mixing. By the method, the heating time in the synthesis process of the organosilicon modified water-based acrylic resin can be reduced, and meanwhile, the cooling time and the using amount of cooling water are reduced, so that the energy consumption in the production process is reduced.
Detailed Description
In order to make the technical solution of the present invention better understood by those skilled in the art, the technical solution will be clearly and completely described in connection with the embodiments of the present invention, and it is obvious that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the present invention without making any inventive effort, shall fall within the scope of the present invention.
Example 1
The preparation of the environment-friendly water-based ink varnish for the photovoltaic glass glaze in the embodiment comprises the following steps:
(1) Preparation of organosilicon modified water-soluble acrylic resin:
(a) Keeping the reaction kettle clean and anhydrous, adding 40 parts of alcohol ether solvent according to parts by weight, introducing nitrogen into the reaction kettle, keeping, introducing cooling water into a condensing tube, and heating the alcohol ether solvent to 140 ℃.
(b) Taking a dispersing kettle, 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 (a) for 6 hours, and controlling the temperature at 140 ℃; after the dripping is finished, the reaction is carried out for 2 hours with the temperature controlled at 140 ℃.
(c) Adding 0.2 part of initiator into the reaction kettle in the step (a) according to parts by weight, and continuously reacting for 2 hours, wherein the temperature is controlled at 140 ℃.
(d) 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.
(e) And (3) 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 stirring for 20min to obtain the organosilicon modified water-soluble acrylic resin.
(2) Preparation of environment-friendly water-based ink varnish for photovoltaic glass glaze:
under the stirring condition, 60 parts of alcohol ether solvent, 32.5 parts of organosilicon modified water-soluble acrylic resin and 5 parts of rheological anti-settling agent are sequentially put into a stirring kettle according to parts by weight, stirred until being uniform, the stirring speed is 300r/min, kept stirring and heated to 90 ℃, and cooled after being completely dissolved. Stirring and cooling to 50 ℃, putting 2.5 parts of dispersing agent into a stirring kettle, stirring uniformly for 20min, and obtaining the environment-friendly water-based ink-transfer oil for the photovoltaic glass glaze.
Example 2
The preparation of the environment-friendly water-based ink varnish for the photovoltaic glass glaze in the embodiment comprises the following steps:
(1) Preparation of organosilicon modified water-soluble acrylic resin:
(a) Keeping the reaction kettle clean and anhydrous, adding 40 parts of alcohol ether solvent according to parts by weight, introducing nitrogen into the reaction kettle, keeping, introducing cooling water into a condensing tube, and heating the alcohol ether solvent to 150 ℃.
(b) Taking a dispersing kettle, and sequentially adding 15 parts of tertiary 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 rotating speed is 300r/min, and the stirring time is 30min; dripping the mixed solution into the reaction kettle in the step (a) for 6 hours, and controlling the temperature at 150 ℃; after the dripping is finished, the reaction is carried out for 2 hours with the temperature controlled at 150 ℃.
(c) Adding 0.3 part of initiator into the reaction kettle in the step (a) according to parts by weight, and continuously reacting for 2 hours, wherein the temperature is controlled at 150 ℃.
(d) Cooling to 70 ℃, 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.
(e) And (3) dropwise adding a pH regulator with the mass concentration of 15%, adjusting the pH value to 9.0, stirring at the speed of 400r/min and stirring for 30min to obtain the organosilicon modified water-soluble acrylic resin.
(2) Preparation of environment-friendly water-based ink varnish for photovoltaic glass glaze:
under the stirring condition, sequentially adding 70 parts of alcohol ether solvent, 25 parts of organosilicon modified water-soluble acrylic resin and 3 parts of rheological anti-settling agent into a stirring kettle according to parts by weight, stirring until the stirring speed is 300r/min, keeping stirring and heating to 85 ℃, and cooling after complete dissolution. Stirring and cooling to 50 ℃, putting 2 parts of dispersing agent into a stirring kettle, stirring uniformly for 25min, and obtaining the environment-friendly water-based ink-transfer oil for the photovoltaic glass glaze.
Example 3
The preparation of the environment-friendly water-based ink 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 of alcohol ether solvent according to parts by weight, introducing nitrogen into the reaction kettle, keeping, introducing cooling water into a condensing tube, and heating the alcohol ether solvent to 145 ℃.
(b) Taking a dispersing kettle, and sequentially adding 12 parts of tertiary 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 rotating speed is 300r/min, and the stirring time is 30min; dripping the mixed solution into the reaction kettle in the step (a) for 8 hours, and controlling the temperature at 145 ℃; after the dripping is finished, the reaction is carried out for 2 hours with the temperature controlled at 145 ℃.
(c) Adding 0.3 part of initiator into the reaction kettle in the step (a) according to parts by weight, and continuously reacting for 1h, wherein the temperature is controlled at 145 ℃.
(d) Cooling to 75 ℃, adding 30 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.
(e) And (3) dropwise adding a pH regulator with the mass concentration of 15%, adjusting the pH value to 8.5, stirring at the speed of 400r/min and stirring for 30min to obtain the organosilicon modified water-soluble acrylic resin.
(2) Preparation of environment-friendly water-based ink varnish for photovoltaic glass glaze:
under the stirring condition, 65 parts of alcohol ether solvent, 25 parts of organosilicon modified water-soluble acrylic resin and 5 parts of rheological anti-settling agent are sequentially put into a stirring kettle according to parts by weight, stirred until being uniform, the stirring speed is 300r/min, kept stirring and heated to 90 ℃, and cooled after being completely dissolved. Stirring and cooling to 40 ℃, putting 5 parts of dispersing agent into a stirring kettle, stirring uniformly for 30min, and obtaining the environment-friendly water-based ink-transfer oil for the photovoltaic glass glaze.
Comparative example 1
The organosilicon modified water-soluble acrylic resin in the comparative example is prepared by a method of polymerizing the water-soluble acrylic resin in advance and adding the organosilicon monomer and the residual alcohol ether solvent after completion, and is specifically as follows:
(1) Polymerization preparation of organosilicon modified water-soluble acrylic resin:
(a) Keeping the reaction kettle clean and anhydrous, adding 40 parts of alcohol ether solvent according to parts by weight, introducing nitrogen into the reaction kettle, keeping, introducing cooling water into a condensing tube, and heating the alcohol ether solvent to 140 ℃.
(b) Taking a dispersing kettle, 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, 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 rotating speed is 300r/min, and the stirring time is 40min; dripping the mixed solution into the reaction kettle in the step (a) for 6 hours, and controlling the temperature at 140 ℃; after the dripping is finished, the reaction is carried out for 2 hours with the temperature controlled at 140 ℃.
(c) Adding 0.2 part of initiator into the reaction kettle in the step (a) according to parts by weight, and continuously reacting for 2 hours, wherein the temperature is controlled at 140 ℃.
(d) Cooling to 80 ℃, adding 5 parts of organic silicon monomer and 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.
(e) And (3) 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 stirring for 20min to obtain the organosilicon modified water-soluble acrylic resin.
(2) Preparation of environment-friendly water-based ink varnish for photovoltaic glass glaze:
under the stirring condition, 60 parts of alcohol ether solvent, 32.5 parts of organosilicon modified water-soluble acrylic resin and 5 parts of rheological anti-settling agent are sequentially put into a stirring kettle according to parts by weight, stirred until being uniform, the stirring speed is 300r/min, kept stirring and heated to 90 ℃, and cooled after being completely dissolved. Stirring and cooling to 50 ℃, putting 2.5 parts of dispersing agent into a stirring kettle, stirring uniformly for 20min, and obtaining the environment-friendly water-based ink-transfer oil for the photovoltaic glass glaze.
Example 4
The environment-friendly aqueous varnish for the photovoltaic glass glaze prepared in examples 1-3 and comparative example 1 was prepared as follows to obtain an aqueous white glaze: putting the ink-regulating oil into a container, starting stirring at a 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 caking, wherein the stirring time is 90-120min; the rotation speed is regulated to be 400-600r/min, and the leveling agent and the defoaming agent are sequentially put into a container and stirred until being uniform for 20-30min. And then the aqueous white glaze is obtained through three-roller milling.
The test results of the photovoltaic module backboard glass coated with the water-based white glaze prepared by the environment-friendly water-based varnish corresponding to the photovoltaic glass glaze in examples 1-3 and comparative example 1 are shown in table 1.
TABLE 1 test indicators described in examples 1-3 and comparative example 1
The results in Table 1 show that the screen printability, the adhesion to photovoltaic glass after heat curing, and the adhesion in examples 1-3 are all superior to those in comparative example 1. Compared with the mode of pre-synthesizing silica sol or pre-polymerizing acrylic resin, the method in the embodiment 1-3 has the advantages that the process is simplified, the organosilicon monomer and other raw materials are pre-mixed uniformly, then the mixture is dripped into an alcohol ether solvent for reaction, and the rupture and polymerization of double bonds are synchronously carried out with the acrylic acid (ester) monomer and the styrene, so that the organosilicon monomer is better at the same time. And the organosilicon can reduce the surface energy, has better wettability to glass powder and titanium pigment, further increases the compatibility of the whole glaze system, and improves the dispersion and grinding efficiency of preparing white glaze.
The above embodiments are only for illustrating the technical concept and features of the present invention, and are intended to enable those skilled in the art to understand the present invention and to implement the same, but are not intended to limit the scope of the present invention, and all equivalent changes or modifications made according to the spirit of the present invention should be included in 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 of:
(1) Preparation of organosilicon modified water-soluble acrylic resin:
mixing acrylic acid monomer and/or acrylic ester monomer, styrene, organic silicon monomer, molecular weight regulator and partial initiator, dripping into partial alcohol ether solvent at 140-150 deg.c, maintaining the temperature for reaction for 1-2 hr; adding the rest initiator into the system, and continuing the reaction for 1-2h; cooling to 70-80deg.C, adding the rest alcohol ether solvent, and mixing; regulating the pH value of the system to 8-9 to obtain the organosilicon modified water-soluble acrylic resin;
(2) Preparation of environment-friendly water-based ink varnish for photovoltaic glass glaze:
under the stirring condition, uniformly mixing an alcohol ether solvent, an organosilicon modified water-soluble acrylic resin and a rheological anti-settling agent, heating to 80-90 ℃, cooling to 40-50 ℃ after the organosilicon modified water-soluble acrylic resin and the rheological anti-settling agent are completely dissolved, adding a dispersing agent into a system, and uniformly mixing to obtain the environment-friendly water-based ink-transfer oil for the photovoltaic glass glaze.
2. The preparation method of the photovoltaic glass glaze according to claim 1, wherein the environment-friendly water-based ink-regulating oil for the photovoltaic glass glaze comprises, by weight, 60-80 parts of alcohol ether solvent, 20-40 parts of organosilicon modified water-soluble acrylic resin, 1-5 parts of rheological anti-settling agent and 1-5 parts of dispersing agent.
3. The preparation method of claim 1, wherein the solid content of the prepared environment-friendly water-based varnish for the photovoltaic glass glaze is 3+/-1%; the viscosity at 25+ -1deg.C is 100-500 mpa.s.
4. The method according to claim 1, wherein the partial alcohol ether solvent accounts for 40-60% of the total mass of the alcohol ether solvent in the organosilicon modified water-soluble acrylic resin raw material; the partial initiator accounts for 80-95% of the total amount of the initiator in the organosilicon modified water-soluble acrylic resin raw material.
5. The preparation method according to claim 1, wherein the dropping time is 6-8 hours, and the system temperature is controlled to be 140-150 ℃.
6. The method according to claim 1, wherein nitrogen 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 water-based varnish for the photovoltaic glass frit and/or the alcohol ether solvent in the organosilicon modified water-soluble acrylic resin is one or more selected from diethylene glycol butyl ether, dipropylene glycol methyl ether, tripropylene glycol methyl ether, dipropylene glycol butyl ether and tripropylene glycol butyl ether.
9. An environmentally friendly aqueous varnish for photovoltaic glass frit 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-regulating oil for photovoltaic glass glaze prepared by the preparation method according to any one of claims 1-8 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 no caking is generated, a leveling agent and a defoaming agent are sequentially put into the container, stirring is carried out until uniformity is realized, and the water-based white glaze is obtained after milling.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211374408.6A CN115612347B (en) | 2021-06-25 | 2021-06-25 | Environment-friendly water-based ink-transfer oil for photovoltaic glass glaze, preparation method of environment-friendly water-based ink-transfer oil and water-based white glaze |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211374408.6A CN115612347B (en) | 2021-06-25 | 2021-06-25 | Environment-friendly water-based ink-transfer oil for photovoltaic glass glaze, preparation method of environment-friendly water-based ink-transfer oil and water-based white glaze |
| CN202110712780.2A CN113512322B (en) | 2021-06-25 | 2021-06-25 | Environment-friendly water-based varnish for photovoltaic glass glaze and preparation method thereof |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110712780.2A Division CN113512322B (en) | 2021-06-25 | 2021-06-25 | Environment-friendly water-based varnish for photovoltaic glass glaze and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115612347A CN115612347A (en) | 2023-01-17 |
| CN115612347B true CN115612347B (en) | 2023-06-02 |
Family
ID=78066101
Family Applications (3)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211374421.1A Active CN115677913B (en) | 2021-06-25 | 2021-06-25 | Organosilicon modified water-soluble acrylic resin, preparation method thereof and environment-friendly water-based ink varnish for photovoltaic glass glaze |
| CN202110712780.2A Active CN113512322B (en) | 2021-06-25 | 2021-06-25 | Environment-friendly water-based varnish for photovoltaic glass glaze and preparation method thereof |
| CN202211374408.6A Active CN115612347B (en) | 2021-06-25 | 2021-06-25 | Environment-friendly water-based ink-transfer oil for photovoltaic glass glaze, preparation method of environment-friendly water-based ink-transfer oil and water-based white glaze |
Family Applications Before (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211374421.1A Active CN115677913B (en) | 2021-06-25 | 2021-06-25 | Organosilicon modified water-soluble acrylic resin, preparation method thereof and environment-friendly water-based ink varnish for photovoltaic glass glaze |
| CN202110712780.2A Active CN113512322B (en) | 2021-06-25 | 2021-06-25 | Environment-friendly water-based varnish for photovoltaic glass glaze and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (3) | CN115677913B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
| CN117602832A (en) * | 2022-06-30 | 2024-02-27 | 吴江南玻玻璃有限公司 | Combined glaze suitable for laminated glaze plating and preparation method 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 |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09216922A (en) * | 1996-02-08 | 1997-08-19 | Showa Denko Kk | Water-resistant additive |
| CN101067011A (en) * | 2007-04-30 | 2007-11-07 | 江苏三木集团有限公司 | Water soluble acrylic resin and its prepn |
| WO2013083956A1 (en) * | 2011-12-08 | 2013-06-13 | Sericol Limited | Radiation curable inks |
| CN107082842A (en) * | 2017-06-02 | 2017-08-22 | 广东深展实业有限公司 | A kind of preparation method of water-soluble organic silicon modified acrylic ester resin |
| CN108530985A (en) * | 2018-04-10 | 2018-09-14 | 佛山市高明绿色德化工有限公司 | Aqueous high covering black ink of a kind of high temperature and preparation method thereof |
| WO2019126449A1 (en) * | 2017-12-21 | 2019-06-27 | Benjamin Moore & Co. | Siloxane-modified binders and compositions thereof |
| JP2019210248A (en) * | 2018-06-05 | 2019-12-12 | Dic株式会社 | Calixarene compound, water-sliding surface modifier, curable resin composition and water-sliding coating film |
| CN111269613A (en) * | 2020-04-14 | 2020-06-12 | 广东佰合新材料科技股份有限公司 | Gravure printing water-based ink and preparation method thereof |
| CN111534149A (en) * | 2020-05-18 | 2020-08-14 | 厦门欧化实业有限公司 | High-adhesion ink and preparation method thereof |
Family Cites Families (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3003166B2 (en) * | 1990-06-18 | 2000-01-24 | 大日本インキ化学工業株式会社 | Marking ink for jet printer |
| JP4936599B2 (en) * | 2001-02-16 | 2012-05-23 | 楠本化成株式会社 | Smoothing agent for paint and ink |
| US20080262144A1 (en) * | 2004-10-19 | 2008-10-23 | Degussa Gmbh | Aqueous, Radiation-Hardenable Resins, Method for the Production Thereof, and Use of the Same |
| JP2009138106A (en) * | 2007-12-06 | 2009-06-25 | Sekisui Chem Co Ltd | Glass paste composition and method for manufacturing plasma display panel |
| JP2009155451A (en) * | 2007-12-26 | 2009-07-16 | Sekisui Chem Co Ltd | Glass paste composition and method for manufacturing plasma display panel |
| CN102101960B (en) * | 2010-12-24 | 2013-06-05 | 大连工业大学 | High-hydroxy silicon-acrylate aqueous glass coating emulsion and synthesis method thereof |
| KR101368223B1 (en) * | 2012-05-17 | 2014-02-28 | 한밭대학교 산학협력단 | UV curable coating composition for LCD tempered glass |
| FR3023295B1 (en) * | 2014-07-02 | 2017-12-08 | Arkema France | ENCAPSULATING A PHOTOVOLTAIC MODULE |
| JP2017078118A (en) * | 2015-10-20 | 2017-04-27 | 綜研化学株式会社 | Binder resin for glass paste, glass paste composition and method for producing the resin |
| CN105368140A (en) * | 2015-12-07 | 2016-03-02 | 佛山市高明绿色德化工有限公司 | Photo-cured high-temperature colored glass printing ink and preparation method therefor and painting method thereof |
| CN105602486B (en) * | 2016-01-28 | 2017-11-24 | 桐乡市正大涂料有限公司 | Clear aqueous glass glue and preparation method thereof |
| CN105948504A (en) * | 2016-05-12 | 2016-09-21 | 东莞泰升玻璃有限公司 | Blue-green tempered glass printing ink |
| CN108147673A (en) * | 2018-01-29 | 2018-06-12 | 福耀玻璃工业集团股份有限公司 | A kind of glass dust, ink and chemically reinforced glass |
| CN108530984B (en) * | 2018-04-04 | 2021-04-06 | 佛山市高明绿色德化工有限公司 | High-temperature environment-friendly frosted ink and preparation method thereof |
| CN108546453B (en) * | 2018-04-10 | 2021-01-19 | 佛山市高明绿色德化工有限公司 | High-temperature water-based high-coverage white ink and preparation method thereof |
| EP3838992A1 (en) * | 2019-12-20 | 2021-06-23 | Daw Se | Aqueous coating material system, use thereof and internal paint, facade paint, splicing mass, plaster, primer, adhesive mass, coating, glaze or pigment paste containing the aqueous coating material system |
| CN111944357A (en) * | 2020-07-21 | 2020-11-17 | 信义光伏产业(安徽)控股有限公司 | Glass ink and high-reflection back plate glass |
| CN112174531A (en) * | 2020-10-19 | 2021-01-05 | 厦门翰森达电子科技有限公司 | Dielectric layer glaze for ceramization of glass substrate and preparation method thereof |
-
2021
- 2021-06-25 CN CN202211374421.1A patent/CN115677913B/en active Active
- 2021-06-25 CN CN202110712780.2A patent/CN113512322B/en active Active
- 2021-06-25 CN CN202211374408.6A patent/CN115612347B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09216922A (en) * | 1996-02-08 | 1997-08-19 | Showa Denko Kk | Water-resistant additive |
| CN101067011A (en) * | 2007-04-30 | 2007-11-07 | 江苏三木集团有限公司 | Water soluble acrylic resin and its prepn |
| WO2013083956A1 (en) * | 2011-12-08 | 2013-06-13 | Sericol Limited | Radiation curable inks |
| CN107082842A (en) * | 2017-06-02 | 2017-08-22 | 广东深展实业有限公司 | A kind of preparation method of water-soluble organic silicon modified acrylic ester resin |
| WO2019126449A1 (en) * | 2017-12-21 | 2019-06-27 | Benjamin Moore & Co. | Siloxane-modified binders and compositions thereof |
| CN108530985A (en) * | 2018-04-10 | 2018-09-14 | 佛山市高明绿色德化工有限公司 | Aqueous high covering black ink of a kind of high temperature and preparation method thereof |
| JP2019210248A (en) * | 2018-06-05 | 2019-12-12 | Dic株式会社 | Calixarene compound, water-sliding surface modifier, curable resin composition and water-sliding coating film |
| CN111269613A (en) * | 2020-04-14 | 2020-06-12 | 广东佰合新材料科技股份有限公司 | Gravure printing water-based ink and preparation method thereof |
| CN111534149A (en) * | 2020-05-18 | 2020-08-14 | 厦门欧化实业有限公司 | High-adhesion ink and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 水性丙烯酸树脂的合成、改性及其应用研究进展;崇云凯;王永春;雷淑媛;代月;马登学;;山东化工(03) * |
| 水性油墨用丙烯酸改性树脂研究进展;曹新鑫;付武昌;吴东森;代鑫;王宾宾;;现代涂料与涂装(04) * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113512322A (en) | 2021-10-19 |
| CN115612347A (en) | 2023-01-17 |
| CN115677913A (en) | 2023-02-03 |
| CN115677913B (en) | 2023-09-22 |
| CN113512322B (en) | 2022-11-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN115612347B (en) | Environment-friendly water-based ink-transfer oil for photovoltaic glass glaze, preparation method of environment-friendly water-based ink-transfer oil and water-based white glaze | |
| CN113636756B (en) | Water-based environment-friendly white glaze for high-reflection anti-PID photovoltaic back plate glass and preparation method thereof | |
| CN113603362B (en) | Water-based environment-friendly white glaze with high adhesion and weather resistance for photovoltaic back plate glass and preparation method thereof | |
| CN106318091B (en) | A kind of aqueous dual-component organic-inorganic hybridization coating resin and preparation method thereof | |
| CN1218981C (en) | Acrylic polyurethane copolymer emulsion, its preparation method and use | |
| CN102101960A (en) | High-hydroxy silicon-acrylate aqueous glass coating emulsion and synthesis method thereof | |
| CN101864025B (en) | Preparation method of polyacrylate microgel emulsion and application thereof | |
| CN114316854B (en) | Acrylic acid adhesive with high solid content and low viscosity and preparation method thereof | |
| CN112159622A (en) | Ultraviolet-curing white butadiene coating and preparation method and application thereof | |
| CN114891215A (en) | Three-dimensional near-infrared photoinitiator and preparation method and application thereof | |
| CN103232566B (en) | Preparation method of high-solid-content low-viscosity acrylate emulsion for sealing gum | |
| CN111978784B (en) | Preparation method of biomass-based environment-friendly UV (ultraviolet) photocuring ink | |
| CN104629605B (en) | Single-component water-based metal flashing paint and preparation method thereof | |
| CN114605598B (en) | Bio-based dispersing agent and preparation method and application thereof | |
| CN113930117B (en) | Simple construction artistic coating and preparation method thereof | |
| CN102295906B (en) | High-strength yellowing-resistant elastic polyurethane adhesive and preparation method as well as application thereof | |
| CN110305326B (en) | Water-based acrylic resin for engineering machinery paint and preparation method thereof | |
| CN110746609B (en) | Electrophoretic paint color paste, modified epoxy grinding resin and preparation method | |
| CN103614059B (en) | A kind of preparation method of water-based tung oil/acrylic resin insulation paint | |
| CN113278140A (en) | Epoxy acrylic acid modified waterborne alkyd resin and preparation method thereof | |
| CN114621385A (en) | High-distinctness of image waterborne acrylic resin and preparation method thereof | |
| CN109456727A (en) | A kind of green photocuring STPU resin and its preparation method and application | |
| CN114213626B (en) | Preparation method of vegetable oil-based photo-curing polyurethane acrylate | |
| CN117209647A (en) | Water-soluble acrylic resin, preparation method thereof and ink-regulating oil for photovoltaic glass glaze | |
| CN113493627B (en) | Water-alcohol UV ink capable of realizing rapid photo-curing and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |