CN109694639B - Water-based glass baking paint and preparation method thereof - Google Patents

Water-based glass baking paint and preparation method thereof Download PDF

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Publication number
CN109694639B
CN109694639B CN201811636434.5A CN201811636434A CN109694639B CN 109694639 B CN109694639 B CN 109694639B CN 201811636434 A CN201811636434 A CN 201811636434A CN 109694639 B CN109694639 B CN 109694639B
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water
agent
methacrylate
ether
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CN109694639A (en
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徐军
付允明
裘家升
顾卓韦
张莉莉
周昶吉
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Zhejiang Casnovo Materials Co ltd
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Zhejiang Casnovo Materials Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • 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
    • C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
    • C09D151/08—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • 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
    • C09D161/00—Coating compositions based on condensation polymers of aldehydes or ketones; Coating compositions based on derivatives of such polymers
    • C09D161/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
    • C09D161/32—Modified amine-aldehyde condensates
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/20—Diluents or solvents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend

Abstract

The invention relates to water-based glass baking paint which is characterized by comprising the following components in percentage by weight: 20-60% of water-based epoxy resin, 10-40% of low-methyl-etherified amino resin, 0-18% of water-based acrylic resin modified polyurethane, 3-30% of a color concentrate dye or a coloring agent, 0.1-0.8% of a flatting agent, 0.1-1.0% of a wetting agent, 0.1-0.8% of an adhesion agent, 0.1-0.8% of an antioxidant, 0.1-0.6% of an antifoaming agent, 0.1-0.4% of a bactericide, 0.5-6% of a pH regulator, and the balance of deionized water. The invention also discloses a preparation method of the water-based glass baking paint. Compared with the prior art, the water-based glass baking paint has good adhesive force on substrates such as glass and the like, and has excellent alcohol resistance, water resistance and wear resistance without using an organic solvent additionally. And the preparation method is simple and environment-friendly.

Description

Water-based glass baking paint and preparation method thereof
Technical Field
The invention belongs to the technical field of coatings, and particularly relates to water-based glass baking paint and a preparation method thereof.
Background
The coating protection and decoration of glass and glass products have wide requirements in the industrial and civil fields, such as wine bottles, cosmetic bottles, perfume bottles, lamp decorations, home decoration glass products, glass instruments and the like, which need to be coated with protective layers and decorative coatings on the surfaces. At present, most of glass coatings applied in China are solvent-based products, are relatively mature and popular, more than 50% of organic solvents (toluene, xylene, industrial alcohol and the like) are required to be added when the oily glass baking varnish is used, the solvents are easy to volatilize, have pungent smell and have different degrees of toxicity to human bodies, and are continuously volatilized into the air or absorbed by the human bodies in the production process, the application process and the drying process, so that the environment is seriously damaged, and the health of the human bodies is injured.
With the increasing awareness of environmental protection and the perfection of environmental laws and regulations, the application of water-based coatings to glass, which contain no or only a small amount of organic solvents, is receiving great attention. The single-component water-based glass paint prepared from the polyurethane aqueous dispersion, the water-soluble polyacrylic resin and the urethane and modified acrylic resin has the defects of poor adhesive force, alcohol resistance, water resistance, wear resistance, low hardness and the like on a glass substrate. The short working life of the aqueous double-component room temperature curing glass paint in the construction process can cause certain difficulty in construction, and simultaneously, the problems of paint waste, uneven mixing in the construction site and the like are caused.
In order to overcome the defects of the water-based paint, the invention patent application with the application number of CN201510703522.2, namely a water-based glass baking paint (with the application publication number of CN106609080A), discloses a water-based glass baking paint which comprises, by weight, 40-70 parts of water-soluble acrylic resin, 2-5 parts of isopropanol, 1-5 parts of triethanolamine, 10-15 parts of low methylated amino resin, 2-5 parts of ethanol and 0.2-0.9 part of titanium dioxide. The water-based glass baking varnish has good adhesive force and tinting strength, has strong adhesive force to the surface of glass, and improves the decorative performance. However, the water-soluble acrylic resin tends to react with the dye to affect the color of the baking varnish.
For another example, an invention patent application with application number CN201711146705.4, an aqueous glass baking paint (application publication number CN107815192A), discloses an aqueous glass baking paint, which comprises the following components in percentage by weight: 60-80% of water-based resin, 0.3-0.8% of acid catalyst, 0.7-5.5% of pH regulator, 0.1-0.5% of thickening agent, 1-8% of cosolvent, 0.1-1% of wetting agent, 1-9% of film-forming assistant, 0-20% of pigment and 5-25% of water. Wherein the water-based resin is one or a mixture of more of hydroxyl acrylic resin, epoxy acrylic resin, melamine resin, polyamide resin and inorganic silicon resin. The prepared glass baking varnish has high glossiness, high hardness and strong weather resistance. But the rapid crosslinking of the matrix resin can be promoted by additionally adding an acid catalyst, so that the curing temperature is reduced, and the curing degree is improved; in addition, although it is an aqueous baking varnish, it is necessary to add a certain amount of an organic solvent (i.e., a cosolvent).
Disclosure of Invention
The first technical problem to be solved by the invention is to provide the green and environment-friendly water-based glass baking paint which is good in adhesive force, and excellent in alcohol resistance, water resistance and wear resistance aiming at the current situation of the prior art.
The second technical problem to be solved by the invention is to provide a preparation method of the water-based glass baking paint, which is simple in process and environment-friendly, aiming at the current situation of the prior art.
The technical scheme adopted by the invention for solving the first technical problem is as follows: the water-based glass baking paint is characterized by comprising the following components in percentage by weight:
20-60% of water-based epoxy resin, 10-40% of low-methyl-etherified amino resin, 0-18% of water-based acrylic resin modified polyurethane, 3-30% of a color concentrate dye or a coloring agent, 0.1-0.8% of a flatting agent, 0.1-1.0% of a wetting agent, 0.1-0.8% of an adhesion agent, 0.1-0.8% of an antioxidant, 0.1-0.6% of an antifoaming agent, 0.1-0.4% of a bactericide, 0.5-6% of a pH regulator, and the balance of deionized water.
The low methylated amino resin is preferably a high imine type partial low methylated amino resin.
The aqueous acrylic resin modified polyurethane is preferably an aromatic isocyanate type aqueous polyurethane.
In the above scheme, the chromophoric dye or the colorant is preferably at least one of transparent pigment, azo pigment, pearlescent pigment, carbon black and titanium dioxide; the leveling agent is preferably at least one of an acrylic leveling agent, an organic silicon leveling agent and a fluorocarbon leveling agent; the wetting agent is preferably at least one of wetting agents such as acetylene glycol, fluorine, acrylic acid, silicone and the like; the adhesion agent is preferably at least one of siloxane coupling agents containing amino groups, diamino groups, methacrylate groups, epoxy groups, vinyl groups, alkyl chloride groups, and the like; the antioxidant is preferably at least one of sodium formaldehyde sulfoxylate, sodium bisulfite, oxalic acid, phytic acid, ammonia water, hydrazine hydrate, ascorbic acid, tea polyphenol, tocopherol, flavonoids, butyl hydroxy anisole, dibutyl hydroxy toluene and tert-butyl hydroquinone; the defoaming agent is preferably at least one of polyether defoaming agent, high-carbon alcohol defoaming agent, silicon defoaming agent, polyether modified silicon defoaming agent, self-emulsifying defoaming agent and polysiloxane defoaming agent; the pH regulator is preferably one of N-aminopropyl-methyl ethanolamine, 2-amino-2-methyl-1-propanol, butyl diethanolamine, N-methyl ethanolamine, 2-amino-2-ethyl-1, 3-propanediol, dimethyl ethanolamine, monoethanolamine, diethanolamine, triethanolamine, butyl ethanolamine and ammonia water.
In order to further improve various performances of the baking varnish, the waterborne epoxy resin with good water solubility and high transparency is selected, and preferably comprises the following components in percentage by weight: 5-15% of a raw material; 2-10% of a raw material b; 1-8% of a raw material c; 26-47% of a raw material d; 14-25% of a raw material e; 5-10% of a raw material f; the balance of deionized water; wherein the raw material a is at least one of secondary amine or tertiary amine; the raw material b is at least one of unsaturated carboxylic acid esters; the raw material c is at least one of alcohol amine, amide, aromatic amine, imine and hydroxylamine raw materials; the raw material d is one of epoxy resins with different epoxy equivalent weights; the raw material e is one of organic solvents; the raw material f is one of acrylic monomers.
The raw material a is preferably at least one of triethylamine, diethanolamine, triethanolamine, diethylenetriamine, hexamethyleneimine, hexamethylenetetramine and N, N-diethylaniline and is used for opening unsaturated bonds in the material b; the raw material b is preferably at least one of methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, isooctyl methacrylate, n-octyl methacrylate, cyclohexyl methacrylate, trifluoroethyl methacrylate, glycidyl methacrylate, isobornyl methacrylate, methyl acrylate, ethyl acrylate, n-butyl acrylate, hydroxypropyl acrylate, isooctyl acrylate, ethylene carbonate, propylene carbonate, lauryl acrylate and isobornyl acrylate; the raw material c is preferably at least one of monoethanolamine, diethanolamine, triethanolamine, 3-propanolamine, acetamide, dimethylformamide, isobutyramide, aniline, o-phenylenediamine, 2, 4-dimethylaniline, N-diethylaniline, para-fluoroaniline, phthalimide and hydroxylamine, and is used for grafting to introduce a polar group; the raw material d is preferably epoxy resin with the epoxy equivalent of 100-5000; the raw material e is preferably one of propylene glycol methyl ether acetate, ethylene glycol monobutyl ether, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol butyl ether, isobutyl vinyl ether, cyclohexyl vinyl ether, N-vinyl imidazole, N-vinyl caprolactam, N-vinyl pyrrolidone, vinyl ethyl ether, diethylene glycol divinyl ether, 1, 4-cyclohexyl dimethanol divinyl ether, hydroxybutyl vinyl ether, 1, 4-cyclohexanediol monovinyl ether and divinyl-1, 4-butanediol ether; the raw material f is preferably one of acrylic acid, methacrylic acid, alpha-hydroxy methacrylic acid, maleic acid and 2-acrylamide-2-methylpropanesulfonic acid, so that the crosslinking degree is improved, and the hardness and the water resistance of the aqueous ring resin are improved.
Preferably, the preparation method of the water-based epoxy resin comprises the following steps:
adding the raw material a and the raw material b, heating to 40-60 ℃, and stirring for 2-7 hours; then heating to 80-130 ℃, adding the raw material c and the raw material d, and stirring for 3-10 hours; and then adding the raw material e, the raw material f and deionized water, continuing to preserve heat for 0.5-4.5 h, cooling to room temperature, adjusting the pH value to 7-8, and filtering to obtain the water-based epoxy resin.
The water-based epoxy resin takes water as a main solvent, so that the volatilization of the solvent and the emission of VOC are reduced in the production process, and meanwhile, the preparation process is environment-friendly and simple in preparation process by taking water as the main solvent; in the preparation method, the raw materials a and b are reacted to open unsaturated bonds in the raw material b, then the raw materials c and d are added to open epoxy groups in the raw material d for grafting crosslinking, and finally the raw materials e and f and deionized water are added to further improve the crosslinking degree of the polymer.
The technical scheme adopted by the invention for solving the second technical problem is as follows: the preparation method of the water-based glass baking paint is characterized by comprising the following steps:
mixing and uniformly stirring a wetting agent, a defoaming agent and deionized water; and then adding the waterborne epoxy resin, the low methylated amino resin and the waterborne acrylic resin modified polyurethane, adding the flatting agent, the adhesion agent, the antioxidant, the bactericide and the pH regulator, stirring and mixing uniformly to obtain a mixed solution, adding the chromogen dye or the colorant according to needs, defoaming, adjusting to the required viscosity, and filtering to obtain the waterborne glass baking varnish.
As an improvement, the mixed solution before the addition of the chromogen dye or the coloring agent is a transparent solution, and the viscosity of the transparent solution at 25 ℃ is 10-1000 centipoises, preferably 90-500 centipoises.
The solid content of the prepared water-based glass baking paint is 25-75%, and preferably 30-50%.
Compared with the prior art, the invention has the advantages that: the water-based epoxy resin and the low methylated amino resin can form a complex three-dimensional network structure through a crosslinking reaction, so that a coating becomes more continuous and compact, and solvent micromolecules can be effectively prevented from migrating and swelling to polymer molecular chains, so that the water resistance, alcohol resistance, adhesive force, low coating viscosity and high mechanical strength of a paint film are improved, the pencil hardness of the prepared paint film is as high as more than 3H, and the paint film has the scratch resistance and wear resistance of a porcelain glaze film; the dye is fixed on the baking varnish and cannot react with the water-based epoxy resin to influence the color of the dye; the addition of the waterborne acrylic resin modified polyurethane can further improve the toughness of a paint film of the baking paint, and simultaneously can prevent the influence of sunlight irradiation on the paint film and prevent the paint film from aging; in addition, the water-based epoxy resin with good water solubility is adopted, so that the invention takes water as a solvent, does not need to add an organic solvent, avoids the volatilization of the solvent in the production process, reduces the emission of Volatile Organic Compounds (VOC), and simultaneously takes water as the solvent, the preparation process is environment-friendly and the preparation process is simple; the water-based glass baking varnish is suitable for surface protection and decoration of products such as wine bottles, cosmetic bottles, perfume bottles, lamp decorations, plastics, home decoration glass products, glass instruments and the like, and has wide application range.
Detailed Description
The present invention will be described in further detail with reference to examples.
Example 1:
the water-based glass baking paint comprises the following components in percentage by weight:
30% of aqueous epoxy resin (the model of GS-5000C aqueous epoxy resin produced by Changzhou Guangshou chemical technology Co., Ltd.), 18% of low-methylated amino resin (high imine type partially low-methylated amino resin is selected), 6.4% of aqueous acrylic resin modified polyurethane (aromatic isocyanate type aqueous polyurethane is selected), 13% of a color concentrate dye or a coloring agent (red color concentrate dye is selected), 0.4% of a leveling agent (silicone oil is selected), 0.3% of an organosilicon wetting agent, 0.3% of an adhesion agent (bisaminosilane coupling agent is selected), 0.5% of an antioxidant (sodium bisulfite is selected), 0.2% of a polyether defoamer, 0.2% of a bactericide, 1.4% of a pH regulator (2-amino-2-methyl-1-propanol is selected), and the balance of deionized water.
The preparation method of the water-based glass baking paint comprises the following steps: mixing and uniformly stirring a wetting agent, a defoaming agent and deionized water; and then adding the waterborne epoxy resin, the low methylated amino resin and the waterborne acrylic resin modified polyurethane, adding the flatting agent, the adhesion agent, the antioxidant, the bactericide and the pH regulator, stirring and mixing uniformly to obtain a transparent solution-shaped mixed solution, wherein the viscosity of the transparent solution-shaped mixed solution is 500 centipoises at 25 ℃, adding the chromogen dye or the colorant, defoaming (by a physical defoaming method such as vacuumizing) and adjusting to the required viscosity, and filtering to obtain the waterborne glass baking varnish.
The solid content of the prepared water-based glass baking paint is 45 percent.
Example 2:
the water-based glass baking paint comprises the following components in percentage by weight:
38% of water-based epoxy resin (the model of which is WE-8216 produced by Shandong Rui Sanhua chemical engineering Co., Ltd.), 13% of low-methylated amino resin (high imine type partially low-methylated amino resin is selected), 13% of water-based acrylic resin modified polyurethane (aromatic isocyanate type water-based polyurethane is selected), 6% of color concentrate dye or colorant (green color concentrate dye is selected), 0.3% of flatting agent (acrylate flatting agent is selected), 0.3% of acetylene glycol wetting agent, 0.3% of adhesion agent (siloxane coupling agent containing methacrylate group is selected), 0.5% of antioxidant (oxalic acid is selected), 0.2% of high-carbon alcohol defoaming agent, 0.2% of bactericide, 1.2% of pH regulator (N-methylethanolamine is selected), and the balance of deionized water.
The preparation method of the water-based glass baking paint comprises the following steps: mixing and uniformly stirring a wetting agent, a defoaming agent and deionized water; and then adding the waterborne epoxy resin, the low methylated amino resin and the waterborne acrylic resin modified polyurethane, adding the flatting agent, the adhesive, the antioxidant, the bactericide and the pH regulator, stirring and mixing uniformly to obtain a transparent solution-shaped mixed solution, wherein the viscosity of the transparent solution-shaped mixed solution is 300 centipoise at 25 ℃, adding the chromogen dye or the colorant, defoaming, adjusting to the required viscosity, and filtering to obtain the waterborne glass baking varnish.
The solid content of the prepared water-based glass baking paint is 30 percent.
Example 3:
the water-based glass baking paint comprises the following components in percentage by weight:
22 percent of waterborne acrylic resin (the model of HOMAAC produced by gold group chemical Co., Ltd.) is selectedTM-5201 aqueous acrylic baking varnish resin), 26% of low methylated amino resin (high imine type partial low methylated amino resin is selected), 5.5% of aqueous acrylic resin modified polyurethane (aromatic isocyanate type aqueous polyurethane is selected), 21% of chromophoric dye or colorant (blue chromophoric dye is selected), 0.3% of leveling agent (fluorocarbon leveling agent is selected), 0.3% of acrylic wetting agent, 0.3% of adhesion agent (siloxane coupling agent containing epoxy group is selected), 0.5% of antioxidant (ammonia water is selected), 0.2% of silicon defoaming agent, 0.2% of bactericide, 1.2% of pH regulator (dimethylethanolamine is selected), and the balance of deionized water.
The preparation method of the water-based glass baking paint comprises the following steps: mixing and uniformly stirring a wetting agent, a defoaming agent and deionized water; and then adding the waterborne epoxy resin, the low methylated amino resin and the waterborne acrylic resin modified polyurethane, adding the flatting agent, the adhesive, the antioxidant, the bactericide and the pH regulator, stirring and mixing uniformly to obtain a transparent solution-shaped mixed solution, wherein the viscosity of the transparent solution-shaped mixed solution is 10 centipoises at 25 ℃, adding the chromogen dye or the colorant, defoaming, adjusting to the required viscosity, and filtering to obtain the waterborne glass baking varnish.
The solid content of the prepared water-based glass baking paint is 25 percent.
Example 4:
the water-based glass baking paint comprises the following components in percentage by weight:
41 percent of water-based epoxy resin (41 percent of water-based resin with the model number of YT-02 provided by Qinghailin Kongmao Co., Ltd.), 13 percent of low-methyl-etherified amino resin (13 percent of high imine type partial low-methyl-etherified amino resin), 5.5 percent of water-based acrylic resin modified polyurethane (aromatic isocyanate type water-based polyurethane), 15 percent of color concentrate dye or colorant (titanium white color paste is selected), 0.3 percent of flatting agent (acrylic flatting agent is selected), 0.5 percent of fluorine wetting agent, 0.3 percent of adhesion agent (siloxane coupling agent containing vinyl is selected), 0.5 percent of antioxidant (hydrazine hydrate is selected), 0.2 percent of self-emulsifying defoaming agent, 0.2 percent of bactericide, 1.2 percent of pH regulator (monoethanolamine is selected, certainly diethanolamine, triethanolamine, butyl ethanolamine, butyl diethanolamine and the like are selected), and the balance is deionized water.
The preparation method of the water-based glass baking paint comprises the following steps: mixing and uniformly stirring a wetting agent, a defoaming agent and deionized water; and then adding the waterborne epoxy resin, the low methylated amino resin and the waterborne acrylic resin modified polyurethane, adding the flatting agent, the adhesive, the antioxidant, the bactericide and the pH regulator, stirring and mixing uniformly to obtain a transparent solution-shaped mixed solution, wherein the viscosity of the transparent solution-shaped mixed solution is 1000 centipoises at 25 ℃, adding the chromogen dye or the colorant, defoaming, adjusting to the required viscosity, and filtering to obtain the waterborne glass baking varnish.
The solid content of the prepared water-based glass baking paint is 75 percent.
Example 5:
the water-based glass baking paint comprises the following components in percentage by weight:
52 percent of water-based epoxy resin (the water-based resin with the model number of PRO-4200 produced by Beijing GaoUnion New materials GmbH), 15 percent of low-methyl-etherified amino resin (high-imine partially low-methyl-etherified amino resin is selected), 5 percent of water-based acrylic resin modified polyurethane (aromatic isocyanate type water-based polyurethane is selected), 30 percent of color concentrate dye or colorant (carbon black color paste is selected), 0.4 percent of flatting agent (acrylic flatting agent is selected), 0.5 percent of fluorine wetting agent, 0.3 percent of adhesion agent (siloxane coupling agent containing chlorinated alkyl is selected), 0.5 percent of antioxidant (tea polyphenol is selected, certainly other antioxidants such as tocopherol, flavonoid, ascorbic acid and the like are also selected), 0.2 percent of polyether modified silicon defoaming agent, 0.2 percent of bactericide, 1.2 percent of pH regulator (2-amino-2-ethyl-1, 3-propylene glycol is selected, the balance of deionized water.
The preparation method of the water-based glass baking paint comprises the following steps: mixing and uniformly stirring a wetting agent, a defoaming agent and deionized water; and then adding the waterborne epoxy resin, the low methylated amino resin and the waterborne acrylic resin modified polyurethane, adding the flatting agent, the adhesive, the antioxidant, the bactericide and the pH regulator, stirring and mixing uniformly to obtain a transparent solution-shaped mixed solution, wherein the viscosity of the transparent solution-shaped mixed solution is 700 centipoises at 25 ℃, adding the chromogen dye or the colorant, defoaming, adjusting to the required viscosity, and filtering to obtain the waterborne glass baking varnish.
The solid content of the prepared water-based glass baking paint is 50 percent.
Example 6:
basically the same as example 1, except that the water-based glass baking paint in this example comprises the following components in percentage by weight:
20% of water-based epoxy resin, 40% of low methylated amino resin (high imine type partial low methylated amino resin is selected), 3% of a color concentrate dye or a coloring agent (pearlescent pigment color paste is selected), 0.1% of a flatting agent (silicone oil is selected), 0.1% of an organosilicon wetting agent, 0.1% of an adhesion agent (diamino silane coupling agent is selected), 0.1% of an antioxidant (sodium bisulfite is selected), 0.1% of a polyether defoaming agent, 0.1% of a bactericide, 6% of a pH regulator (2-amino-2-methyl-1-propanol is selected), and the balance of deionized water.
The solid content of the aqueous glass stoving varnish was 40%.
Example 7:
basically the same as example 1, except that the water-based glass baking paint in this example comprises the following components in percentage by weight:
60% of water-based epoxy resin, 10% of low-methylated amino resin (high imine type partial low-methylated amino resin is selected), 4% of a color concentrate dye or a coloring agent (azo pigment color paste is selected), 0.8% of a leveling agent (silicone oil is selected), 1.0% of an organosilicon wetting agent, 0.8% of an adhesion agent (diamino silane coupling agent is selected), 0.8% of an antioxidant (sodium bisulfite is selected), 0.6% of a polyether defoaming agent, 0.4% of a bactericide, 0.5% of a pH regulator (2-amino-2-methyl-1-propanol is selected), and the balance of deionized water.
The solid content of the aqueous glass stoving varnish was 55%.
Example 8:
basically the same as example 1, except that the water-based glass baking paint in this example comprises the following components in percentage by weight:
20% of water-based epoxy resin, 10% of low-methylated amino resin (selected from high imine type partial low-methylated amino resin), 18% of water-based acrylic resin modified polyurethane (selected from aromatic isocyanate type water-based polyurethane), 30% of color concentrate dye or colorant (selected from metal pigment color paste), 0.8% of flatting agent (selected from silicone oil), 1.0% of organic silicon wetting agent, 0.8% of adhesion agent (selected from diamino silane coupling agent), 0.8% of antioxidant (selected from sodium bisulfite), 0.6% of polyether defoamer, 0.4% of bactericide, 0.5% of pH regulator (selected from 2-amino-2-methyl-1-propanol) and the balance of deionized water.
The solid content of the aqueous glass stoving varnish was 30%.
Example 9:
basically the same as the example 1, except that the waterborne epoxy resin in the example is prepared by self-made, and comprises the following components by weight percent: raw material a 6.5% (triethylamine); 7.8% of a raw material b (methyl methacrylate is selected as the raw material b in this example, but ethyl methacrylate, isopropyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, isooctyl methacrylate, n-octyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, etc. may be selected as the raw material b, and the same effects are obtained); 2.3% of raw material c (monoethanolamine is selected as raw material c in this embodiment, and alcamines with similar properties such as diethanolamine, triethanolamine and the like can be selected); raw material d 35.6% (epoxy resin of 300 epoxy equivalent); raw material e 20.2% (propylene glycol methyl ether acetate); raw material f 6.7% (acrylic acid); the balance of deionized water.
The preparation method of the waterborne epoxy resin comprises the following steps: adding the raw material a, the raw material b, into a four-neck flask, heating to 59 ℃, stirring for 5 hours, heating to 85 ℃, adding the raw material c and the raw material d, stirring for 8 hours, adding the raw material e, the raw material f and deionized water, keeping the temperature for 3 hours, cooling to room temperature, adjusting the pH value to 7 by using a neutralizing agent, and filtering to obtain the waterborne epoxy resin. The resulting waterborne epoxy resin was in the form of a clear solution with a viscosity of 500 cps at 25 ℃.
Example 10:
basically the same as the example 1, except that the waterborne epoxy resin in the example is prepared by self-made, and comprises the following components by weight percent: raw material a 11.2% (triethanolamine); 4.5% of raw material b (in this example, ethyl acrylate is selected, and methyl acrylate, n-butyl acrylate, hydroxypropyl acrylate, isooctyl acrylate and the like can be used as raw material b); raw material c 5.1% (acetamide is selected in this example, but dimethylformamide, isobutyramide, etc. may be used); raw material d 27.9% (epoxy resin of 850 epoxy equivalent); 15.6% of raw material e (ethylene glycol monobutyl ether, of course, other ether raw materials can be used as cosolvent); feed f 7.4% (methacrylic acid); the balance of deionized water.
The preparation method of the waterborne epoxy resin comprises the following steps: adding the raw material a, the raw material b, into a four-neck flask, heating to 43 ℃, stirring for 3h, heating to 94 ℃, adding the raw material c and the raw material d, stirring for 6.2h, adding the raw material e, the raw material f and deionized water, keeping the temperature for 3h, cooling to room temperature, adjusting the pH value to 8 by using a neutralizing agent, and filtering to obtain the waterborne epoxy resin. The resulting waterborne epoxy resin was in the form of a clear solution with a viscosity of 300 cps at 25 ℃.
Example 11:
basically the same as the example 1, except that the waterborne epoxy resin in the example is prepared by self-made, and comprises the following components by weight percent: starting material a 7.5% (hexamethyleneimine); 6.6% of raw material b (ethylene carbonate is selected in the embodiment, and propylene carbonate can be selected, of course); 2.2% of a raw material c (in this example, aniline is selected, but o-phenylenediamine, 2, 4-dimethylaniline, N-diethylaniline, p-fluoroaniline, etc. may be used); raw material d 33.6% (epoxy resin of 550 epoxy equivalent); feed e 16.6% (vinyl ethyl ether); 9.7% of starting material f (acrylic acid); the balance of deionized water.
The preparation method of the waterborne epoxy resin comprises the following steps: adding the raw material a, the raw material b, into a four-neck flask, heating to 56 ℃, stirring for 4 hours, heating to 88 ℃, adding the raw material c and the raw material d, stirring for 5 hours, adding the raw material e, the raw material f and deionized water, keeping the temperature for 3 hours, cooling to room temperature, adjusting the pH value to 8 by using a neutralizing agent, and filtering to obtain the waterborne epoxy resin. The resulting waterborne epoxy resin was in the form of a clear solution with a viscosity of 800 cps at 25 ℃.
Example 12:
basically the same as the example 1, except that the waterborne epoxy resin in the example is prepared by self-made, and comprises the following components by weight percent: feed a 5.8% (N, N-diethylaniline); raw material b 8.4% (lauryl acrylate); starting material c 1.5% (N, N-diethylaniline); raw material d 26.3% (1200 epoxy equivalent epoxy resin); feed e 15.6% (propylene glycol butyl ether); raw material f 10% (maleic acid); the balance of deionized water.
The preparation method of the waterborne epoxy resin comprises the following steps: adding the raw material a, the raw material b, into a four-neck flask, heating to 51 ℃, stirring for 4.4h, heating to 114 ℃, adding the raw material c and the raw material d, stirring for 7h, adding the raw material e, the raw material f and deionized water, keeping the temperature for 3h, cooling to room temperature, adjusting the pH value to 8 by using a neutralizing agent, and filtering to obtain the waterborne epoxy resin. The resulting waterborne epoxy resin was in the form of a clear solution having a viscosity of 150 cps at 25 ℃.
Example 13:
basically the same as the example 1, except that the waterborne epoxy resin in the example is prepared by self-made, and comprises the following components by weight percent: raw material a 12.5% (hexamethylenetetramine); feed b 3.8% (glycidyl methacrylate); starting material c 4.8% (phthalimide); raw material d 40.3% (660 epoxy equivalent epoxy resin); starting material e 16.4% (N-vinylimidazole); raw material f 5.5% (methacrylic acid); the balance of deionized water.
The preparation method of the waterborne epoxy resin comprises the following steps: adding the raw material a, the raw material b, into a four-neck flask, heating to 50 ℃, stirring for 5.8 hours, heating to 123 ℃, adding the raw material c and the raw material d, stirring for 8 hours, adding the raw material e, the raw material f and deionized water, continuing to keep the temperature for 3 hours, cooling to room temperature, adjusting the pH value to 8 by using a neutralizing agent, and filtering to obtain the waterborne epoxy resin. The resulting waterborne epoxy resin was in the form of a clear solution with a viscosity of 900 centipoise at 25 ℃.
Example 14:
basically the same as the example 1, except that the waterborne epoxy resin in the example is prepared by self-made, and comprises the following components by weight percent: starting material a 5% (diethylenetriamine); raw material b 2% (trifluoroethyl methacrylate); raw material c 1% (hydroxylamine); raw material d 47% (100 epoxy equivalent epoxy resin); raw material e 14% (divinyl-1, 4-butanediol ether); raw material f 5% (alpha-hydroxymethylacrylic acid); the balance of deionized water.
The preparation method of the waterborne epoxy resin comprises the following steps: adding the raw material a, the raw material b, into a four-neck flask, heating to 40 ℃, stirring for 7h, heating to 130 ℃, adding the raw material c and the raw material d, stirring for 3h, adding the raw material e, the raw material f and deionized water, continuing to keep the temperature for 0.5h, cooling to room temperature, adjusting the pH value to 7.5 by using a neutralizing agent, and filtering to obtain the waterborne epoxy resin. The resulting waterborne epoxy resin was in the form of a clear solution with a viscosity of 1000 cps at 25 ℃.
Example 15:
basically the same as the example 1, except that the waterborne epoxy resin in the example is prepared by self-made, and comprises the following components by weight percent: raw material a 15% (diethanolamine); raw material b 10% (isobornyl acrylate); raw material c 8% (3-propanolamine); raw material d 26% (5000 epoxy equivalent epoxy resin); feed e 25% (N-vinylcaprolactam); raw material f 5% (2-acrylamide-2-methylpropanesulfonic acid); the balance of deionized water.
The preparation method of the waterborne epoxy resin comprises the following steps: adding the raw material a, the raw material b, into a four-neck flask, heating to 60 ℃, stirring for 2h, heating to 80 ℃, adding the raw material c and the raw material d, stirring for 10h, adding the raw material e, the raw material f and deionized water, continuously keeping the temperature for 4.5h, cooling to room temperature, adjusting the pH value to 7 by using a neutralizing agent, and filtering to obtain the waterborne epoxy resin. The resulting waterborne epoxy resin was in the form of a clear solution with a viscosity of 90 centipoise at 25 ℃.
The water-based glass baking varnish paint films prepared in the above examples are tested, and the test results are shown in the following table:
Figure GDA0001982270770000101

Claims (8)

1. the water-based glass baking paint is characterized by comprising the following components in percentage by weight:
20-60% of water-based epoxy resin, 10-40% of low-methyl-etherified amino resin, 0-18% of water-based acrylic resin modified polyurethane, 3-30% of a color concentrate dye or a coloring agent, 0.1-0.8% of a flatting agent, 0.1-1.0% of a wetting agent, 0.1-0.8% of an adhesion agent, 0.1-0.8% of an antioxidant, 0.1-0.6% of an antifoaming agent, 0.1-0.4% of a bactericide, 0.5-6% of a pH regulator, and the balance of deionized water;
the waterborne epoxy resin comprises the following components in percentage by weight: 5-15% of a raw material; 2-10% of a raw material b; 1-8% of a raw material c; 26-47% of a raw material d; 14-25% of a raw material e; 5-10% of a raw material f; the balance of deionized water; wherein the raw material a is at least one of secondary amine or tertiary amine; the raw material b is at least one of unsaturated carboxylic acid esters; the raw material c is at least one of alcohol amine, amide, aromatic amine, imine and hydroxylamine raw materials; the raw material d is one of epoxy resins with different epoxy equivalent weights; the raw material e is one of organic solvents; the raw material f is one of acrylic monomers;
the preparation method of the water-based epoxy resin comprises the following steps:
adding the raw material a and the raw material b, heating to 40-60 ℃, and stirring for 2-7 hours; then heating to 80-130 ℃, adding the raw material c and the raw material d, and stirring for 3-10 hours; and then adding the raw material e, the raw material f and deionized water, continuing to preserve heat for 0.5-4.5 h, cooling to room temperature, adjusting the pH value to 7-8, and filtering to obtain the water-based epoxy resin.
2. The aqueous glass stoving varnish according to claim 1, characterised in that: the low methylated amino resin is high imine type partial low methylated amino resin.
3. The aqueous glass stoving varnish according to claim 1, characterised in that: the waterborne acrylic resin modified polyurethane is aromatic isocyanate type waterborne polyurethane.
4. The aqueous glass stoving varnish according to claim 1, characterised in that: the dye or colorant is at least one of transparent pigment, azo pigment, pearlescent pigment, carbon black and titanium pigment; the flatting agent is at least one of acrylic flatting agent, organic silicon flatting agent and fluorocarbon flatting agent; the wetting agent is at least one of acetylene glycol, fluorine, acrylic acid and organic silicon wetting agents; the adhesion agent is at least one of siloxane coupling agents containing amino, methacrylate group, epoxy group, vinyl and alkyl chloride; the antioxidant is at least one of sodium formaldehyde sulfoxylate, sodium bisulfite, oxalic acid, phytic acid, ammonia water, hydrazine hydrate, ascorbic acid, tea polyphenol, tocopherol, flavonoids, butyl hydroxy anisole, dibutyl hydroxy toluene and tert-butyl hydroquinone; the defoaming agent is at least one of polyether, high-carbon alcohol, silicon, polyether modified silicon, self-emulsifying type defoaming agent and polysiloxane defoaming agent; the pH regulator is one of N-aminopropyl-methyl ethanolamine, 2-amino-2-methyl-1-propanol, butyl diethanolamine, N-methyl ethanolamine, 2-amino-2-ethyl-1, 3-propanediol, dimethyl ethanolamine, monoethanolamine, diethanolamine, triethanolamine, butyl ethanolamine and ammonia water.
5. The aqueous glass stoving varnish according to claim 1, characterised in that: the raw material a is at least one of triethylamine, diethanolamine, triethanolamine, diethylenetriamine, hexamethyleneimine, hexamethylenetetramine and N, N-diethylaniline; the raw material b is at least one of methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, isooctyl methacrylate, n-octyl methacrylate, cyclohexyl methacrylate, trifluoroethyl methacrylate, glycidyl methacrylate, isobornyl methacrylate, methyl acrylate, ethyl acrylate, n-butyl acrylate, hydroxypropyl acrylate, isooctyl acrylate, ethylene carbonate, propylene carbonate, lauryl acrylate and isobornyl acrylate; the raw material c is at least one of monoethanolamine, diethanolamine, triethanolamine, 3-propanolamine, acetamide, dimethylformamide, isobutyramide, aniline, o-phenylenediamine, 2, 4-dimethylaniline, N-diethylaniline, p-fluoroaniline, phthalimide and hydroxylamine; the raw material e is one of propylene glycol methyl ether acetate, ethylene glycol monobutyl ether, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol butyl ether, isobutyl vinyl ether, cyclohexyl vinyl ether, N-vinyl imidazole, N-vinyl caprolactam, N-vinyl pyrrolidone, vinyl ethyl ether, diethylene glycol divinyl ether, 1, 4-cyclohexyl dimethanol divinyl ether, hydroxybutyl vinyl ether, 1, 4-cyclohexanediol monovinyl ether and divinyl-1, 4-butanediol ether; the raw material f is one of acrylic acid, methacrylic acid, alpha-hydroxy methacrylic acid, maleic acid and 2-acrylamide-2-methylpropanesulfonic acid.
6. A method for preparing the water-based glass baking paint according to any one of claims 1 to 5, characterized by comprising the steps of:
mixing and uniformly stirring a wetting agent, a defoaming agent and deionized water; and then adding the waterborne epoxy resin, the low methylated amino resin and the waterborne acrylic resin modified polyurethane, adding the flatting agent, the adhesion agent, the antioxidant, the bactericide and the pH regulator, stirring and mixing uniformly to obtain a mixed solution, adding the chromogen dye or the colorant according to needs, defoaming, adjusting to the required viscosity, and filtering to obtain the waterborne glass baking varnish.
7. The method of claim 6, wherein: the mixed solution before the dye or the colorant is added is a transparent solution, and the viscosity of the transparent solution is 10-1000 centipoises at 25 ℃.
8. The method of claim 6, wherein: the solid content of the prepared water-based glass baking paint is 25-75%.
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Denomination of invention: Water based glass baking varnish and its preparation method

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