CN114672228B - Environment-friendly color steel plate and preparation method thereof - Google Patents
Environment-friendly color steel plate and preparation method thereof Download PDFInfo
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- CN114672228B CN114672228B CN202210308575.4A CN202210308575A CN114672228B CN 114672228 B CN114672228 B CN 114672228B CN 202210308575 A CN202210308575 A CN 202210308575A CN 114672228 B CN114672228 B CN 114672228B
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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
- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
- C09D167/06—Unsaturated polyesters having carbon-to-carbon unsaturation
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- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
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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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
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- 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
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
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- 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
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/63—Additives non-macromolecular organic
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- 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
- C09D7/40—Additives
- C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/14—Cleaning or pickling metallic material with solutions or molten salts with alkaline solutions
- C23G1/19—Iron or steel
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
- C08K2003/3045—Sulfates
Abstract
The invention relates to the field of color steel plates, in particular to an environment-friendly color steel plate and a preparation method thereof. Firstly, two photocuring materials of bisphenol A epoxy diacrylate and polyester acrylate are selected as base materials of the environment-friendly coating, 1-3 parts of 2-hydroxy-2-methyl-1-phenyl-1-acetone is used as a photocuring agent, and an acid corrosion agent and hydrofluoric acid are added into the photocuring agent, so that a binary structure oxide taking Cu-Ti as a main salt element and a passivation film combined with organic matters can be rapidly generated on the surface of a steel plate, the corrosion resistance of the surface of the steel plate is improved, and the adhesiveness of the steel plate to the environment-friendly coating is improved. Furthermore, the imidazole zinc modified nano silicon ball synthesized by the invention has certain performance of catalyzing and degrading organic pollutants, can enhance the adhesive force of the environment-friendly coating prepared by the invention on a steel plate, is assisted by a silane coupling agent, a leveling agent and acidic silica sol, realizes strong adhesion of a photocuring coating on the steel plate, and improves the corrosion resistance and the environmental protection.
Description
Technical Field
The invention relates to the field of color steel plates, in particular to an environment-friendly color steel plate and a preparation method thereof.
Background
The color steel plate has the properties of high mechanical strength and easy forming of steel materials, and also has good decoration and corrosion resistance of coating materials, so the color steel plate becomes a new material which is worried by the world at present. With the improvement of science and technology and the enhancement of environmental awareness and the improvement of the living standard of people, the color steel plate prefabricated house increasingly shows strong vitality and wide market prospect and is favored by buildings, household appliances, electromechanics, transportation, interior decoration, office appliances and other industries. The color steel plate prefabricated house has the advantages of light weight, high strength, heat preservation, heat insulation, attractive appearance, durability and the like, and is a high-grade building integrating the building and decoration into a whole, and the installation is rapid. The color steel plate prefabricated house is clean in construction and widely applied to large-span plants, warehouses, office buildings, villas, roof floors, air purification rooms, cold storages, shops, kiosks and temporary rooms. The weight of the light color steel plate sandwich plate in square meter is lower than 14KG, so that the structural load can be fully reduced, and the construction cost of the movable house is reduced. The characteristics of light dead weight, splicing installation and random cutting of the color steel plate prefabricated house determine the simplicity and convenience of the prefabricated house installation, can greatly improve the benefit and save the construction period. The surface material and the heat insulation material of the fireproof color steel plate sandwich plate are non-combustible materials, and the fireproof standard requirement of the prefabricated house can be completely met. The wide use over 40 years abroad proves that: the quality guarantee period of the color steel plate treated by the special coating is 10-15 years, and the anti-corrosion coating is sprayed every 10 years later, so that the service life of the prefabricated house plate can reach more than 35 years. The clear lines of the profiled color steel plate can be dozens of colors, and the profiled color steel plate can meet the requirements of movable house buildings of any style to achieve satisfactory effect. The common heat insulation material for the color steel plate composite plate comprises the following components: rock wool, glass fiber cotton, polystyrene, polyurethane and the like, and has low heat conductivity coefficient, so that the movable house has good heat preservation and heat insulation effects. The high-strength color steel plate adopts a high-strength steel plate as a base material (tensile strength of 5600 kg/cm) and is formed by the most advanced design and rolling. Therefore, the color steel plate prefabricated house has excellent structural characteristics.
The corrosion prevention of color steel plates is a constantly studied problem, and among the measures for reducing and controlling the corrosion of metals, the application of anticorrosive coatings is one of the most economical and effective methods. Most of anticorrosive coatings are solvent-based coatings, but a large amount of Volatile Organic Compounds (VOC) volatilize in the curing process, pollute the environment and damage human bodies, and meanwhile, the environment-friendly coatings are popular in the market along with the enhancement of the environment-friendly consciousness of people. The photocuring coating has the advantages of high curing speed, no VOC (volatile organic compounds) emission, energy conservation and the like, is a commonly used green environment-friendly coating, is widely applied to the fields of protection and decoration of paper, woodware, glass and plastic surfaces, and is less applied to the field of metal corrosion prevention. If the photocureable coating is applied to the field of color steel plate corrosion prevention, the production efficiency of the corrosion-resistant coating can be improved, the cost is reduced, and the pollution problem of a solvent type corrosion-resistant coating can be solved. However, since the interface force (adhesion) between the photo-cured coating and the metal substrate is weak, the corrosive medium is very likely to damage the coating/metal interface, causing metal corrosion, because the huge internal stress generated by the photo-cured coating during the curing process cannot be released in time and is accumulated between the substrate and the coating, so that the photo-cured coating is very likely to peel off from the metal substrate during long-term use. Therefore, it is important for researchers to improve the adhesion between the photocured coating and the surface of the metal substrate and reduce VOC so as to further improve the corrosion resistance of the photocured coating.
CN 103073990A discloses an ultraviolet light curing coating composition for coating color steel plate, comprising the following components: high-functional polyester acrylate, polyurethane acrylate, epoxy acrylate, a monofunctional acrylate monomer, a high-functional acrylate monomer, acrylated acrylate, a photoinitiator, a leveling agent, a polymerization inhibitor and a solvent. It does not take into account the problem of interfacial forces between the photocurable coating and the metal substrate.
Disclosure of Invention
A preparation method of an environment-friendly color steel plate comprises the following steps:
s1, degreasing, cleaning and drying the surface of a steel plate;
s2, coating the environment-friendly coating on the steel plate subjected to degreasing and cleaning treatment by using a coating device, leveling for 7-9h at 50-70 ℃ with the wet film thickness of 70-90 mu m, and then exposing for 4-6 times by using a photocuring machine with the total irradiation energy of 700-900mJ/cm 2 And obtaining the environment-friendly color steel plate.
The degreasing and cleaning treatment is carried out on a steel plate according to a bath ratio of 1g: (18-22) mL of the steel plate is placed in 24-26wt% of sodium bicarbonate water solution at the temperature of 60-70 ℃ to be soaked for 4-5min, then the steel plate is washed for 3-4 times by water at the temperature of 20-30 ℃, and the steel plate is dried to obtain the clean steel plate.
The environment-friendly coating comprises the following raw materials in parts by mass: 4-8 parts of acidic silica sol, 2-8 parts of acid etching agent, 0.2-1 part of hydrofluoric acid with the concentration of 45-55wt%, 0.1-0.5 part of flatting agent, 2-4 parts of silane coupling agent, 4-8 parts of imidazole zinc modified nano silicon spheres, 25-30 parts of bisphenol A epoxy diacrylate, 40-50 parts of polyester acrylate and 1-3 parts of 2-hydroxy-2-methyl-1-phenyl-1-acetone.
The acid etching agent is one or a mixture of copper sulfate and fluotitanic acid; preferably, the acid etching agent is prepared from copper sulfate and fluotitanic acid in a mass ratio of (0.5-4): (0.5-3.5) mixing.
The silane coupling agent is one of gamma-aminopropyl trimethoxy silane, gamma- (2, 3-epoxy propoxy) propyl trimethoxy silane, gamma-methacryloxy propyl trimethoxy silane and vinyl trimethoxy silane; preferably, the silane coupling agent is vinyltrimethoxysilane.
The leveling agent is one of polyether modified organic silicon leveling agent and polyester modified organic silicon leveling agent.
The preparation method of the imidazole zinc modified nano silicon spheres comprises the following steps:
(1) Adding 2-4 parts of polyvinylpyrrolidone into 20-30 parts of n-amyl alcohol, then adding 2-5 parts of absolute ethyl alcohol, 0.1-0.5 part of sodium citrate and 5-10 parts of ammonia water with the concentration of 20-24wt%, stirring at the rotating speed of 100-200r/min for 5-10min, then adding 1-2 parts of tetraethyl orthosilicate, continuing stirring at the rotating speed of 100-200r/min for 2-3h, filtering to obtain a filter cake, washing and drying to obtain nano silicon spheres;
(2) Mixing 35-45 parts by mass of absolute ethyl alcohol, 5-15 parts by mass of water, 1-2 parts by mass of ammonia water with the concentration of 20-24wt% and 0.1-0.5 part by mass of nano silicon spheres prepared in the step (1), adding 0.5-1 part by mass of vinyl trimethoxy silane after ultrasonic dispersion for 4-6min, stirring and reacting at the temperature of 65-75 ℃ at the rotating speed of 100-200r/min for 20-30h, filtering to obtain a filter cake, washing and drying to obtain the vinyl trimethoxy silane modified nano silicon spheres;
(3) Adding 1-2 parts by mass of the vinyltrimethoxysilane modified nano silicon spheres prepared in the step (2) and 1-2 parts by mass of N, N' -methylene bisacrylamide into 50-70 parts by mass of acetonitrile, uniformly mixing, adding 3-5 parts by mass of 1-vinylimidazole and 0.1-0.5 part by mass of azobisisobutyronitrile, ultrasonically dispersing for 4-6min, reacting at 100-115 ℃ for 10-30min, filtering, washing and drying to obtain 1-vinylimidazole modified nano silicon spheres;
(4) Adding 2-3 parts by mass of zinc chloride into 9-11 parts by mass of water, and stirring at the rotating speed of 100-200r/min for 5-10min to obtain a zinc chloride solution; and (3) adding 1-2 parts of the 1-vinylimidazole modified nano-silicon spheres prepared in the step (3) into the zinc chloride solution, stirring at room temperature at the rotating speed of 100-200r/min for 20-30h, filtering to obtain a filter cake, washing and drying to obtain the imidazole zinc modified nano-silicon spheres.
The power of the ultrasonic wave in the steps (2) - (3) is 50-70W, and the frequency is 70-90kHz.
As the conventional anticorrosive coatings adopted by the color steel plates are mostly solvent-based coatings, a large amount of Volatile Organic Compounds (VOC) volatilize in the curing process, so that the environment is polluted and the human body is injured. Aiming at the defect, the invention projects the light to the photocureable coating, has the advantages of high curing speed, no VOC emission, energy conservation and the like, and can improve the production efficiency of an anticorrosive coating, reduce the cost and solve the pollution problem of a solvent type anticorrosive coating if the photocureable coating is applied to the field of corrosion prevention of color steel plates. The invention selects two photo-curing materials of bisphenol A epoxy diacrylate and polyester acrylate as the base materials of the coating, and 1-3 parts of 2-hydroxy-2-methyl-1-phenyl-1-acetone as the photo-curing agent to obtain the environment-friendly photo-curing type environment-friendly coating for the color steel plate.
However, since the interface force between the photocurable coating and the metal substrate is weak, the corrosive medium is very likely to damage the coating/metal interface, resulting in metal corrosion, because the huge internal stress generated by the photocurable coating during the curing process cannot be released in time and is accumulated between the substrate and the coating, so that the photocurable coating is very likely to peel off from the metal substrate during long-term use.
Therefore, the acid corrosion agent and the hydrofluoric acid are further added into the photocureable coating, countless galvanic cells are formed on a micro-area of the surface of the steel plate according to a cathode film-forming mechanism to generate electrochemical reaction, so that the replacement of iron atoms by copper ions and titanic acid ions is realized, a binary structure oxide taking Cu-Ti as a main salt element and a passivation film combined with organic matters can be rapidly generated on the surface of the steel plate, the corrosion resistance of the surface of the steel plate is further improved, and the adhesion of the steel plate to the photocureable coating is improved.
In order to further improve the adhesive force of the environment-friendly coating prepared by the invention on the surface of a steel plate and simultaneously improve the capabilities of preventing corrosion and reducing VOC (volatile organic compounds) emission, the invention further synthesizes imidazole zinc modified nano silicon spheres. Firstly, tetraethyl orthosilicate is hydrolyzed to obtain nano silicon spheres, vinyl trimethoxy silane is used for modifying the nano silicon spheres to facilitate grafting of 1-vinyl imidazole, and finally, the 1-vinyl imidazole modified nano silicon spheres are immersed in zinc chloride solution to form imidazole zinc modified nano silicon spheres by strong chelation of zinc ions and imidazole molecules. The invention discovers that the coating has certain performance of catalyzing and degrading organic pollutants, can enhance the adhesive force of the environment-friendly coating prepared by the invention on a steel plate, is assisted by a silane coupling agent, a flatting agent and acidic silica sol, realizes strong adhesion of the photocureable coating on the steel plate, and improves the corrosion resistance and the environment friendliness of the photocureable coating.
The invention has the beneficial effects that:
1. the invention selects two photocureable materials of bisphenol A epoxy diacrylate and polyester acrylate as base materials of the environment-friendly coating, takes 1-3 parts of 2-hydroxy-2-methyl-1-phenyl-1-acetone as a photocuring agent, and adds an acid etching agent and hydrofluoric acid into the photocuring agent, so that a binary structure oxide taking Cu-Ti as a main salt element and a passivation film combined with organic matters can be rapidly generated on the surface of a steel plate, the corrosion resistance of the surface of the steel plate is further improved, and the adhesiveness of the steel plate to the environment-friendly coating is improved.
2. The invention further synthesizes imidazole zinc modified nano-silicon spheres which have certain performance of catalyzing and degrading organic pollutants, can enhance the adhesive force of the environment-friendly coating prepared by the invention on a steel plate, is assisted by a silane coupling agent, a flatting agent and acidic silica sol, realizes the strong adhesive force of the photocuring coating on the steel plate, and improves the corrosion resistance and the environmental protection.
Detailed Description
Steel plate, item number: 14614311, tianjin Steel science and technology development Co., ltd.
Acid silica sol, cat No.: 172003, shanghai Raman reagent, inc.
Bisphenol a epoxy diacrylate, type: g500, guangzhou five elements materials science and technology ltd.
Polyester acrylate, type: DR-E524, changxing materials industries, inc.
2-hydroxy-2-methyl-1-phenyl-1-propanone, cat #: r011849, shanghai Yi En chemical technology, inc.
Vinyltrimethoxysilane, cat # s: r007332, shanghai Yien chemical technology, inc.
The leveling agent adopted in the embodiment is a polyether modified organic silicon leveling agent, and the type is as follows: BYK-333, BYK chemical, germany.
Polyvinylpyrrolidone, type: PVPK30, kulanchebuco new material ltd.
N, N' -methylenebisacrylamide, cat #: r095978, shanghai yan chemical technology limited.
1-vinylimidazole, cat No.: r017676, shanghai yan chemical technology ltd.
Azobisisobutyronitrile, cat # n: 258, chemical Limited in the Minam century.
Example 1
The preparation method of the environment-friendly color steel plate comprises the following steps:
s1, degreasing, cleaning and drying the surface of a steel plate;
s2, coating the environment-friendly coating on the steel plate after degreasing and cleaning treatment by using a coating device, wherein the wet film thickness is 80 mu m, the coating is leveled for 8 hours at 60 ℃, then, the coating is exposed for 5 times by using a photocuring machine, and the total irradiation energy is 800mJ/cm 2 And obtaining the environment-friendly color steel plate.
The degreasing and cleaning treatment is carried out on a steel plate according to a bath ratio of 1g: and (3) soaking 20mL of the steel plate in a 25wt% sodium bicarbonate aqueous solution at 65 ℃ for 5min, washing the steel plate with water at 25 ℃ for 3 times, and drying to obtain the degreased and cleaned steel plate.
The environment-friendly coating comprises the following raw materials in parts by mass: 0.6 part of hydrofluoric acid with the concentration of 50wt%, 0.3 part of flatting agent, 3 parts of silane coupling agent, 28 parts of bisphenol A epoxy diacrylate, 45 parts of polyester acrylate and 2 parts of 2-hydroxy-2-methyl-1-phenyl-1-acetone.
The silane coupling agent is vinyl trimethoxy silane.
Example 2
The preparation method of the environment-friendly color steel plate comprises the following steps:
s1, degreasing, cleaning and drying the surface of a steel plate;
s2, coating the environment-friendly coating on the degreased and cleaned steel plate by using a coating device, wherein the thickness of a wet film is 80 mu m, the wet film flows flat for 8 hours at 60 ℃, then, the steel plate is exposed for 5 times by using a photocuring machine, and the total irradiation energy is 800mJ/cm 2 And obtaining the environment-friendly color steel plate.
The degreasing and cleaning treatment is carried out on a steel plate according to a bath ratio of 1g: and (3) soaking 20mL of the steel plate in a 25wt% sodium bicarbonate aqueous solution at 65 ℃ for 5min, washing with 25 ℃ water for 3 times, and drying to obtain the clean steel plate.
The environment-friendly coating comprises the following raw materials in parts by mass: 5 parts of acid etching agent, 0.6 part of hydrofluoric acid with the concentration of 50wt%, 0.3 part of flatting agent, 3 parts of silane coupling agent, 28 parts of bisphenol A epoxy diacrylate, 45 parts of polyester acrylate and 2 parts of 2-hydroxy-2-methyl-1-phenyl-1-acetone.
The acid etching agent is prepared from copper sulfate and fluotitanic acid in a mass ratio of (3): 2.6 mixing.
The silane coupling agent is vinyl trimethoxy silane.
Example 3
A preparation method of an environment-friendly color steel plate comprises the following steps:
s1, degreasing, cleaning and drying the surface of a steel plate;
s2, coating the environment-friendly coating on the degreased and cleaned steel plate by using a coating device, wherein the thickness of a wet film is 80 mu m, the wet film flows flat for 8 hours at 60 ℃, then, the steel plate is exposed for 5 times by using a photocuring machine, and the total irradiation energy is 800mJ/cm 2 And obtaining the environment-friendly color steel plate.
The degreasing and cleaning treatment is carried out on a steel plate according to a bath ratio of 1g:20mL of the steel plate is placed in a 25wt% sodium bicarbonate aqueous solution at 65 ℃ to be soaked for 5min, and then is washed by water at 25 ℃ for 3 times and dried to obtain the degreased and cleaned steel plate.
The environment-friendly coating comprises the following raw materials in parts by mass: 6 parts of acidic silica sol, 5 parts of acid etching agent, 0.6 part of hydrofluoric acid with the concentration of 50wt%, 0.3 part of flatting agent, 3 parts of silane coupling agent, 6 parts of vinyltrimethoxysilane modified nano silicon spheres, 28 parts of bisphenol A epoxy diacrylate, 45 parts of polyester acrylate and 2 parts of 2-hydroxy-2-methyl-1-phenyl-1-acetone.
The acid etching agent is prepared from copper sulfate and fluotitanic acid in a mass ratio of (3): 2.6 mixing.
The silane coupling agent is vinyl trimethoxy silane.
The preparation method of the vinyltrimethoxysilane modified nano silicon spheres comprises the following steps:
(1) Adding 3 parts of polyvinylpyrrolidone into 26 parts of n-amyl alcohol, then adding 3 parts of ethanol, 0.3 part of sodium citrate and 7 parts of ammonia water with the concentration of 21wt%, stirring at the rotating speed of 180r/min for 8min, then adding 1.6 parts of tetraethyl orthosilicate, continuing stirring at the rotating speed of 180r/min for 2.4h, and obtaining nano silicon spheres after filtering, washing and drying;
(2) Mixing 40 parts by mass of absolute ethyl alcohol, 10 parts by mass of water, 1.5 parts by mass of ammonia water with the concentration of 21wt% and 0.3 part by mass of the nano silicon spheres prepared in the step (1), adding 0.6 part by mass of vinyltrimethoxysilane after ultrasonic dispersion is carried out for 5min, then stirring and reacting at the rotating speed of 180r/min at 70 ℃ for 24h, filtering to obtain a filter cake, washing and drying to obtain the vinyltrimethoxysilane modified nano silicon spheres. The power of the ultrasound in the step (2) is 60W, and the frequency is 80kHz.
Example 4
The preparation method of the environment-friendly color steel plate comprises the following steps:
s1, degreasing, cleaning and drying the surface of a steel plate;
s2, coating the environment-friendly coating on the degreased and cleaned steel plate by using a coating device, wherein the thickness of a wet film is 80 mu m, the wet film flows flat for 8 hours at 60 ℃, then, the steel plate is exposed for 5 times by using a photocuring machine, and the total irradiation energy is 800mJ/cm 2 And obtaining the environment-friendly color steel plate.
The degreasing and cleaning treatment is carried out on a steel plate according to a bath ratio of 1g:20mL of the steel plate is placed in a 25wt% sodium bicarbonate aqueous solution at 65 ℃ to be soaked for 5min, and then is washed by water at 25 ℃ for 3 times and dried to obtain the degreased and cleaned steel plate.
The environment-friendly coating comprises the following raw materials in parts by mass: 6 parts of acidic silica sol, 5 parts of acid etching agent, 0.6 part of hydrofluoric acid with the concentration of 50wt%, 0.3 part of flatting agent, 3 parts of silane coupling agent, 6 parts of 1-vinylimidazole modified nano-silicon spheres, 28 parts of bisphenol A epoxy diacrylate, 45 parts of polyester acrylate and 2 parts of 2-hydroxy-2-methyl-1-phenyl-1-acetone.
The acid etching agent is prepared from copper sulfate and fluotitanic acid in a mass ratio of (3): 2.6 mixing.
The silane coupling agent is vinyl trimethoxy silane.
The preparation method of the imidazole 1-vinylimidazole modified nano silicon spheres comprises the following steps:
(1) Adding 3 parts by mass of polyvinylpyrrolidone into 26 parts by mass of n-amyl alcohol, then adding 3 parts by mass of ethanol, 0.3 part by mass of sodium citrate and 7 parts by mass of 21wt% ammonia water, stirring at a rotating speed of 180r/min for 8min, then adding 1.6 parts by mass of tetraethyl orthosilicate, continuing stirring at a rotating speed of 180r/min for 2.4h, and filtering, washing and drying to obtain nano silicon spheres;
(2) Mixing 40 parts by mass of absolute ethyl alcohol, 10 parts by mass of water, 1.5 parts by mass of ammonia water with the concentration of 21wt% and 0.3 part by mass of nano silicon spheres prepared in the step (1), adding 0.6 part by mass of vinyl trimethoxy silane after ultrasonic dispersion for 5min, stirring and reacting at the temperature of 70 ℃ at the rotating speed of 180r/min for 24h, filtering to obtain a filter cake, washing and drying to obtain vinyl trimethoxy silane modified nano silicon spheres;
(3) Adding 1 part of vinyltrimethoxysilane modified nano silicon ball prepared in the step (2) and 1 part of N, N' -methylene bisacrylamide into 60 parts of acetonitrile by mass, uniformly mixing, adding 4 parts of 1-vinylimidazole and 0.4 part of azobisisobutyronitrile, carrying out ultrasonic dispersion for 5min, reacting at 110 ℃ for 15min, filtering to obtain a filter cake, washing and drying to obtain the 1-vinylimidazole modified nano silicon ball. The power of the ultrasound in the steps (2) - (3) is 60W, and the frequency is 80kHz.
Example 5
The preparation method of the environment-friendly color steel plate comprises the following steps:
s1, degreasing, cleaning and drying the surface of a steel plate;
s2, coating the environment-friendly coating on the steel plate after degreasing and cleaning treatment by using a coating device, wherein the wet film thickness is 80 mu m, the coating is leveled for 8 hours at 60 ℃, then, the coating is exposed for 5 times by using a photocuring machine, and the total irradiation energy is 800mJ/cm 2 And obtaining the environment-friendly color steel plate.
The degreasing and cleaning treatment comprises the following steps of mixing a steel plate according to a bath ratio of 1g: and (3) soaking 20mL of the steel plate in a 25wt% sodium bicarbonate aqueous solution at 65 ℃ for 5min, washing the steel plate with water at 25 ℃ for 3 times, and drying to obtain the degreased and cleaned steel plate.
The environment-friendly coating comprises the following raw materials in parts by mass: 6 parts of acidic silica sol, 5 parts of acid etching agent, 0.6 part of hydrofluoric acid with the concentration of 50wt%, 0.3 part of flatting agent, 3 parts of silane coupling agent, 6 parts of imidazole zinc modified nano silicon spheres, 28 parts of bisphenol A epoxy diacrylate, 45 parts of polyester acrylate and 2 parts of 2-hydroxy-2-methyl-1-phenyl-1-acetone.
The acid etching agent is prepared from copper sulfate and fluotitanic acid in a mass ratio of (3): 2.6 mixing.
The silane coupling agent is vinyl trimethoxy silane.
The preparation method of the imidazole zinc modified nano silicon ball comprises the following steps:
(1) Adding 3 parts of polyvinylpyrrolidone into 26 parts of n-amyl alcohol, then adding 3 parts of absolute ethyl alcohol, 0.3 part of sodium citrate and 7 parts of ammonia water with the concentration of 21wt%, stirring at the rotating speed of 180r/min for 8min, then adding 1.6 parts of tetraethyl orthosilicate, continuing stirring at the rotating speed of 180r/min for 2.4h, filtering to obtain a filter cake, washing and drying to obtain nano silicon spheres;
(2) Mixing 40 parts by mass of absolute ethyl alcohol, 10 parts by mass of water, 1.5 parts by mass of ammonia water with the concentration of 21wt% and 0.3 part by mass of nano silicon spheres prepared in the step (1), adding 0.6 part by mass of vinyl trimethoxy silane after ultrasonic dispersion for 5min, stirring and reacting at the rotating speed of 180r/min for 24h at 70 ℃, filtering to obtain a filter cake, washing and drying to obtain vinyl trimethoxy silane modified nano silicon spheres;
(3) Adding 1 part of the vinyltrimethoxysilane modified nano silicon ball prepared in the step (2) and 1 part of N, N' -methylenebisacrylamide into 60 parts of acetonitrile by mass, uniformly mixing, adding 4 parts of 1-vinylimidazole and 0.4 part of azobisisobutyronitrile, carrying out ultrasonic dispersion for 5min, then placing at 110 ℃ for reaction for 15min, filtering, washing to obtain a filter cake, washing and drying to obtain the 1-vinylimidazole modified nano silicon ball;
(4) Adding 2.72 parts of zinc chloride into 10 parts of water by mass, and stirring at the rotating speed of 180r/min for 8min to obtain a zinc chloride solution; and (3) adding 1 part of the 1-vinylimidazole modified nano-silicon spheres prepared in the step (3) into the zinc chloride solution, stirring at the room temperature at the rotating speed of 180r/min for 24 hours, filtering to obtain a filter cake, washing and drying to obtain the imidazole zinc modified nano-silicon spheres. The power of the ultrasound in the steps (2) - (3) is 60W, and the frequency is 80kHz.
Example 6
The preparation method of the environment-friendly color steel plate comprises the following steps:
s1, degreasing, cleaning and drying the surface of a steel plate;
s2, coating the environment-friendly coating on the steel plate after degreasing and cleaning treatment by using a coating device, wherein the wet film thickness is 80 mu m, the coating is leveled for 8 hours at 60 ℃, then, the coating is exposed for 5 times by using a photocuring machine, and the total irradiation energy is 800mJ/cm 2 And obtaining the environment-friendly color steel plate.
The degreasing and cleaning treatment comprises the following steps of mixing a steel plate according to a bath ratio of 1g: and (3) soaking 20mL of the steel plate in a 25wt% sodium bicarbonate aqueous solution at 65 ℃ for 5min, washing the steel plate with water at 25 ℃ for 3 times, and drying to obtain the degreased and cleaned steel plate.
The environment-friendly coating comprises the following raw materials in parts by mass: 6 parts of acidic silica sol, 5 parts of acid etching agent, 0.6 part of hydrofluoric acid with the concentration of 50wt%, 0.3 part of flatting agent, 3 parts of silane coupling agent, 28 parts of bisphenol A epoxy diacrylate, 45 parts of polyester acrylate and 2 parts of 2-hydroxy-2-methyl-1-phenyl-1-acetone.
The acid etching agent is prepared from copper sulfate and fluotitanic acid in a mass ratio of (3): 2.6 mixing.
The silane coupling agent is vinyl trimethoxy silane.
Example 7
The preparation method of the environment-friendly color steel plate comprises the following steps:
s1, degreasing, cleaning and drying the surface of a steel plate;
s2, coating the environment-friendly coating on the steel plate after degreasing and cleaning treatment by using a coating device, wherein the wet film thickness is 80 mu m, the coating is leveled for 8 hours at 60 ℃, then, the coating is exposed for 5 times by using a photocuring machine, and the total irradiation energy is 800mJ/cm 2 And obtaining the environment-friendly color steel plate.
The degreasing and cleaning treatment is carried out on a steel plate according to a bath ratio of 1g: and (3) soaking 20mL of the steel plate in a 25wt% sodium bicarbonate aqueous solution at 65 ℃ for 5min, washing the steel plate with water at 25 ℃ for 3 times, and drying to obtain the degreased and cleaned steel plate.
The environment-friendly coating comprises the following raw materials in parts by mass: 6 parts of acidic silica sol, 0.6 part of hydrofluoric acid with the concentration of 50wt%, 0.3 part of flatting agent, 3 parts of silane coupling agent, 6 parts of imidazole zinc modified nano silicon spheres, 28 parts of bisphenol A epoxy diacrylate, 45 parts of polyester acrylate and 2 parts of 2-hydroxy-2-methyl-1-phenyl-1-acetone.
The silane coupling agent is vinyl trimethoxy silane.
The preparation method of the imidazole zinc modified nano silicon ball comprises the following steps:
(1) Adding 3 parts by mass of polyvinylpyrrolidone into 26 parts by mass of n-amyl alcohol, then adding 3 parts by mass of ethanol, 0.3 part by mass of sodium citrate and 7 parts by mass of 21wt% ammonia water, stirring at a rotating speed of 180r/min for 8min, then adding 1.6 parts by mass of tetraethyl orthosilicate, continuing stirring at a rotating speed of 180r/min for 2.4h, and filtering, washing and drying to obtain nano silicon spheres;
(2) Mixing 40 parts by mass of absolute ethyl alcohol, 10 parts by mass of water, 1.5 parts by mass of ammonia water with the concentration of 21wt% and 0.3 part by mass of nano silicon spheres prepared in the step (1), adding 0.6 part by mass of vinyl trimethoxy silane after ultrasonic dispersion for 5min, stirring and reacting at the temperature of 70 ℃ at the rotating speed of 180r/min for 24h, filtering to obtain a filter cake, washing and drying to obtain vinyl trimethoxy silane modified nano silicon spheres;
(3) Adding 1 part of the vinyltrimethoxysilane modified nano silicon ball prepared in the step (2) and 1 part of N, N' -methylenebisacrylamide into 60 parts of acetonitrile by mass, uniformly mixing, adding 4 parts of 1-vinylimidazole and 0.4 part of azobisisobutyronitrile, performing ultrasonic dispersion for 5min, reacting at 110 ℃ for 15min, filtering to obtain a filter cake, washing and drying to obtain the 1-vinylimidazole modified nano silicon ball;
(4) Adding 2.72 parts of zinc chloride into 10 parts of water by mass, and stirring at the rotating speed of 180r/min for 8min to obtain a zinc chloride solution; and (3) adding 1 part of the 1-vinylimidazole modified nano-silicon spheres prepared in the step (3) into the zinc chloride solution, stirring at the room temperature at the rotating speed of 180r/min for 24 hours, filtering to obtain a filter cake, washing and drying to obtain the imidazole zinc modified nano-silicon spheres. The power of the ultrasound in the steps (2) - (3) is 60W, and the frequency is 80kHz.
Test example 1
The coating adhesion of the environment-friendly color steel plate prepared in each example is tested by referring to GB/T9286-2021 test of drawing a grid of colored paint and varnish. An electrically driven multi-edge cutting tool is adopted, and the distance between the cutting edges is 1mm; the thickness of the environment-friendly color steel plate is 0.3mm, and the thickness of the coating film is 74 mu m.
Table 1: adhesion test results
As can be seen from Table 1, the environmental color steel plate prepared in example 5 has the best adhesion, smooth cut edge and no falling off. This is due to the addition of imidazole zinc modified nano silicon spheres. The imidazole zinc modified nano silicon spheres can form intermolecular acting force with strong polar groups in a coating system, and silicon and zinc ions in the imidazole zinc modified nano silicon spheres can be condensed with hydroxyl on the surface of a metal substrate to form a chemical bond; meanwhile, the imidazole zinc group is an excellent cross-linking agent and can participate in resin curing, so that a bridge is formed between the coating and the substrate to improve the adhesion of the coating. Example 4 the 1-vinylimidazole modified nano-silica spheres lacked the crosslinking effect of zinc ions on acrylic resin and hydroxyl groups, and therefore, the adhesion of the obtained coating film was reduced. Example 3 is nano silicon spheres modified by vinyltrimethoxysilane, which has a certain capacity of crosslinking resin, but lacks imidazole groups and zinc ions, and has weak adhesion capacity to a steel plate, although the adhesion level is 1, the cut intersection is larger than the shedding area of example 4. The adhesion force of the embodiment 2 is superior to that of the embodiment 1 because the acid corrosion agent is added, countless galvanic cells are formed on a micro area of the surface of the steel plate according to a cathode film forming mechanism to generate electrochemical reaction, so that the replacement of iron atoms by copper ions and titanic acid ions is realized, a binary structure oxide mainly comprising Cu-Ti and a passivation film combined with organic matters can be rapidly generated on the surface of the steel plate, and compared with iron atoms, the binary structure oxide has stronger adsorption capacity on hydroxyl and organic matters, can be condensed with more silicon hydroxyl to form a 'bridge' between the steel plate and organic paint, and enhances the adhesion capacity of the paint. The acid etching agent corrodes the steel plate, increases the surface area of the steel plate and increases the content of hydroxyl; the imidazole zinc modified nano silicon spheres, the connecting steel plate and the coating are synergistic, so that the adhesive force of the coating is greatly improved. This is also illustrated by a comparison of example 6, example 7 and example 5.
Test example 2
Neutral salt spray test
The salt fog resistance of the environment-friendly color steel plate prepared in each example is tested by referring to GB/T1771-2007 'determination of neutral salt fog resistance of colored paint and varnish'. The size of the plate is as follows: 150mm x 100mm, film thickness 74 μm, temperature of salt fog box 35 deg.C, salt fog collection rate 2mL/h, and sodium chloride concentration 50g/L. The time to pitting was recorded and the results are shown in table 2.
Table 2: salt spray resistance test results
| Salt spray resistance time/h | |
| Example 1 | 157 |
| Example 2 | 281 |
| Example 3 | 362 |
| Example 4 | 409 |
| Example 5 | 478 |
| Example 6 | 446 |
| Example 7 | 451 |
It can be seen from table 2 that the environmental-friendly color steel plate prepared in example 5 has the best salt spray resistance, which is the result of the combined action of the acid corrosion agent and the imidazole zinc modified nano silicon spheres. The imidazole zinc modified nano silicon spheres can form intermolecular acting force with strong polar groups in a coating system, and silicon and zinc ions in the imidazole zinc modified nano silicon spheres can be condensed with hydroxyl on the surface of a metal substrate to form a chemical bond; meanwhile, the imidazole zinc group is an excellent cross-linking agent and can participate in resin curing, so that a bridge is formed between the coating and the substrate to improve the adhesion of the coating. The acid corrosion agent is added, countless galvanic cells are formed on a micro-area of the surface of the steel plate to generate electrochemical reaction according to a cathode film forming mechanism, so that the replacement of copper ions and titanic acid ions for iron atoms is realized, a binary structure oxide mainly comprising Cu-Ti and a passivation film combined with organic matters can be rapidly generated on the surface of the steel plate, and compared with the iron atoms, the copper-titanium-based composite passivation film has stronger adsorption capacity for hydroxyl and the organic matters, can be condensed with more silicon hydroxyl to form a 'bridge' of the steel plate and the organic coating, and enhances the adhesion capacity of the coating. The improvement of the adhesive force increases the contact between the coating and the steel plate and reduces the damage of a corrosion medium to a coating/metal interface. Meanwhile, a passivation film formed by the acid etching agent also has certain salt spray resistance.
Claims (5)
1. The preparation method of the environment-friendly color steel plate is characterized by comprising the following steps of:
s1, degreasing, cleaning and drying the surface of a steel plate;
s2, coating the environment-friendly coating on the steel plate subjected to degreasing and cleaning treatment by using a coating device, leveling for 7-9h at 50-70 ℃ with the wet film thickness of 70-90 microns, and then exposing for 4-6 times by using a photocuring machine to obtain the environment-friendly color steel plate;
the environment-friendly coating comprises the following raw materials in parts by mass: 4-8 parts of acidic silica sol, 2-8 parts of acid etching agent, 0.2-1 part of hydrofluoric acid with the concentration of 45-55wt%, 0.1-0.5 part of flatting agent, 2-4 parts of silane coupling agent, 4-8 parts of imidazole zinc modified nano silicon spheres, 25-30 parts of bisphenol A epoxy diacrylate, 40-50 parts of polyester acrylate and 1-3 parts of 2-hydroxy-2-methyl-1-phenyl-1-acetone;
the acid etching agent is prepared from copper sulfate and fluotitanic acid according to the mass ratio (0.5-4): (0.5-3.5) mixing;
the preparation method of the imidazole zinc modified nano silicon ball comprises the following steps:
(1) Adding 2-4 parts of polyvinylpyrrolidone into 20-30 parts of n-amyl alcohol, then adding 2-5 parts of ethanol, 0.1-0.5 part of sodium citrate and 5-10 parts of ammonia water with the concentration of 20-24wt%, stirring at the rotating speed of 100-200r/min for 5-10min, then adding 1-2 parts of tetraethyl orthosilicate, continuing stirring at the rotating speed of 100-200r/min for 2-3h, and filtering, washing and drying to obtain nano silicon spheres;
(2) Mixing 35-45 parts by mass of absolute ethyl alcohol, 5-15 parts by mass of water, 1-2 parts by mass of ammonia water with the concentration of 20-24wt% and 0.1-0.5 part by mass of nano silicon spheres prepared in the step (1), adding 0.5-1 part by mass of vinyl trimethoxy silane after ultrasonic dispersion for 4-6min, stirring and reacting at the temperature of 65-75 ℃ at the rotating speed of 100-200r/min for 20-30h, filtering to obtain a filter cake, washing and drying to obtain the vinyl trimethoxy silane modified nano silicon spheres;
(3) Adding 1-2 parts by mass of the vinyltrimethoxysilane modified nano silicon spheres prepared in the step (2) and 1-2 parts by mass of N, N' -methylene bisacrylamide into 50-70 parts by mass of acetonitrile, uniformly mixing, adding 3-5 parts by mass of 1-vinylimidazole and 0.1-0.5 part by mass of azobisisobutyronitrile, ultrasonically dispersing for 4-6min, reacting at 100-115 ℃ for 10-30min, filtering to obtain a filter cake, washing and drying to obtain the 1-vinylimidazole modified nano silicon spheres;
(4) Adding 2-3 parts of zinc chloride into 9-11 parts of water by mass, and stirring at the rotating speed of 100-200r/min for 5-10min to obtain a zinc chloride solution; and (3) adding 1-2 parts of the 1-vinylimidazole modified nano-silicon spheres prepared in the step (3) into the zinc chloride solution, stirring at room temperature at the rotating speed of 100-200r/min for 20-30h, filtering to obtain a filter cake, washing and drying to obtain the imidazole zinc modified nano-silicon spheres.
2. The method for manufacturing the environment-friendly color steel plate according to claim 1, wherein the degreasing and cleaning treatment is performed by mixing the steel plate in a bath ratio of 1g: (18-22) mL, soaking in 24-26wt% sodium bicarbonate water solution at 60-70 ℃ for 4-5min, washing with water at 20-30 ℃ for 3-4 times, and drying to obtain the clean steel plate.
3. The method for preparing environment-friendly color steel plate according to claim 1, wherein the total irradiation energy of the light curing machine is 700-900mJ/cm 2 。
4. The method for preparing environment-friendly color steel plate as claimed in claim 1, wherein the silane coupling agent is one of gamma-aminopropyltrimethoxysilane, gamma- (2, 3-epoxypropoxy) propyltrimethoxysilane, gamma-methacryloxypropyltrimethoxysilane and vinyltrimethoxysilane.
5. An environment-friendly color steel plate, which is manufactured by the method for manufacturing the environment-friendly color steel plate according to any one of claims 1 to 4.
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