CN112538294A - Environment-friendly zinc-aluminum-magnesium coating surface treating agent and preparation method and use method thereof - Google Patents
Environment-friendly zinc-aluminum-magnesium coating surface treating agent and preparation method and use method thereof Download PDFInfo
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- CN112538294A CN112538294A CN202011415141.1A CN202011415141A CN112538294A CN 112538294 A CN112538294 A CN 112538294A CN 202011415141 A CN202011415141 A CN 202011415141A CN 112538294 A CN112538294 A CN 112538294A
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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
- C09D143/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium, or a metal; Coating compositions based on derivatives of such polymers
- C09D143/04—Homopolymers or copolymers of monomers containing silicon
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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
- 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
- C09D167/08—Polyesters modified with higher fatty oils or their acids, or with natural resins or resin acids
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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
- 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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- 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
- C09D7/63—Additives non-macromolecular organic
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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
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/04—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the coating material
- C23C2/06—Zinc or cadmium or alloys based thereon
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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
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/26—After-treatment
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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
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/34—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the shape of the material to be treated
- C23C2/36—Elongated material
- C23C2/40—Plates; Strips
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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
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/07—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
- C23C22/08—Orthophosphates
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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
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/68—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous solutions with pH between 6 and 8
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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
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/324—Alkali metal phosphate
Abstract
The invention discloses an environment-friendly zinc-aluminum-magnesium coating surface treating agent, and a preparation method and a use method thereof, and belongs to the technical field of zinc-aluminum-magnesium alloy coating steel plate surface treatment. The invention provides an environment-friendly zinc-aluminum-magnesium coating surface treating agent for meeting the requirements of blackening resistance and environmental protection of a hot-dip zinc-aluminum-magnesium alloy coating steel plate, in particular to a hot and humid environment, which comprises the following components: 10-30 parts of aqueous organic emulsion, 5-20 parts of titanate, 2-15 parts of organic acid or acidic organic acid salt, 0.3-5 parts of phosphate, 5-20 parts of silica sol and 100 parts of water. According to the invention, a compact framework of the zinc-aluminum-magnesium surface coating is formed by crosslinking and cooperating aqueous organic emulsion and titanate under organic weak acid, phosphate is precipitated on the surface of a steel plate, silica sol is filled in the gaps of the framework, the contact between a coating and water vapor and oxygen in the environment is hindered by the synergistic action of various substances, and the corrosion resistance, black degeneration resistance, water resistance and fingerprint resistance of the surface coating are improved.
Description
Technical Field
The invention belongs to the technical field of surface treatment of a zinc-aluminum-magnesium alloy coated steel plate, and particularly relates to an environment-friendly zinc-aluminum-magnesium coating surface treating agent, and a preparation method and a use method thereof.
Background
The Zn-Al-Mg alloy coating steel plate has better corrosion resistance and excellent processing application performance (formability, weldability and paintability), and has increasingly obvious trend of replacing the prior corresponding hot-dip galvanized or zinc alloy coating steel plate.
The existing hot dip Zn-Al-Mg alloy coated steel plate can be divided into three types of low aluminum (WAl is less than 5 percent), medium aluminum (WAl is more than or equal to 5 percent and less than 13 percent) and high aluminum (WAl is more than or equal to 47 percent and less than or equal to 57 percent). As the content of Al and Mg increases, the corrosion resistance of the plating layer increases, but the formability and weldability decrease. In the field of household appliance and automobile application, in order to ensure that a Zn-Al-Mg alloy coating steel plate meets the punch forming requirement of a user, a low-aluminum component system is required to have good formability.
The surface of the zinc-aluminum-magnesium alloy coating has a large amount of Al and Mg elements, and the zinc-aluminum-magnesium alloy coating is very easy to oxidize, blacken and rusted in severe cases in the storage and transportation processes. In order to improve the corrosion resistance of the zinc-aluminum-magnesium alloy coating steel plate and prevent blackening, surface passivation treatment is required. However, the domestic environment-friendly surface treatment technology of the zinc-aluminum-magnesium coated steel plate is not mature, and domestic few enterprises research the surface treatment technology of the zinc-aluminum-magnesium coating of a low-aluminum system.
CN107418328A discloses a special chromium-free fingerprint-resistant liquid for a zinc-aluminum-magnesium coated steel plate and a preparation method thereof, wherein the product comprises the following components in parts by mass: 10-20 parts of a silane coupling agent; 10-20 parts of water-based acrylic resin; 10-20 parts of waterborne polyurethane resin; 1-10 parts of a metal compound; 1-10 parts of a lubricating additive; 30-60 parts of deionized water. CN111020549A provides a chromium-free passivation solution for zinc aluminum magnesium plating plates, comprising an aqueous medium and at least the following components present in the aqueous medium in a dissolved/dispersed state: aluminum ions, phosphates, fluoroacids, oxidizing agents, and resins; aluminum ions are introduced as film forming ions through the combination of an oxidant, phosphate and fluoric acid, the corrosion resistance and the water resistance of a zinc-magnesium-aluminum coating are improved through the synergistic effect of the phosphorization and the oxidation processes, the blackening tendency of magnesium-aluminum metal is effectively inhibited, and the adhesive force of the coating is greatly improved through the introduction of resin. CN105814239A discloses a method for treating a zinc-aluminum-magnesium alloy plated steel sheet with a chemical conversion coating having extremely excellent corrosion resistance and adhesion to a resin coating, which comprises treating the surface of the zinc-aluminum-magnesium alloy plated steel sheet with a metal surface treating agent, wherein the metal surface treating agent comprises a predetermined amount of a compound (a) having a zirconyl ([ Zr ═ O ]2+) structure, a vanadium compound (B), a titanium-fluorine complex compound (C), an organic phosphorus compound (Da) containing a phosphoric acid group and/or a phosphonic acid group, an inorganic phosphorus compound (Db), a specific aqueous acrylic resin (E), and an oxazoline group-containing polymer (F) as a curing agent, and the pH of the metal surface treating agent is 3 to 6.
Although the three coatings disclose that the environment-friendly passivation coating has good corrosion resistance and black degeneration resistance, the three coatings are not characterized by a clear or standard test method, and the performance of the three coatings cannot be determined; the blackening agent is obtained by production practice and use of users, the blackening is a chronic disease of zinc-aluminum-magnesium products, and no environment-friendly surface coating with excellent blackening resistance is found in China at present. Therefore, in order to realize the application of the zinc-aluminum-magnesium alloy coated steel plate product variety in the field of household appliances, research on an environment-friendly zinc-aluminum-magnesium coating surface treating agent and a preparation method of a hot-dip zinc-aluminum-magnesium alloy coated steel plate with excellent blackening resistance needs to be carried out.
Disclosure of Invention
The invention provides an environment-friendly zinc-aluminum-magnesium alloy coating surface treating agent suitable for improving the performance of a hot-dip zinc-aluminum-magnesium alloy coating steel plate, which aims to meet the requirements of household appliances and automobile users on blackening resistance and environmental protection of the hot-dip zinc-aluminum-magnesium alloy coating steel plate, in particular the use requirements in a damp-heat environment, and comprises the following components in parts by weight: 10-30 parts of aqueous organic emulsion, 5-20 parts of titanate, 2-15 parts of organic acid or acidic organic acid salt, 0.3-5 parts of phosphate, 5-20 parts of silica sol and 100 parts of water.
In the environment-friendly zinc-aluminum-magnesium coating surface treating agent, the pH value of the environment-friendly zinc-aluminum-magnesium coating surface treating agent is 5.0-7.0.
In the environment-friendly zinc-aluminum-magnesium coating surface treating agent, the water is at least one of deionized water or distilled water.
In the environment-friendly zinc-aluminum-magnesium coating surface treating agent, the water-based organic emulsion is at least one of acrylic emulsion, styrene-acrylic emulsion, water-based silicone-acrylic emulsion, water-based epoxy resin emulsion or water-based alkyd emulsion.
In the environment-friendly zinc-aluminum-magnesium coating surface treating agent, the titanate is at least one of alcohol amine titanate, di (triethanolamine) diisopropyl titanate, chelate phosphate titanium coupling agent quaternary ammonium salt, oxyacetic acid chelate titanate or ethylene glycol chelate titanate.
In the environment-friendly zinc-aluminum-magnesium plating surface treating agent, the organic acid or acidic organic acid salt is at least one of acetic acid, oxalic acid, citric acid, propionic acid, glucose, lactic acid, maleic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, fruit acid, monosodium fruit acid, sodium maleate, benzoic acid or monosodium oxalate.
In the environment-friendly zinc-aluminum-magnesium coating surface treating agent, the phosphate is at least one of sodium monohydrogen phosphate, potassium monohydrogen phosphate, cesium monohydrogen phosphate, ammonium phosphate, sodium dihydrogen phosphate or potassium dihydrogen phosphate.
Wherein, in the environment-friendly zinc-aluminum-magnesium coating surface treating agent, the solid content (mass content) of the aqueous organic emulsion is 46-60%.
In the environment-friendly zinc-aluminum-magnesium coating surface treating agent, the mass content of silica sol is 20-30 wt%.
Further, the invention also provides a preparation method of the environment-friendly zinc-aluminum-magnesium coating surface treating agent, which comprises the following steps: the components are taken according to the parts by weight, firstly, organic acid or acidic organic acid salt is dissolved in water, then phosphate is added, titanate is added after complete dissolution, aqueous resin emulsion is added after the titanate is hydrolyzed, finally, silica sol is added, and the components are stirred uniformly.
Further, the invention also provides a using method of the environment-friendly zinc-aluminum-magnesium coating surface treating agent, which comprises the following steps: the environment-friendly zinc-aluminum-magnesium coating surface treating agent is coated on the surface of a hot-dip zinc-aluminum-magnesium alloy coating steel plate and is dried and solidified.
In the use method of the environment-friendly zinc-aluminum-magnesium coating surface treating agent, the coating mode is reverse coating through a roller coating process.
In the use method of the environment-friendly zinc-aluminum-magnesium coating surface treating agent, the chemical components of a coating of the hot-dip zinc-aluminum-magnesium alloy coated steel plate are 1-3 wt% of Al, 0.5-2.0 wt% of Mg and the balance of Zn.
In the use method of the environment-friendly zinc-aluminum-magnesium coating surface treating agent, the thickness of the chromium-free coating of the hot-dip zinc-aluminum-magnesium alloy coating steel plate is 0.5-1.5 mu m.
In the use method of the environment-friendly zinc-aluminum-magnesium coating surface treating agent, the drying and curing temperature is 80-110 ℃.
In the use method of the environment-friendly zinc-aluminum-magnesium coating surface treating agent, the drying and curing time is 10-60 s.
By adopting the environment-friendly zinc-aluminum-magnesium coating surface treating agent, the surface treatment is carried out on the coating of the hot-dip zinc-aluminum-magnesium alloy coating steel plate through the process, so that the corrosion resistance, the blackening resistance, the water resistance and the fingerprint resistance of the surface coating are obviously improved, and the invention also provides the hot-dip zinc-aluminum-magnesium alloy coating steel plate obtained through the surface treatment.
The invention has the beneficial effects that:
according to the invention, a compact framework of the zinc-aluminum-magnesium surface coating is formed by the cross-linking synergistic effect of the aqueous organic emulsion and the titanate in the organic weak acid environment, phosphate is precipitated on the surface of the steel plate, the combination of the coating and the coating is enhanced, and the silica sol is filled in the gaps of the framework, so that the compactness of the surface coating is greatly improved, the contact of the coating and water vapor and oxygen in the environment is hindered by the synergistic effect of various substances, the corrosion resistance, the black degeneration resistance, the water resistance and the fingerprint resistance of the surface coating are improved, and the use requirements of users are met.
Detailed Description
Specifically, the environment-friendly zinc-aluminum-magnesium coating surface treating agent comprises the following components in parts by weight: 10-30 parts of aqueous organic emulsion, 5-20 parts of titanate, 2-15 parts of organic acid or acidic organic acid salt, 0.3-5 parts of phosphate, 5-20 parts of silica sol and 100 parts of water.
In the environment-friendly zinc-aluminum-magnesium coating surface treating agent, the pH value of the system is a precondition for titanate hydrolysis, and is also a precondition for phosphate stabilization, and is also helpful for the reaction of the surface treating agent and the coating; if the size is too large, the titanate cannot be hydrolyzed or is not hydrolyzed completely, the stability of the phosphate is poor, the reaction speed with the coating is slow, and the film forming speed is reduced and the quality of the film layer is poor; if the pH is too low, the organic resin will agglomerate and have poor stability. Therefore, the pH value of the environment-friendly zinc-aluminum-magnesium coating surface treating agent is controlled to be 5.0-7.0.
In the present invention, the water is at least one of deionized water or distilled water.
In the invention, the water-based organic emulsion is at least one of acrylic emulsion, styrene-acrylic emulsion, water-based silicone-acrylic emulsion, water-based epoxy resin emulsion or water-based alkyd emulsion; meanwhile, the higher the solid content of the aqueous organic emulsion is, the higher the concentration is, the more the active ingredients are, and the better the surface compactness of the alloy is, so that the aqueous organic emulsion with the solid content of 46-60% is selected.
In the invention, the titanate is at least one of alcohol amine titanate, di (triethanolamine) diisopropyl titanate, chelate phosphate titanium coupling agent quaternary ammonium salt, oxyacetic acid chelate titanate or ethylene glycol chelate titanate.
In the invention, the organic acid or acidic organic acid salt is at least one of acetic acid, oxalic acid, citric acid, propionic acid, glucose, lactic acid, maleic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, fruit acid, monosodium fruit acid, sodium maleate, benzoic acid or monosodium oxalate.
In the invention, the phosphate is at least one of sodium monohydrogen phosphate, potassium monohydrogen phosphate, cesium monohydrogen phosphate, ammonium phosphate, sodium dihydrogen phosphate or potassium dihydrogen phosphate.
In the invention, the colloidal silicon dioxide mainly plays a role in filling, the compactness of the film layer is enhanced, the higher the solid content is, the higher the concentration is, the more the active ingredients are, and the better the performance is in a certain range; if the content is too high, the powder falling defect is easy to occur; therefore, the invention selects the silica sol with the mass content of 20-30 wt% of silica.
Further, the invention also provides a preparation method of the environment-friendly zinc-aluminum-magnesium coating surface treating agent, which comprises the following steps: the components are taken according to the parts by weight, firstly, organic acid or acidic organic acid salt is dissolved in water, then phosphate is added, titanate is added after complete dissolution, aqueous resin emulsion is added after the titanate is hydrolyzed, finally, silica sol is added, and the components are uniformly stirred.
In the preparation method of the surface treating agent, the organic acid is added to accelerate the dissolution of phosphate, the titanate is hydrolyzed under an acidic condition, and after the hydrolysis is finished (generally, 20-60 min is needed), the aqueous organic resin and the silica sol are added, so that the stability of the surface treating agent is better; if the inorganic salt and the titanate are directly mixed, the inorganic salt is not easy to dissolve, the titanate cannot be hydrolyzed, and the coagulation and precipitation of resin and silica sol are easy to occur; therefore, the invention controls the adding sequence of the materials.
Further, the invention also provides a using method of the environment-friendly zinc-aluminum-magnesium coating surface treating agent, which comprises the following steps: the environment-friendly zinc-aluminum-magnesium coating surface treating agent is coated on the surface of a hot-dip zinc-aluminum-magnesium alloy coating steel plate and is dried and solidified.
The surface treating agent contains titanate coupling agent, needs crosslinking to form a film, has poor spraying effect, slightly poor stability of a forward coating process, thin film thickness and difficult control, and is coated by reverse coating preferably through a roller coating process.
Although the surface treating agent is designed for low-aluminum alloy, phosphate in the surface treating agent can have better performance only by reacting with Al and Mg, and the effect is not good when the contents of Mg and Al are too low; however, the higher the contents of Mg and Al, the gas is easily and rapidly generated by reaction in an acid environment, which is not favorable for the compactness of the film layer. Therefore, the environment-friendly zinc-aluminum-magnesium coating surface treating agent is particularly suitable for hot-dip zinc-aluminum-magnesium alloy coated steel plates with coatings containing 1-3 wt% of Al, 0.5-2.0 wt% of Mg and the balance of Zn.
In the use method of the environment-friendly zinc-aluminum-magnesium coating surface treating agent, after drying and curing, the thickness of a non-chromium coating (namely the surface treating agent after drying and curing on the coating surface) of a hot-dip zinc-aluminum-magnesium alloy coating steel plate is 0.5-1.5 mu m.
After the surface treating agent is coated on the surface of the hot-dip galvanized aluminum-magnesium alloy coating steel plate, drying and curing are needed under certain process conditions; through tests: if the temperature is too low, the coating cannot be completely dried, the film is not completely formed, the compactness of the film layer is poor, the coating is easy to fall off, and the performance is poor; if the temperature is too high, the water in the coating is volatilized too fast, the film is not formed sufficiently, and the organic resin is possibly damaged at the high temperature, so that the performance is deteriorated; the baking time is too long, which has no obvious influence, but is not beneficial to the production of a production line (the efficiency is low). Therefore, the temperature of drying and curing is controlled to be 80-110 ℃ and the time is 10-60 s.
By adopting the environment-friendly zinc-aluminum-magnesium coating surface treating agent, the surface treatment is carried out on the coating of the hot-dip zinc-aluminum-magnesium alloy coating steel plate through the process, so that the corrosion resistance, the blackening resistance, the water resistance and the fingerprint resistance of the surface coating are obviously improved, and the invention also provides the hot-dip zinc-aluminum-magnesium alloy coating steel plate obtained through the surface treatment.
The present invention is further illustrated by the following examples, which are not intended to limit the scope of the invention.
The contents of the components of the zinc-aluminum-magnesium plating surface treatment agent in examples 1 to 9 and comparative examples 1 to 5 are shown in table 1.
TABLE 1 content (parts by weight) of the surface treating agent component in the examples and comparative examples
In examples 1 to 8 and comparative examples 1 to 5, the specific selection of each component was as follows:
in examples 1 to 5 and comparative examples 1 to 5, water was first distilled water, the aqueous organic emulsion was aqueous silicone-acrylic emulsion (solid content: 50%), titanate was oxoacetate chelate titanate, organic acid or acidic organic acid salt was propionic acid, phosphate was sodium monohydrogen phosphate, and silica content in silica sol was 25%.
In example 6, unlike example 1, the aqueous organic emulsion is an aqueous alkyd emulsion.
In example 7, the titanate is an alcohol amine titanate, unlike example 1.
In example 8, the organic acid or acidic organic acid salt was lactic acid, which is different from example 1.
Preparation of surface treating agent
The components are taken according to the parts by weight, firstly, organic acid or acidic organic acid salt is dissolved in water, then, phosphate is added, titanate is added after complete dissolution, aqueous resin emulsion is added after uniform mixing for 30min, finally, silica sol is added, and the mixture is placed for 30min after uniform stirring.
Surface treatment of hot-dip zinc-aluminum-magnesium alloy coating steel plate
The surface treatment agents of examples 1 to 8 and comparative examples 1 to 5 were respectively roll-coated on hot-dip galvanized aluminum-magnesium alloy coated steel sheets of 1.5 wt% Al to 1.5 wt% Mg-Zn, and cured at a curing temperature of 80 ℃ (the curing temperature was measured by using a temperature measuring test paper) for 15 seconds to obtain hot-dip galvanized aluminum-magnesium coated sheets 1 to 8 and comparative examples L1 to L5.
TABLE 2 coating thicknesses of steel plates in examples and comparative examples
| Coating thickness (μm) | Coating thickness (μm) | ||
| Example 1 | 1.0 | Example 8 | 0.9 |
| Example 2 | 0.9 | Comparative example 1 | 0.8 |
| Example 3 | 1.1 | Comparative example 2 | 1.0 |
| Example 4 | 0.9 | Comparative example 3 | 1.0 |
| Example 5 | 0.8 | Comparative example 4 | 0.9 |
| Example 6 | 1.0 | Comparative example 5 | 1.0 |
| Example 7 | 1.0 |
Performance testing
1. The stability of the surface treatment liquid of the hot-dip galvanized aluminum-magnesium alloy coated steel plate is measured by the test example, and the test method comprises the following steps: the prepared passivation solution is placed in a ventilation place in a room, and the time for stable storage (no adverse phenomena such as color change, precipitation, agglomeration and the like) of the solution is observed, and the result is shown in table 3 (the quality guarantee period of the coating treatment solution accepted in the industry at present is 90 d).
Table 3 stability testing of surface treatment agents
2. The corrosion resistance, blackening resistance, fingerprint resistance, water resistance and coating properties of the coatings of 1 to 8 and L1 to L5 on the surface of the hot-dip galvanized aluminum-magnesium alloy plated steel sheet were measured by the test examples. The results are shown in Table 4.
Wherein, the corrosion resistance is tested according to the method and the conditions specified in GB/T10125, and then the corrosion result is evaluated according to the specification of GB12335-90 (expressed by the percentage of the corrosion area after 72h and 96h to the total area). Wherein, the smaller the corrosion area, the better (NSST/72 h corrosion area is required to be less than or equal to 5 percent generally at present).
The blackening resistance is good if no obvious color change is seen on the surface, namely the color difference value is less than or equal to 2, according to the color difference change before and after a damp-heat test at 50 ℃ and 95% RH.
The fingerprint resistance is judged according to the change of the color difference value before and after the surface of the sample is coated with vaseline: if the change of the front and rear color difference is less than 1, the color difference is A level; if the change of the front and rear chromatic aberration is more than 1 and less than 2, the grade is B; if the change of the front and rear color difference is more than 2 and less than 4, the color is C-level; and if the change of the front and rear color difference is more than 4, the D level is obtained. The fingerprint resistance of current coatings is generally B-grade and above.
Water resistance was determined by dropping deionized water at 100 ℃ onto the test specimen: if the sample has no water mark completely, the sample is A grade; if the water stain is slight, the grade B is obtained; obvious water stain, grade C. At present, the water resistance of the coating is generally A grade or B grade.
TABLE 4 Hot-dip galvanizing Al-Mg coated plate Performance test
Through comparison between examples 1 to 8 and comparative examples 1 to 5 and combination of data in tables 3 and 4, it can be seen that the hot dip galvanized aluminum magnesium alloy coating environment-friendly treatment liquid provided by the invention has good stability, and a hot dip galvanized aluminum magnesium coating plate formed after coating and curing has good corrosion resistance, black degeneration resistance, fingerprint resistance, water resistance and other properties.
Claims (10)
1. The environment-friendly zinc-aluminum-magnesium coating surface treating agent is characterized by comprising the following components in parts by weight: comprises the following components in parts by weight: 10-30 parts of aqueous organic emulsion, 5-20 parts of titanate, 2-15 parts of organic acid or acidic organic acid salt, 0.3-5 parts of phosphate, 5-20 parts of silica sol and 100 parts of water.
2. The environment-friendly zinc-aluminum-magnesium coating surface treating agent as claimed in claim 1, wherein: the pH value of the environment-friendly zinc-aluminum-magnesium coating surface treating agent is 5.0-7.0.
3. The environment-friendly zinc-aluminum-magnesium coating surface treating agent as claimed in claim 1, wherein: the water is at least one of deionized water or distilled water.
4. The environment-friendly zinc-aluminum-magnesium coating surface treating agent as claimed in claim 1, wherein: at least one of the following is satisfied:
the water-based organic emulsion is at least one of acrylic emulsion, styrene-acrylic emulsion, water-based silicone-acrylic emulsion, water-based epoxy resin emulsion or water-based alkyd emulsion;
the titanate is at least one of alcohol amine titanate, di (triethanolamine) diisopropyl titanate, chelate phosphate titanium coupling agent quaternary ammonium salt, oxyacetic acid chelate titanate or glycol chelate titanate;
the organic acid or the acidic organic acid salt is at least one of acetic acid, oxalic acid, citric acid, propionic acid, glucose, lactic acid, maleic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, fruit acid, monosodium fruit acid, sodium maleate, benzoic acid or monosodium oxalate;
the phosphate is at least one of sodium monohydrogen phosphate, potassium monohydrogen phosphate, cesium monohydrogen phosphate, ammonium phosphate, sodium dihydrogen phosphate or potassium dihydrogen phosphate.
5. The environment-friendly zinc-aluminum-magnesium coating surface treating agent as claimed in any one of claims 1 to 4, characterized in that: the solid content of the aqueous organic emulsion is 46-60%.
6. The environment-friendly zinc-aluminum-magnesium coating surface treating agent as claimed in any one of claims 1 to 4, characterized in that: the mass content of silicon dioxide in the silica sol is 20-30 wt%.
7. The preparation method of the environment-friendly zinc-aluminum-magnesium coating surface treating agent as claimed in any one of claims 1 to 6, which is characterized in that: the method comprises the following steps: the components are taken according to the parts by weight, firstly, organic acid or acidic organic acid salt is dissolved in water, then phosphate is added, titanate is added after complete dissolution, aqueous resin emulsion is added after the titanate is hydrolyzed, finally, silica sol is added, and the components are stirred uniformly.
8. The use method of the environment-friendly zinc-aluminum-magnesium coating surface treating agent as claimed in any one of claims 1 to 6, characterized in that: the method comprises the following steps: the environment-friendly zinc-aluminum-magnesium coating surface treating agent is coated on the surface of a hot-dip zinc-aluminum-magnesium alloy coating steel plate and is dried and solidified.
9. The use method of the environment-friendly zinc-aluminum-magnesium coating surface treating agent according to claim 8, characterized in that: at least one of the following is satisfied:
the coating mode is reverse coating through a roller coating process;
the chemical components of the coating of the hot-dip galvanized aluminum-magnesium alloy coated steel plate are 1-3 wt% of Al, 0.5-2.0 wt% of Mg and the balance of Zn;
after drying and curing, the thickness of the non-chromium coating of the hot-dip galvanized aluminum-magnesium alloy coating steel plate is 0.5-1.5 mu m;
the drying and curing temperature is 80-110 ℃;
the drying and curing time is 10-60 s.
10. A hot-dip zinc aluminum magnesium alloy coated steel sheet surface-treated according to claim 8 or 9.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113699514A (en) * | 2021-07-29 | 2021-11-26 | 马鞍山钢铁股份有限公司 | Zinc-aluminum-magnesium coating passivator, passivation film and passivation plate |
| CN114150319A (en) * | 2021-11-29 | 2022-03-08 | 沈阳理工大学 | Water-based environment-friendly steel plate antirust treatment liquid and preparation and use methods thereof |
| CN114774905A (en) * | 2022-03-30 | 2022-07-22 | 马鞍山钢铁股份有限公司 | Special environment-friendly passivator and passivation process for chromium-free galvanized aluminum-magnesium steel plate |
Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003155451A (en) * | 2001-11-19 | 2003-05-30 | Nippon Paint Co Ltd | Aqueous coating agent for steel, coating method, and coated steel |
| EP1498510A2 (en) * | 2003-07-17 | 2005-01-19 | Nippon Paint Co., Ltd. | Metal surface treatment composition, metal surface treatment method, and galvanized steel plate |
| JP2005240125A (en) * | 2004-02-27 | 2005-09-08 | Nippon Steel Corp | Non-oriented electromagnetic steel sheet with insulating layer having adequate properties |
| US20080081196A1 (en) * | 2006-10-02 | 2008-04-03 | Nippon Steel Corporation | Surface-treated metal sheet |
| CN101326308A (en) * | 2005-12-15 | 2008-12-17 | 日本帕卡濑精株式会社 | Surface treatment for metal materials, surface treatment process, and surface- treated metal materials |
| CN102477552A (en) * | 2010-11-29 | 2012-05-30 | 攀钢集团钢铁钒钛股份有限公司 | Surface treatment liquid and galvanized metal material |
| CN102666920A (en) * | 2009-11-25 | 2012-09-12 | 杰富意钢铁株式会社 | Surface-treating composition, and surface-treated steel sheet |
| US20130177779A1 (en) * | 2010-09-29 | 2013-07-11 | Jfe Steel Corporation | Method for manufacturing zinc or zinc alloy coated steel sheet and zinc or zinc alloy coated steel sheet manufactured by the method |
| TW201420809A (en) * | 2012-11-20 | 2014-06-01 | Great Fortune Steel Co Ltd | A visible surface coated layer with composite of inorganic and organic, a anti-fingerprint Zn-plated steel sheet therewith and manufacturing method thereof |
| CN105111807A (en) * | 2015-09-22 | 2015-12-02 | 攀钢集团攀枝花钢铁研究院有限公司 | High-corrosion-resistant coating solution and preparation method of hot-dip galvanized coating plate |
| CN107418328A (en) * | 2017-06-16 | 2017-12-01 | 上海兴赛尔表面材料有限公司 | A kind of special chromium-free fingerprint-resistant liquid of zinc-aluminum-magnesium clad steel sheet and preparation method thereof |
| CN109321908A (en) * | 2018-10-26 | 2019-02-12 | 四川理工学院 | A kind of metal surface multifunction environment-protection type nanometer vitrification liquid and preparation method thereof and application method |
| CN111733410A (en) * | 2020-07-07 | 2020-10-02 | 奎克化学（中国）有限公司 | Chromium-free passivation solution for zinc-aluminum-magnesium steel plate and preparation method thereof |
-
2020
- 2020-12-04 CN CN202011415141.1A patent/CN112538294B/en active Active
Patent Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003155451A (en) * | 2001-11-19 | 2003-05-30 | Nippon Paint Co Ltd | Aqueous coating agent for steel, coating method, and coated steel |
| EP1498510A2 (en) * | 2003-07-17 | 2005-01-19 | Nippon Paint Co., Ltd. | Metal surface treatment composition, metal surface treatment method, and galvanized steel plate |
| JP2005240125A (en) * | 2004-02-27 | 2005-09-08 | Nippon Steel Corp | Non-oriented electromagnetic steel sheet with insulating layer having adequate properties |
| CN101326308A (en) * | 2005-12-15 | 2008-12-17 | 日本帕卡濑精株式会社 | Surface treatment for metal materials, surface treatment process, and surface- treated metal materials |
| US20080081196A1 (en) * | 2006-10-02 | 2008-04-03 | Nippon Steel Corporation | Surface-treated metal sheet |
| CN102666920A (en) * | 2009-11-25 | 2012-09-12 | 杰富意钢铁株式会社 | Surface-treating composition, and surface-treated steel sheet |
| US20130177779A1 (en) * | 2010-09-29 | 2013-07-11 | Jfe Steel Corporation | Method for manufacturing zinc or zinc alloy coated steel sheet and zinc or zinc alloy coated steel sheet manufactured by the method |
| CN102477552A (en) * | 2010-11-29 | 2012-05-30 | 攀钢集团钢铁钒钛股份有限公司 | Surface treatment liquid and galvanized metal material |
| TW201420809A (en) * | 2012-11-20 | 2014-06-01 | Great Fortune Steel Co Ltd | A visible surface coated layer with composite of inorganic and organic, a anti-fingerprint Zn-plated steel sheet therewith and manufacturing method thereof |
| CN105111807A (en) * | 2015-09-22 | 2015-12-02 | 攀钢集团攀枝花钢铁研究院有限公司 | High-corrosion-resistant coating solution and preparation method of hot-dip galvanized coating plate |
| CN107418328A (en) * | 2017-06-16 | 2017-12-01 | 上海兴赛尔表面材料有限公司 | A kind of special chromium-free fingerprint-resistant liquid of zinc-aluminum-magnesium clad steel sheet and preparation method thereof |
| CN109321908A (en) * | 2018-10-26 | 2019-02-12 | 四川理工学院 | A kind of metal surface multifunction environment-protection type nanometer vitrification liquid and preparation method thereof and application method |
| CN111733410A (en) * | 2020-07-07 | 2020-10-02 | 奎克化学（中国）有限公司 | Chromium-free passivation solution for zinc-aluminum-magnesium steel plate and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 周杰等: "热镀锌板复合钛盐钝化膜的耐腐蚀性能", 《材料保护》 * |
| 宫丽等: "纳米硅溶胶／丙烯酸复合防蚀薄膜的研究", 《材料保护》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113699514A (en) * | 2021-07-29 | 2021-11-26 | 马鞍山钢铁股份有限公司 | Zinc-aluminum-magnesium coating passivator, passivation film and passivation plate |
| CN113699514B (en) * | 2021-07-29 | 2022-12-27 | 马鞍山钢铁股份有限公司 | Zinc-aluminum-magnesium coating passivator, passivation film and passivation plate |
| CN114150319A (en) * | 2021-11-29 | 2022-03-08 | 沈阳理工大学 | Water-based environment-friendly steel plate antirust treatment liquid and preparation and use methods thereof |
| CN114150319B (en) * | 2021-11-29 | 2023-08-29 | 沈阳理工大学 | Water-based environment-friendly steel plate rust-proof treatment fluid and preparation and use methods thereof |
| CN114774905A (en) * | 2022-03-30 | 2022-07-22 | 马鞍山钢铁股份有限公司 | Special environment-friendly passivator and passivation process for chromium-free galvanized aluminum-magnesium steel plate |
| CN114774905B (en) * | 2022-03-30 | 2024-03-01 | 马鞍山钢铁股份有限公司 | Passivating agent and passivating process special for environment-friendly chromium-free galvanized aluminum magnesium steel plate |
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