CN111534815A - Pretreatment liquid capable of forming washable natural color conversion film on metal surface and preparation method thereof - Google Patents
Pretreatment liquid capable of forming washable natural color conversion film on metal surface and preparation method thereof Download PDFInfo
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- CN111534815A CN111534815A CN202010441096.0A CN202010441096A CN111534815A CN 111534815 A CN111534815 A CN 111534815A CN 202010441096 A CN202010441096 A CN 202010441096A CN 111534815 A CN111534815 A CN 111534815A
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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
- C23C22/78—Pretreatment of the material to be coated
Abstract
The invention discloses a pretreatment liquid capable of forming a washable true color conversion coating on a metal surface and a preparation method thereof, wherein the pretreatment liquid comprises the following components: 0-10% of chelating agent, 1-12% of modified chelating agent, 0.1-0.2% of salt assistant, 0.5-1% of auxiliary agent, 0.05-2% of complexing agent, 0-10% of neutralizing agent and the balance of water; the modified chelating agent comprises at least 3 elements of C, N, O, H, P, S, B, Na, Ca, Mg, Fe, Zn, Cl, F and Si. The metal surface treatment liquid of the invention contains few substances, is simple and easy to operate, and has environmental-friendly and pollution-free waste liquid. The treated workpiece can be washed by water to obtain a colorless and uniform natural color conversion film, so that the appearance of the metal workpiece is kept from being damaged, and the application range of the pretreatment liquid is expanded to a great extent. The conversion coating obtained by the invention greatly increases the surface roughness of the base material, the film layer is firmly combined with the base material, and the adhesion and corrosion resistance of the coating and the surface of the base material are effectively improved.
Description
Technical Field
The invention belongs to the technical field of metal surface pretreatment, and particularly relates to a pretreatment liquid capable of forming a washable natural color conversion film on a metal surface and a preparation method thereof.
Background
The information in this background section is only for enhancement of understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art that is already known to a person of ordinary skill in the art.
At present, the surface treatment of metal is generally carried out by adopting phosphating solution in the aspect of industrial production, and a layer of compact porous film is formed on the surface of a workpiece. Although the corrosion resistance of the metal surface can be improved, the carcinogenicity of hexavalent chromium brings great hidden danger to the industrial production process and waste liquid treatment, and the problem of environmental pollution is not ignored. In recent years, environmental protection type anticorrosion treatment has been receiving more and more attention. In order to maintain sustainable development ecological environment, a simple, feasible, green and pollution-free metal surface treatment technology is developed to replace the traditional phosphating technology, and the method has important economic value and social benefit.
Workpieces obtained by treating metals with different pretreatment liquids in the market have different colors, subsequent treatment procedures are added, and the appearance and the application range of the metals are greatly influenced. For example: the conversion film obtained by the treatment of the zinc phosphating solution presents light gray, gray and dark gray, the iron phosphating solution presents blue, bluish purple and color after forming a film, the manganese phosphating solution presents black and dark black after forming a film, a workpiece usually presents gold, brown and light blue after no phosphorus zirconium treatment, and the surface of the metal base material obtained by the silane treatment solution presents faint yellow, bluish purple and the like. Although the appearance of the alkaline silane treatment liquid reduces the natural color of the metal to a great extent in recent years, the treated workpiece cannot be washed by water, the adhesion is insufficient, some production quality problems are easy to occur in the using process, and the like, so that certain limitation is caused to the metal pretreatment industry.
Disclosure of Invention
In order to solve the technical problems in the prior art, the invention aims to provide a pretreatment liquid capable of forming a washable natural color conversion coating on the surface of metal and a preparation method thereof.
In order to achieve the above object, one or more embodiments of the present invention disclose the following technical solutions:
in a first aspect, the invention provides a pretreatment liquid capable of forming a washable natural color conversion coating on a metal surface, which comprises the following components:
0-10% of chelating agent, 1-12% of modified chelating agent, 0.1-0.2% of salt assistant, 0.5-1% of auxiliary agent, 0.05-2% of complexing agent, 0-10% of neutralizing agent and the balance of water;
the modified chelating agent comprises at least 3 elements of C, N, O, H, P, S, B, Na, Ca, Mg, Fe, Zn, Cl, F and Si.
In a second aspect, a method for preparing the pretreatment liquid is provided, which comprises the following steps:
dissolving a chelating agent and an auxiliary modified material into an aqueous solution of alcohol, and reacting to obtain a modified chelating agent; the auxiliary modified material comprises at least three elements of C, N, O, H, P, S, B, Cl, F and Si;
then, the chelating agent, the modified chelating agent, the salt assistant, the auxiliary agent, the complexing agent, the neutralizer and the water are compounded to prepare the pretreatment liquid.
In a third aspect, there is provided a method for surface-pretreating a metal substrate with the pretreatment liquid, comprising the steps of:
degreasing and washing the metal base material, and soaking the metal base material in the pretreatment liquid to form a film;
and after film forming is finished, taking out, washing and drying.
Compared with the prior art, the above one or more embodiments of the present invention achieve the following beneficial effects:
1. the pretreatment liquid is environment-friendly, does not contain phosphate, and greatly reduces the pollution of waste liquid to the environment.
2. The application range of the pretreatment liquid is wide, and the treated workpiece can be washed by water without changing the performance of a surface conversion film.
3. The surface of the metal base material treated by the pretreatment liquid is covered with a colorless chemical conversion film, so that the original color of the workpiece is kept to the maximum extent, and the unique metallic luster of the workpiece is not damaged, so that the workpiece can be directly applied without further treatment.
4. The metal workpiece is treated by the pretreatment liquid, so that the corrosion resistance of the metal base material can be effectively improved, and the service life of the metal is prolonged.
5、After the pretreatment liquid is utilized to pretreat the metal base material, the roughness of the surface of the metal base material is increased, and the adhesive force between the metal base material and a paint film is effectively improved. After the treated cold-rolled steel plate is sprayed with plastics, a cross-cut and cross-cut experiment can reach zero level (no paint film falls off). The impact force experiment can reach 60N/cm2No radial cracks appeared. After being scratched, the coating is bent after being soaked in 5 percent saline solution for 5 days, and no paint film falls off. The plastic-sprayed scratch fork can resist salt fog for 500 hours, the electrophoretic scratch fork can resist salt fog for 1000 hours, and no paint film falls off.
6. The components contained in the pretreatment liquid are common and easy to obtain, the operation is simple and convenient, and the cost is low.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate exemplary embodiments of the invention and together with the description serve to explain the invention and not to limit the invention.
FIG. 1 is a photograph showing a metal substrate pretreated with the pretreatment liquid prepared in example 1 of the present invention.
Detailed Description
It is to be understood that the following detailed description is exemplary and is intended to provide further explanation of the invention as claimed. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the invention. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
In a first aspect, the invention provides a pretreatment liquid capable of forming a washable natural color conversion coating on a metal surface, which comprises the following components:
0-10% of chelating agent, 1-12% of modified chelating agent, 0.1-0.2% of salt assistant, 0.5-1% of auxiliary agent, 0.05-2% of complexing agent, 0-10% of neutralizing agent and the balance of water;
the modified chelating agent comprises at least 3 elements of C, N, O, H, P, S, B, Na, Ca, Mg, Fe, Zn, Cl, F and Si.
The modified chelating agent has more anchor points (hydroxyl groups), so that the adhesive force between the effective components and the metal can be greatly enhanced, meanwhile, the molecular weight of the modified chelating agent is larger, the volume is increased to a certain degree, the amount of the metal elements complexed by the coating with the same area is greatly reduced, and the color development of the metal elements is relieved, so that the conversion film is in a macroscopic colorless state.
And the addition of a small amount of chelating agent can increase the coverage of the coating and make the surface of the coating more uniform and ordered.
In some embodiments, the pretreatment liquid consists of:
2-10% of chelating agent, 5-12% of modified chelating agent, 0.1-0.2% of salt assistant, 0.5-1% of auxiliary agent, 0.05-2% of complexing agent, 0-10% of neutralizing agent and the balance of water.
Further, the pretreatment liquid consists of the following components:
2% of chelating agent, 5% of modified chelating agent, 0.1-0.2% of salt assistant, 0.5-1% of auxiliary agent, 0.05-2% of complexing agent, 0-10% of neutralizing agent and the balance of water.
Further, the pretreatment liquid consists of the following components:
7% of chelating agent, 10% of modified chelating agent, 0.1-0.2% of salt assistant, 0.5-1% of auxiliary agent, 0.05-2% of complexing agent, 0-10% of neutralizing agent and the balance of water.
Further, the pretreatment liquid consists of the following components:
9% of chelating agent, 7% of modified chelating agent, 0.1-0.2% of salt assistant, 0.5-1% of auxiliary agent, 0.05-2% of complexing agent, 0-10% of neutralizing agent and the balance of water.
In some embodiments, the chelating agent is aminotrimethylene phosphonic acid, alendronic acid, phytic acid, ethanolamine phosphate, hydroxyethylidene diphosphonic acid.
In some embodiments, the auxiliary salt is one or a mixture of magnesium nitrate, zinc oxide, calcium nitrate, zinc gluconate, magnesium sulfate, aluminum sulfate, zinc sulfate, aluminum nitrate, manganese sulfate, manganese nitrate, cerium nitrate, lanthanum nitrate, zirconium fluoride, zirconium sulfate, fluorozirconic acid, metatitanic acid, titanyl sulfate, vanadyl oxalate, fluorotitanic acid, barium sulfate, or barium nitrate. The salt aid can provide crystal nucleus for the formation of the film layer, promote the mutual chelation among effective substances and accelerate the film forming process. And the corrosion resistance of the film can be further enhanced by the aid of the salt with the corrosion resistance.
In some embodiments, the adjuvant is one or two of sodium borate, sodium gluconate, sodium sulfate, ammonium borate, sodium molybdate, ammonium molybdate, sodium nitrate, sodium chlorate, sodium bromate, sodium tungstate, hydrogen peroxide, sodium peroxide, or nitrobenzene.
In some embodiments, the complexing agent is one or a mixture of disodium EDTA, tetrasodium EDTA, tartaric acid, sodium tartrate, sodium citrate, aminotriacetic acid, and citric acid.
In some embodiments, the neutralizing agent is one or more of sodium carbonate, sodium bicarbonate, monoethanolamine, diethanolamine, ammonium carbonate, sodium hydroxide, potassium hydroxide, calcium hydroxide, triethanolamine, ammonia, and ammonium bicarbonate.
In some embodiments, the pH of the pretreatment liquid is 2 to 7, further 3 to 6.
In a second aspect, a method for preparing the pretreatment liquid is provided, which comprises the following steps:
dissolving a chelating agent and an auxiliary modified material into an aqueous solution of alcohol, and reacting to obtain a modified chelating agent; the auxiliary modified material comprises at least three elements of C, N, O, H, P, S, B, Cl, F and Si;
then, the chelating agent, the modified chelating agent, the salt assistant, the auxiliary agent, the complexing agent, the neutralizer and the water are compounded to prepare the pretreatment liquid.
In some embodiments, the auxiliary modifying material is titanium dioxide, silicon dioxide, silane coupling agent KH-560, KH-540, KH-550, KH-8252, KH-792, silicon powder, polypropylene, sodium polystyrene sulfonate, Tween 20, Tween 40, Tween 60, Tween 80, polyvinyl alcohol 2000, polyvinyl alcohol 4000, polyvinyl alcohol 6000, and polyvinyl alcohol 10000.
Further, the molar ratio of the chelating agent to the auxiliary modification material is 1:10-10: 1.
Furthermore, the mixing reaction temperature of the chelating agent and the auxiliary modified material is 50-100 ℃, and the reaction time is 8-12 h.
Further, the volume ratio of ethanol to water in the alcohol aqueous solution is 1:2-2: 1.
In some embodiments, the pH of the pretreatment liquor is adjusted to 2-7 by adding a neutralizing agent to the pretreatment liquor.
In a third aspect, there is provided a method for surface-pretreating a metal substrate with the pretreatment liquid, comprising the steps of:
degreasing and washing the metal base material, and soaking the metal base material in the pretreatment liquid to form a film;
and after film forming is finished, taking out, washing and drying.
In some embodiments, the metal substrate is immersed in the pretreatment liquid for a period of time ranging from 1 to 17 min.
Furthermore, the time for soaking the metal base material in the pretreatment liquid is 5-17 min.
The raw materials in the examples are all conventional raw materials and are commercially available products.
Example 1
A pretreatment liquid capable of forming a washable natural color conversion coating on a metal surface comprises the following components:
2% of chelating agent (hydroxyethylidene diphosphonic acid), 5% of modified chelating agent, 0.1% of salt assistant (aluminum nitrate), 1% of auxiliary agent (sodium nitrate), 1% of complexing agent (sodium tartrate), 5% of neutralizing agent (sodium carbonate) and the balance of water.
The preparation method of the modified chelating agent comprises the following steps:
respectively dissolving a chelating agent and an auxiliary modified material (titanium dioxide) into an alcohol-water mixed solution (the volume ratio of ethanol to water is 1:2), sequentially adding the uniformly dissolved chelating agent and the auxiliary modified material into a reactor while stirring, wherein the ratio of the chelating agent to the auxiliary modified material is controlled at 2:3, heating to 70 ℃, and keeping the temperature for 10 hours to obtain the modified chelating agent.
Preparing pretreatment liquid according to the proportion, adjusting the pH value of the solution to be 5, and treating the cold-rolled steel plate, wherein the method comprises the following specific steps:
(1) soaking the cold-rolled steel plate in a degreasing agent for degreasing, and washing with water;
(2) placing the degreased cold-rolled steel plate in a pretreatment liquid for 5 minutes at normal temperature for soaking treatment;
(3) and (3) taking out the cold-rolled steel plate treated in the step (2), washing with water, and naturally airing to finish surface treatment.
In this example, as shown in FIG. 1, the appearance of the cold-rolled steel sheet treated with the pretreatment liquid showed a colorless uniform conversion coating layer.
Example 2
A pretreatment liquid capable of forming a washable natural color conversion coating on a metal surface comprises the following components:
7% of chelating agent (amino trimethylene phosphonic acid), 10% of modified chelating agent, 0.2% of salt assistant (aluminum nitrate), 1% of auxiliary agent (sodium nitrate), 2% of complexing agent (sodium tartrate), 7% of neutralizing agent (sodium carbonate) and the balance of water.
The preparation method of the modified chelating agent comprises the following steps:
respectively dissolving a chelating agent and an auxiliary modified material (silicon dioxide) into an alcohol-water mixed solution (the volume ratio of ethanol to water is 1:1), sequentially adding the uniformly dissolved chelating agent and the auxiliary modified material into a reactor while stirring, wherein the ratio of the chelating agent to the auxiliary modified material is controlled at 1:10, heating to 100 ℃, and keeping the temperature for 8 hours to obtain the modified chelating agent.
The treatment solution was prepared according to the examples, the pH of the solution was adjusted to 4, and cold rolled steel sheets were treated as follows:
(1) soaking the cold-rolled steel plate in a degreasing agent for degreasing, and washing with water;
(2) soaking the degreased cold-rolled steel plate in the treatment solution for 10 minutes at normal temperature;
(3) and (3) taking out the cold-rolled steel plate treated in the step (2), washing with water, and naturally airing to finish surface treatment.
Example 3
The water-washable natural color conversion film pretreatment liquid is formed on the surface of metal on the basis of a chelating agent, and comprises the following raw materials in percentage by mass:
9 percent of chelating agent (alendronic acid), 7 percent of modified chelating agent, 0.15 percent of salt assistant (aluminum nitrate), 0.7 percent of auxiliary agent (sodium nitrate), 0.05 percent of complexing agent (sodium tartrate), 0 percent of neutralizing agent (sodium carbonate) and the balance of water.
The preparation method of the modified chelating agent comprises the following steps:
respectively dissolving a chelating agent and an auxiliary modified material (silicon powder) into an alcohol-water mixed solution (the volume ratio of ethanol to water is 1:1), sequentially adding the uniformly dissolved chelating agent and the auxiliary modified material into a reactor while stirring, wherein the ratio of the chelating agent to the auxiliary modified material is controlled at 10:1, heating to 60 ℃, and keeping the temperature for 8 hours to obtain the modified chelating agent.
The treatment solution is prepared according to the examples, the pH of the solution is adjusted to 6, and the cold-rolled steel plate is treated, and the specific steps are as follows:
(1) soaking the cold-rolled steel plate in a degreasing agent for degreasing, and washing with water;
(2) soaking the degreased cold-rolled steel plate in the treatment solution for 15 minutes at normal temperature;
(3) and (3) taking out the cold-rolled steel plate treated in the step (2), washing with water, and naturally airing to finish surface treatment.
Example 4
The water-washable natural color conversion film pretreatment liquid is formed on the surface of metal on the basis of a chelating agent, and comprises the following raw materials in percentage by mass:
0% of chelating agent (hydroxyethylidene diphosphonic acid), 7% of modified chelating agent, 0.15% of salt assistant (aluminum nitrate), 0.7% of auxiliary agent (sodium nitrate), 0.05% of complexing agent (sodium tartrate), 9% of neutralizing agent (sodium carbonate) and the balance of water.
The preparation method of the modified chelating agent comprises the following steps:
respectively dissolving a chelating agent and an auxiliary modified material (polypropylene) into an alcohol-water mixed solution (the volume ratio of ethanol to water is 1:1), sequentially adding the uniformly dissolved chelating agent and the auxiliary modified material into a reactor while stirring, wherein the ratio of the chelating agent to the auxiliary modified material is controlled at 10:1, heating to 60 ℃, and keeping the temperature for 8 hours to obtain the modified chelating agent.
The treatment solution is prepared according to the examples, the pH of the solution is adjusted to 6, and the cold-rolled steel plate is treated, and the specific steps are as follows:
(1) soaking the cold-rolled steel plate in a degreasing agent for degreasing, and washing with water;
(2) soaking the degreased cold-rolled steel plate in the treatment solution for 15 minutes at normal temperature;
(3) and (3) taking out the cold-rolled steel plate treated in the step (2), washing with water, and naturally airing to finish surface treatment.
Analysis of results
The cold rolled steel sheets of examples 1 to 4 after surface treatment were further examined, and the test items and results were as follows:
(a) appearance of cold rolled steel sheet after treatment: a uniform colorless chemical conversion film is formed on the surface of the substrate.
(b) Paint film adhesion experiment:
marking a hundred grids after plastic spraying experiment: the cold-rolled steel sheets of examples 1 to 4 were subjected to electrostatic spray molding, and then the cold-rolled steel sheets of examples 1 to 4 were subjected to a check test using a check machine, and all adhesion levels could reach zero level.
Impact resistance test after plastic spraying: the cold rolled steel sheets treated in examples 1 to 4 were subjected to electrostatic spray molding and then subjected to a hot rolling treatment at a temperature of 60N/cm2The surface of the steel plate has no radial cracks when subjected to an impact resistance test.
Saline soaking experiment after plastic spraying: the cold-rolled steel sheets treated in examples 1 to 4 were subjected to electrostatic spray molding, and then cross-cut was drawn on the surface of the paint film, so that a part of the base material was exposed to 5% saline, and was taken out after being soaked for 120 hours. No paint film falling phenomenon exists when the cold-rolled steel plate is bent at the intersection at 90 degrees.
Salt spray experiment after plastic spraying: the cold-rolled steel sheets treated in the examples 1 to 4 are subjected to electrostatic spraying, then the surface of a paint film is scratched in a cross shape, part of the base material is exposed, the paint film is placed in a salt spray box for 500 hours, and the paint film is peeled off by using an adhesive tape after being taken out, so that the phenomenon of peeling is avoided.
Salt spray experiment after electrophoresis: the cold-rolled steel sheets treated in the examples 1 to 4 were subjected to electrophoretic painting, then the surface of the paint film was scratched in a cross shape to expose a part of the base material, the base material was placed in a salt spray box for 1000 hours, and the paint film was peeled off with an adhesive tape after being taken out without a peeling phenomenon.
(c) Copper sulfate spot experiment: preparing a copper sulfate solution according to the national standard:
13mL/L 0.1mol/L HCl；
41g/L CuSO4·5H2O；
35g/L NaCl。
the copper sulfate titration resistance time of the cold-rolled steel sheet treated by the treatment solution of the present invention is as follows:
example 1: 70 seconds;
example 2: 90 seconds;
example 3: 78 seconds;
example 4: for 65 seconds.
The copper sulfate resistance experiment exceeds that of the similar products.
(d) Bare membrane 3.5 wt% saline soak experiment:
example 1: no significant rust spots appeared within 180 minutes;
example 2: no significant rust spots appeared within 120 minutes;
example 3: no significant rust spots appeared within 150 minutes;
example 4: no significant rust spots appeared within 110 minutes.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A pretreatment liquid capable of forming a washable natural color conversion coating on a metal surface is characterized by comprising the following components in parts by weight: the composition consists of the following components:
0-10% of chelating agent, 1-12% of modified chelating agent, 0.1-0.2% of salt assistant, 0.5-1% of auxiliary agent, 0.05-2% of complexing agent, 0-10% of neutralizing agent and the balance of water;
the modified chelating agent comprises at least 3 elements of C, N, O, H, P, S, B, Na, Ca, Mg, Fe, Zn, Cl, F and Si.
2. The pretreatment liquid according to claim 1, wherein the pretreatment liquid is a solution for forming a water-washable natural color conversion coating on a metal surface, and the solution comprises: the composition consists of the following components:
2-10% of chelating agent, 5-12% of modified chelating agent, 0.1-0.2% of salt assistant, 0.5-1% of auxiliary agent, 0.05-2% of complexing agent, 0-10% of neutralizing agent and the balance of water.
3. The pretreatment liquid according to claim 1, wherein the pretreatment liquid is a solution for forming a water-washable natural color conversion coating on a metal surface, and the solution comprises: the composition consists of the following components:
2% of chelating agent, 5% of modified chelating agent, 0.1-0.2% of salt assistant, 0.5-1% of auxiliary agent, 0.05-2% of complexing agent, 0-10% of neutralizing agent and the balance of water;
or the pretreatment liquid consists of the following components:
7% of chelating agent, 10% of modified chelating agent, 0.1-0.2% of salt assistant, 0.5-1% of auxiliary agent, 0.05-2% of complexing agent, 0-10% of neutralizing agent and the balance of water;
or the pretreatment liquid consists of the following components:
9% of chelating agent, 7% of modified chelating agent, 0.1-0.2% of salt assistant, 0.5-1% of auxiliary agent, 0.05-2% of complexing agent, 0-10% of neutralizing agent and the balance of water.
4. The pretreatment liquid according to claim 1, wherein the pretreatment liquid is a solution for forming a water-washable natural color conversion coating on a metal surface, and the solution comprises: the chelating agent is aminotrimethylene phosphonic acid, alendronic acid, phytic acid, ethanolamine phosphate and hydroxyl ethylidene diphosphonic acid.
5. The pretreatment liquid according to claim 1, wherein the pretreatment liquid is a solution for forming a water-washable natural color conversion coating on a metal surface, and the solution comprises: the auxiliary salt is one or a mixture of more of magnesium nitrate, zinc oxide, calcium nitrate, zinc gluconate, magnesium sulfate, aluminum sulfate, zinc sulfate, aluminum nitrate, manganese sulfate, manganese nitrate, cerium nitrate, lanthanum nitrate, zirconium fluoride, zirconium sulfate, fluorozirconic acid, metatitanic acid, titanyl sulfate, vanadyl oxalate, fluotitanic acid, barium sulfate or barium nitrate;
or the auxiliary agent is one or two of sodium borate, sodium gluconate, anhydrous sodium sulphate, ammonium borate, sodium molybdate, ammonium molybdate, sodium nitrate, sodium chlorate, sodium bromate, sodium tungstate, hydrogen peroxide, sodium peroxide or nitrobenzene;
or the complexing agent is one or a mixture of more of EDTA disodium, EDTA tetrasodium, tartaric acid, sodium tartrate, sodium citrate, amino tricarboxylic acid and citric acid;
or the neutralizing agent is one or a mixture of more of sodium carbonate, sodium bicarbonate, monoethanolamine, diethanolamine, ammonium carbonate, sodium hydroxide, potassium hydroxide, calcium hydroxide, triethanolamine, ammonia water and ammonium bicarbonate.
6. The pretreatment liquid according to claim 1, wherein the pretreatment liquid is a solution for forming a water-washable natural color conversion coating on a metal surface, and the solution comprises: the pH value of the pretreatment liquid is 2 to 7, and further 3 to 6.
7. A method for producing the pretreatment liquid according to any one of claims 1 to 6, characterized by comprising: the method comprises the following steps:
dissolving a chelating agent and an auxiliary modified material into an aqueous solution of alcohol, and reacting to obtain a modified chelating agent; the auxiliary modified material comprises at least three elements of C, N, O, H, P, S, B, Cl, F and Si;
then, the chelating agent, the modified chelating agent, the salt assistant, the auxiliary agent, the complexing agent, the neutralizer and the water are compounded to prepare the pretreatment liquid.
8. The method for preparing a pretreatment liquid according to claim 7, characterized in that: the auxiliary modified material is titanium dioxide, silicon dioxide, silane coupling agent KH-560, KH-540, KH-550, KH-8252, KH-792, silicon powder, polypropylene, sodium polystyrene sulfonate, Tween 20, Tween 40, Tween 60, Tween 80, polyvinyl alcohol 2000, polyvinyl alcohol 4000, polyvinyl alcohol 6000 and polyvinyl alcohol 10000;
or the molar ratio of the chelating agent to the auxiliary modified material is 1:10-10: 1;
or the mixing reaction temperature of the chelating agent and the auxiliary modified material is 50-100 ℃, and the reaction time is 8-12 h;
or the volume ratio of ethanol to water in the alcohol aqueous solution is 1:2-2: 1;
or adding a neutralizing agent into the pretreatment liquid to adjust the pH value of the pretreatment liquid to 2-7.
9. A method for surface-pretreating a metal substrate with the pretreatment liquid according to any one of claims 1 to 6, comprising: the method comprises the following steps:
degreasing and washing the metal base material, and soaking the metal base material in the pretreatment liquid to form a film;
and after film forming is finished, taking out, washing and drying.
10. The method of surface pre-treating a metal substrate of claim 9, wherein: soaking the metal base material in the pretreatment liquid for 1-17 min;
furthermore, the time for soaking the metal base material in the pretreatment liquid is 5-17 min.
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| CN112480814A (en) * | 2020-11-26 | 2021-03-12 | 汪元亮 | Surface treating agent and surface protection method for porous loose material |
| CN113502075A (en) * | 2021-07-28 | 2021-10-15 | 安徽大学绿色产业创新研究院 | Preparation method of environment-friendly metal pretreatment liquid capable of self-adsorption and rapid film formation |
| CN114231190A (en) * | 2021-12-27 | 2022-03-25 | 北京化工大学 | Modification method for improving adhesion performance of zinc-aluminum-magnesium steel plate |
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