JP4719546B2 - Anodic electrolysis treatment liquid, electrolysis treatment method and electrolysis metal material - Google Patents

Description

  The present invention relates to various metal materials {for example, metal materials composed of one or more metals selected from the group of iron-based, zinc-based, aluminum-based and magnesium-based materials (for example, metal plates and metal components (for example, The present invention relates to a non-chromium surface treatment agent that can form a surface film excellent in adhesion and corrosion resistance with a top coating, used for temporary rust prevention, coating base, etc. of automobile bodies and household electrical appliances))}.

  For example, treatment agents containing chromic acid, dichromic acid, or chromate as a temporary rust prevention and coating base method for galvanized steel sheets, aluminum or aluminum alloy sheets that have been used in a wide range of fields such as home appliances, building materials and food containers Chromate treatment using is known. The chromate treatment is performed for the purpose of improving rust prevention and adhesion with the top coating on the surface of galvanized or aluminum alloy. The surface-treated galvanized or aluminum alloy sheet subjected to the chromate treatment is excellent in terms of high productivity and surface treatment uniformity. However, since the chromate treatment has a problem that it leads to environmental pollution and adverse effects on the human body, recently there has been an increasing demand for a non-chromium rust prevention treatment.

  Here, as a typical technique of non-chromate type surface treatment not containing chromium, Patent Document 1 discloses a vanadium compound and at least one compound selected from the group consisting of a titanium salt, a zirconium salt, and a zinc salt. The chemical conversion liquid characterized by consisting of the aqueous solution containing is disclosed. However, this treatment method employs a technique that is not very reasonable as a surface treatment method for a metal plate material, such as immersing an aluminum alloy in the chemical conversion solution for 1 to 20 minutes (preferably 3 to 5 minutes). is doing.

Furthermore, Patent Document 2, Patent Document 3 and Patent Document 4 include chemical conversions containing V ions, Zr ions, PO ₄ ions, and effective F ions whose pH is adjusted to 1.5 to 4.0. A treatment agent and a chemical conversion treatment method using the same are disclosed. However, since it is a chemical conversion treatment system, line management, wastewater treatment, and the like are complicated and inefficient from the viewpoint of workability. In addition, there is a limit to the amount of film that can be obtained, and there is a problem that the corrosion resistance and adhesion cannot be secured depending on the application.
JP-A-56-136978 JP-A-1-246370 JP-A-7-310189 Japanese Patent Laid-Open No. 11-1312254

  Therefore, an object of the present invention is to provide a non-chromium surface treatment solution for a metal material excellent in corrosion resistance and coating adhesion, and a method for treating the same, in which the problems associated with conventional non-chromium surface treatments are eliminated.

  Here, among a number of surface treatment methods, there is a method widely used as a surface treatment of an aluminum material, referred to as “anodic electrolytic treatment”. However, although anodic electrolysis of an aluminum material can form a porous aluminum oxide film on the aluminum surface, it is extremely difficult to form a dense film in a short time of several seconds. It is also necessary to have a post-treatment step that fills the porous holes in the membrane to provide corrosion resistance.

  Under such circumstances, the present inventor has intensively studied to solve the problems of the prior art, and as a result, when the surface treatment liquid combined with a specific component is subjected to an anodic electrolysis treatment, the electrode is removed. The present inventors have found that a coating having extremely excellent corrosion resistance and coating adhesion can be formed in a very short time on the surface of the metal material to be constructed, and have completed the present inventions (1) to (12) based on the findings. .

  The present invention (1) is characterized by containing at least one selected from the group consisting of zirconium, titanium and vanadium (component A), phosphoric acids (component B), and a gelation / precipitation inhibitor (component C). A treatment solution for anodic electrolysis.

  The present invention (2) is the anodic electrolysis treatment liquid of the invention (1), wherein the component C is an organic nitrogen compound and / or an inorganic nitrogen compound.

  This invention (3) is the said invention (1) whose content of the component A, the component B, and the component C is 20-20000 ppm in metal conversion, 20-20000 ppm in P conversion, and 10-10000 ppm in solid content concentration, respectively. ) Or (2).

  The present invention (4) further comprises at least one component selected from the group consisting of silicon, cerium, lithium, zinc, magnesium, calcium, aluminum and manganese, and a group consisting of a water-soluble polymer. The anodic electrolysis treatment liquid according to any one of the inventions (1) to (3).

  The present invention (5) is the anodic electrolysis treatment liquid according to any one of the inventions (1) to (4), wherein the pH is 2 to 13.

  This invention (6) is the process liquid for anodic electrolysis of any one of said invention (1)-(5) as a temporary rust preventive agent and / or a coating base agent.

  In the present invention (7), the gelation product and / or the precipitate of the component A and the component B are obtained by subjecting the anodic electrolysis treatment to the anodic electrolysis treatment liquid according to any one of the inventions (1) to (6). It is an electrolytic treatment method characterized by including the process of forming the film to contain on the metal material surface.

The present invention (8) is the electrolytic treatment method of the invention (7), wherein the anodic electrolysis is direct current electrolysis having a voltage of 0.2 to 200 V and an anode current density of 0.1 to 100 A / dm ² .

  The present invention (9) is the electrolytic treatment method of the invention (7) or (8), wherein the metal material is an iron-based substrate, a zinc-based substrate, an aluminum-based substrate and / or a magnesium-based substrate. is there.

  The present invention (10) is an electrolytically treated metal material having a film formed by the electrolytic treatment method according to any one of the inventions (7) to (9).

This invention (11) is the electrolytically treated metal material of the said invention (10) whose weight of the film | membrane of the said electrolytic treatment is 0.01-5 g / m < ² >.

  It is assumed that the basic mechanism of the present invention is as follows. First, when metal compounds such as zirconium, titanium, and vanadium compounds are combined with phosphate ions, gelation or precipitation occurs under certain conditions. However, when gelation / precipitation inhibitors such as ammonia, amines, quaternary ammonium compounds and other organic nitrogen compounds are added to this system, the gelation or precipitation is suppressed, resulting in stable sol or dispersed electrolysis. A liquid is formed. When the electrolytic solution is used for anodic electrolysis, for example, the gelation / precipitation inhibitor is attracted from the anode to the cathode, the phosphate ion concentration increases near the anode, and the hydrogen ion concentration increases (pH). As a result of the complex overlap of factors such as elution of the metal constituting the anode as ions, the stable sol or dispersion state of the electrolyte solution collapses, causing gelation or precipitation and depositing on the anode surface It will be.

Here, the meaning of each term in the claims and the specification will be described. The significance of specific compounds such as “phosphoric acids” will be described later. The “gelation / precipitation inhibitor” means an agent that prevents or suppresses gelation and / or precipitation of component A and component B. “Ppm” refers to 10 ⁻⁶ wt / wt.

  ADVANTAGE OF THE INVENTION According to this invention, the effect that the precise | minute film | membrane (a metal phosphate film | membrane of a zirconium, titanium, and vanadium) excellent in corrosion resistance and adhesiveness with topcoat can be formed in the surface of a metal material in a short time. Play. Furthermore, in addition to being applicable to various metal materials other than aluminum, there is an effect that the restriction of the film components and the adjustment of the electrolytic solution are extremely simple as compared with general chemical conversion treatment and anodic electrolysis. That is, as compared with the conventional chemical conversion treatment, the line management is simplified and the line speed is increased, and there is an effect that there is no sludge.

  The best mode of the present invention will be described below. However, the following description is only the best mode and is not limited to the description. For example, although the upper limit and lower limit of the numerical range are described as preferred ranges, even if the upper limit and lower limit are exceeded, as long as the constituent requirements of the present invention are satisfied, they are within the technical scope of the present invention. .

  First, the treatment solution for anodic electrolysis according to the best mode will be described in detail. The treatment liquid contains at least one selected from the group consisting of zirconium, titanium and vanadium (component A), phosphoric acids (component B), and a gelation / precipitation inhibitor (component C). Here, this processing liquid contains “component A” to “component C” uniformly in a solution state, a sol state, or a dispersed state. For example, the element or element group which exists in the liquid as an ion, or the aspect which exists in the liquid as a colloid can be mentioned. The “ion” means that the corresponding element or element group exists in an ionic state, and the valence (for example, tetravalent) and the existence form (for example, a metal single ion or a metal-containing complex ion) are not limited. Hereinafter, each component will be described.

  First, a metal compound that is a supply source of zirconium, titanium and / or vanadium constituting “component A” is not particularly limited. Examples of the zirconium source include water-dispersible zirconium colloids, zircon hydrofluoric acid, ammonium zircon carbonate, potassium zircon fluoride, sodium zircon fluoride, basic zirconium carbonate, zirconium nitrate, and zirconium acetate. Examples of the titanium source include water-dispersible titanium colloids, water-soluble inorganic titanium compounds such as titanium sulfate, titanium oxysulfate, titanium hydrofluoric acid, and titanium ammonium fluoride, and titanium alkoxides. Examples of vanadium sources include metavanadic acid, vanadic acid and salts thereof (for example, sodium, potassium and ammonium), vanadium oxide such as vanadium pentoxide, vanadium halides such as vanadium pentachloride and vanadium pentafluoride, vanadyl sulfate, Examples thereof include vanadium sulfate, vanadium nitrate, vanadium phosphate, vanadium biphosphate, vanadium acetate, and organic vanadium compounds such as vanadium acetylacetonate and vanadyl acetylacetonate.

  Next, the phosphoric acid constituting “component B” is not particularly limited as long as it is a phosphate compound that can form a gel or a precipitate with “component A”. For example, a water-soluble phosphate compound, for example, Phosphoric acid compounds such as phosphoric acid, polyphosphoric acid, hypophosphorous acid, tripolyphosphoric acid, hexametaphosphoric acid, primary phosphoric acid, secondary phosphoric acid, tertiary phosphoric acid, polymetaphosphoric acid, heavy phosphoric acid, organic phosphonic acid, and the like These salts can be mentioned.

  Next, the gelation / precipitation inhibitor constituting “component C” is not particularly limited as long as it prevents or suppresses gelation and / or precipitation of component A and component B. Here, the concept of “gelation / precipitation prevention” can be confirmed by, for example, the test shown in FIG. That is, in a situation where a certain amount of component A + component B (1000 ppm; component A concentration is converted to Zr, for example, component B concentration is converted to P), the ratio between component A and component B is changed and predetermined Leave under conditions (40 ° C., 120 h). At this time, as the ratio of component B increases, the viscosity of the liquid increases. For example, in the example of FIG. 1, the viscosity of the liquid exceeds 200 mPa · s when the ratio exceeds 20%. On the other hand, when a certain amount (100 ppm) of component C is present, the liquid viscosity remains low even at the above ratio (for example, about 1/10). In this manner, a drug that maintains the viscosity of one liquid in excess of 200 mPa · s and the viscosity of the other liquid in less than that under the condition that only the presence / absence of component C is different is “gel” It can also be called “prevention / precipitation prevention”. Here, specific compounds of “Component C” include organic nitrogen compounds and inorganic nitrogen compounds such as ammonia (ammonium hydroxide), amine compounds, and quaternary ammonium compounds.

Here, the amine compound may be any of aliphatic amines, aromatic amines and derivatives thereof, such as primary amine (RNH ₂ ), secondary amine (R ₂ NH) and tertiary amine (R _3). N) (wherein R represents a monovalent group), monoamine compounds, diamine compounds and triamine compounds, polyamine compounds, derivatives thereof and salts thereof. Examples of the R group include an alkyl group, an alkoxy group, a phenyl group, a benzyl group, and a naphthyl group. Specifically, for example, triethylamine, tripropylamine, triethanolamine, diethanolamine, monoethanolamine, tripropanolamine, dipropanolamine, monopropanolamine, triisopropanolamine, diisopropanolamine, monoisopropanolamine, N, N -Amines such as dimethylethanolamine, ethyleneimine, pyrrolidine, piperidine, aniline, diphenylamine, and meta-phenylenediamine. These may be used alone or in combination of two or more.

Next, as the quaternary ammonium compound, a compound represented by the formula R ₄ NX (wherein R is as defined above, X represents a monovalent anionic group such as a halogen or a hydroxy anion) is used. Can be mentioned. For example, halides and hydroxy compounds such as tetraalkylammonium salts, specifically chlorides, bromides, fluorides such as tetramethylammonium chloride, tetraethylammonium chloride, tetrabutylammonium chloride, cetyltrimethylammonium bromide (CTAB) And salts of iodides and hydroxides, ClO ₃ compounds, BrO ₃ compounds and IO ₃ compounds.

Examples of other organic nitrogen compounds include amide compounds, amino group-containing aqueous cationic resins, amino group-containing silane coupling agents, and the like. Here, as the amide compound, a primary amide (—CO—NH ₂ ), a secondary amide {(—CO) ₂ NH}, a tertiary amide {(—CO) ₃ N} (where R is as defined above) And the same, and represents a monovalent group), carboxyamide compounds, carbonic acid amide compounds and derivatives thereof, and salts thereof. Specific examples include acetamide, asparagine, para-ethoxyphenylurea, acetanilide, phenylacetamide and the like. Examples of the amino group-containing aqueous cationic resin include melamine resin, aqueous urethane resin, and amino-modified aqueous phenol resin. As amino group-containing silane coupling agents, N-2 (aminoethyl) 3-aminopropylmethyldimethoxysilane, N-2 (aminoethyl) 3-aminopropyltrimethoxysilane, N-2 (aminoethyl) 3 -Aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, N- (vinylbenzyl)- Examples include 2-aminoethyl-3-aminopropyltrimethoxysilane, N, N-bis [3- (trimethoxysilyl) propyl] ethylenediamine, and the like.

  Here, a suitable example of the gelling / precipitating agent constituting “Component C” is a cationic gelling / precipitating agent. When the cationic gelation / precipitation inhibitor is used, since the inhibitor is uniformly present in the liquid before the electrolytic treatment, the gelation of the component A and the component B over the entire liquid and / or Precipitation is prevented. And at the time of electrolytic treatment, as a result of the said inhibitor moving to the negative electrode side electrically, the density | concentration of the said inhibitor in the anode side falls relatively. As a result, component A and component B are released from inhibition by the inhibitor and form a gel film and / or a precipitate film on the anode. In addition, regarding a suitable example, it is also possible to use the term organic cation instead of the functional expression “gelling / precipitating agent”. In particular, a nitrogen-based cation generated by dissociation of an ammonium compound or an amine compound is preferable.

  Next, the electrolytic treatment liquid according to the best mode further includes at least one (component D) selected from the group consisting of silicon, cerium, lithium, zinc, magnesium, calcium, aluminum, and manganese, and a water-soluble polymer (component). It is preferable to further contain at least one component selected from the group consisting of E). By containing these components, corrosion resistance and coating film adhesion can be further improved. The presence form of component (D) may be in the form of ions, particles or fine particles of oxides, or a mixture thereof.

  Here, the metal compound constituting the “component D” and serving as the supply source of the metal is not particularly limited, and is preferably a component that does not adversely affect the electrolytic deposition, such as nitrate, phosphate, carbonate, or the like. Mention may be made of fluoride. Specifically, for example, for silicon compounds, silica such as water-dispersible silica, water-soluble silicate compounds such as sodium silicate, potassium silicate, and lithium silicate, silicate esters, alkyl silicates such as diethyl silicate And silane coupling agents. Among these, silica is preferable because it has an effect of increasing the barrier property of the film, and water-dispersible silica is more preferable because of its high dispersibility in the electrolytic treatment solution. The water-dispersible silica is not particularly limited, and examples thereof include “Snowtex” type (all manufactured by Nissan Chemical Industries, Ltd.), fumed silica such as “Aerosil” (manufactured by Nippon Aerosil Co., Ltd.), etc. Can be mentioned.

  Next, the water-soluble polymer constituting “component E” is not particularly limited, and examples thereof include various water-soluble or water-dispersible resins. Of these, water-soluble polyacrylic resin, water-soluble urethane resin, water-soluble epoxy resin and the like are preferable. In particular, an anionic aqueous resin that is easily deposited by anodic electrolysis is more preferable.

  In addition, this process liquid may contain well-known various additives, such as a wetting agent, an antifoamer, an antibacterial agent, antiseptic | preservative, a viscosity modifier, and a solvent as needed. Furthermore, it is preferable to add an acid or an alkali component to the treatment liquid in order to adjust the pH within the range described below. It does not specifically limit as an acid component which can be used in order to adjust pH, An acetic acid, phosphoric acid, etc. can be mentioned. It does not specifically limit as an alkali component, Sodium hydroxide, potassium hydroxide, ammonia, an amine compound, etc. can be mentioned. In addition, when phosphoric acid is added as a pH adjuster, the phosphoric acid corresponds not only as a pH adjuster but also as “component B”. In addition, when ammonia or an amine compound is added as a pH adjuster, the ammonia or the like corresponds to “component C” as well as the pH adjuster.

  Next, the content and physical properties of each component in the anodic electrolysis treatment liquid according to the best mode will be described. First, the content of “component A” is preferably 20 to 20000 ppm in terms of metal. When “Component A” is less than 20 ppm, a non-uniform chemical conversion film is likely to be formed. On the other hand, if it exceeds 20000 ppm, improvement in film deposition cannot be expected, and the amount used is increased, which is not preferable in terms of cost. The lower limit is more preferably 100 ppm, and the upper limit is more preferably 10,000 ppm. For example, it is more preferably 250 to 1000 ppm.

  Next, the content of “component B” is preferably 20 to 20000 ppm in terms of P. When “Component B” is less than 20 ppm, it is difficult to form a film. On the other hand, if it exceeds 20000 ppm, improvement in film deposition cannot be expected, and the amount used is increased, which is not preferable in terms of cost. The lower limit is more preferably 100 ppm, and the upper limit is more preferably 10,000 ppm. For example, it is more preferably 250 to 1000 ppm.

  Next, the content of “Component C” is preferably 10 to 10,000 ppm in terms of solid content. When “Component C” is less than 20 ppm, the electrolytic treatment solution becomes unstable and it is difficult to deposit a film. On the other hand, even if it exceeds 10000 ppm, improvement in film deposition cannot be expected, and the amount used is increased, which is not preferable in terms of cost. The lower limit is more preferably 50 ppm, and the upper limit is further preferably 10,000 ppm. For example, it is more preferably 50 to 2000 ppm.

  Here, the ratio of the component A and the component B is not particularly limited. For example, the ratio of the component B to the component A is preferably 0.5 to 2. Moreover, the ratio of the component C and the other component is not particularly limited. For example, the ratio of the component C to the component A + the component B is preferably 0.05 to 2.

  Next, the content of “component D” is preferably 1 to 5000 ppm. If it is less than 1 ppm, the corrosion resistance of the resulting chemical conversion film is lowered, which is not preferable. If it exceeds 5000 ppm, no further improvement in the effect is observed, which is economically disadvantageous, and the adhesion after coating may be reduced. The lower limit is more preferably 20 ppm, and the upper limit is more preferably 2000 ppm.

  Next, the content of “component E” is preferably 5 to 5000 ppm as a solid content. If it is less than 5 ppm, the barrier properties and corrosion resistance of the resulting film are undesirably lowered. If it exceeds 5000 ppm, no further improvement in the effect is observed, which is economically disadvantageous, and the adhesion after coating may be reduced. The lower limit is more preferably 10 ppm, and the upper limit is more preferably 2000 ppm.

  “Component D” to “Component E” may be used alone or in combination with two or more components as necessary. When two or more components are used simultaneously, the content of each component is preferably within the above range. In this case, the total amount of each component is not particularly limited.

  Next, as a physical property of this processing liquid, it is suitable that pH is 2-13. If the pH is less than 2, formation of a dense film by dissolution of the metal material may not sufficiently proceed. On the other hand, when the pH exceeds 13, the electrolytic treatment solution tends to cause gel and precipitation and becomes unstable. The lower limit is more preferably 4 (more preferably 5), and the upper limit is more preferably 10.

  Next, the manufacturing method of this processing liquid is demonstrated. The manufacturing method of this process liquid is not specifically limited, It can obtain by dissolving or disperse | distributing said each component in a solvent. Here, the solvent is preferably water. In addition, the above components may be present in the liquid in separate sources or in the same source. For example, when zircon ammonium carbonate is added to a solvent, component (A) and component (C) are simultaneously provided in the liquid.

  Next, a method for using the treatment liquid (electrolytic treatment method) will be described. This treatment liquid is subjected to an anodic electrolytic treatment. As a result, a film containing the gel and / or precipitate of component A and component B is formed on the surface of the metal material. Hereinafter, this method will be described.

First, suitable anodic electrolysis conditions are direct current electrolysis with a voltage of 0.2 to 200 V and an anode current density of 0.1 to 100 A / dm ² . When the DC voltage is less than 0.2 V or the current density is less than 0.1 A / dm ² , the coating is difficult to deposit and the coating amount is small, so that the corrosion resistance and paint adhesion are insufficient. Conversely, when the DC voltage is 200 V or higher or the current density is 100 A / dm ² or higher, a dense film cannot be obtained. Furthermore, current efficiency is low, which is disadvantageous in terms of cost. A more preferable range is a DC voltage of 5 V or more and a current density of 0.5 A / dm ² or more, or a DC voltage of 120 V or less and a current density of 60 A / dm ² or less.

  The target metal materials are cold-rolled steel plate, hot-rolled steel plate, hot-dip galvanized steel plate, electrogalvanized steel plate, hot-dip galvanized steel plate, aluminum-plated steel plate, aluminum-zinc alloyed steel plate, stainless steel plate, aluminum It can be applied to generally known metal materials and plated plates such as plates, copper plates, titanium plates, magnesium plates and the like. In addition, it is not limited to when a metal is a base material, For example, a metal may be films | membranes, such as a plating film and a vapor phase growth film. Furthermore, it is possible to deal with mixed processing of multiple kinds of materials. These metal plates may be subjected to ordinary treatments such as hot water washing, alkali degreasing, and etching before the treatment.

Next, a metal material having a film formed by the electrolytic treatment will be described. First, the film to be formed is preferably a film having a film weight of 0.01 to 5 g / m ² (dry weight). When the thickness of the coating is less than 0.01 g / m ² , the corrosion resistance tends to be insufficient because the coating amount is small. On the other hand, if the coating is thicker than 5 g / m ² , the film forming property is deteriorated. Furthermore, the adhesiveness is insufficient, which is disadvantageous in terms of cost. A more preferable range is 0.02 g / m ² or more and 1.5 g / m ² or less.

  Here, the film to be formed contains a gelled product or a precipitate of “component A” and “component B”. The chemical composition of the film varies depending on the processing conditions and the like, and thus cannot be mentioned uniformly, but is presumed to be a salt of the metal constituting “Component A” and the phosphoric acids constituting “Component B”. More specifically, it is presumed to be a metal phosphate of zirconium, titanium and vanadium. These are often used as non-chromic surface treatment agents in place of chromium compounds, and have been confirmed to have a rust prevention effect, a crosslinking function to water-based resins, and the like. These components are presumed to develop corrosion resistance and adhesion to metal materials. In addition, it is understood that the metal eluted from the positive electrode and components derived from the treatment liquid are also contained in the film.

  Next, a method for using a metal material having a film formed by the electrolytic treatment will be described. The type of the surface treatment material on which the film is formed is not particularly limited, and for example, various top coat films and film laminate layers are provided. For example, examples of the top coat include electrodeposition coating, general water-based, solvent-based coating, and special coatings such as a hydrophilic coating layer, a lubricating organic coating layer, and an antibacterial and antibacterial coating. Examples of the laminate film include a PET film, a polyamide film, and a polyethylene film. Any type of organic film, inorganic film, or organic-inorganic composite film may be used. Further, depending on the desired level of rust prevention, it can also be used for applications in which no top coat film or film laminate layer is provided on the surface treatment material on which the base treatment film of the present invention is formed.

  Hereinafter, the present invention will be described with specific examples. In addition, this invention is not limited at all by these Examples.

1. Preparation of test plate Cold rolled steel plate (SPCC-SD)
Alloyed hot-dip galvanized steel sheet (GA) Plating adhesion 45g / m ² per side (double-sided plating)
Hot-dip galvanized steel sheet (GI) Zinc adhesion amount 60 g / m ² per side (double-sided plating)
Electrolytic galvanized steel sheet (EG) Zinc adhesion amount 40g / m ² per side (double-sided plating)
55% aluminum galvanized steel sheet (GL) Zinc adhesion amount 60g / m ² per side (double-sided plating)
Aluminum plate (Al)
Stainless steel sheet (SUS)
Magnesium material (Mg)
Dimensions of each test material 70mm x 150mm x 0.8mm

2. Pretreatment The sample material was immersed in an aqueous solution having a concentration of 20 g / L and a temperature of 60 ° C. for 10 seconds using an alkaline degreasing agent Pulclean N364S (manufactured by Nihon Parkerizing Co., Ltd.), and washed with pure water. Dried.

3. Surface treatment [Examples 1 to 26, Comparative Examples 1 to 4]
Anodic electrolysis was performed using an electrolytic treatment solution having the composition shown in Table 1 to deposit a base treatment film of cationic electrodeposition coating having a predetermined film weight on the SPCC material, GA material or Al material. Further, anodic electrolysis is performed using the electrolytic treatment solution having the composition shown in Table 1, and a corrosion-resistant film for temporary rust prevention having a predetermined film weight and / or on the EG material, GI material, GL material, SUS material, or Al material. A base coating film for general coating was deposited. Table 2 shows the electrolytic treatment conditions. Here, the voltage is a constant voltage, but unlike the constant current, the current density is not constant. FIG. 2 shows the relationship between voltage and current density.
[Comparative Example 5 (zinc phosphate treatment)]
SPCC material, GA material or Al material is used, and 1 g / L of preparene ZN (manufactured by Nihon Parkerizing Co., Ltd.) as a surface conditioner is spray-applied for 20 seconds at room temperature. ) It was immersed in 48 g / L at 42 ° C. for 120 seconds to perform zinc phosphate treatment. Thereafter, it was washed with water and dried.
[Comparative Example 6 (Coating chromate treatment)]
Using EG material, GI material, GL material, Al material or Mg material, using Zinchrome 1300AN (manufactured by Nihon Parkerizing Co., Ltd.) as a coating chromate agent, the amount of adhesion is 40 mg / m ² by roll coating. It applied so that it might become, and it dried so that the ultimate board temperature might be 80 degreeC with a hot air drying furnace.

4). Top coating Cationic electrodeposition coating was performed under the following conditions (SPCC material, GA material, and Al material).
Paint: GT-10V (cationic electrodeposition paint manufactured by Kansai Paint)
Coating method: Coulomb control / 30 seconds slow start Baking: 175 ° C., 25 minutes Film thickness: 20 μm
General coating was performed under the following conditions (EG material, GI material, GL material, SUS material, Al material or Mg material).
Paint: Amirac # 1000 (manufactured by Kansai Paint)
Coating method: Bar coating method Baking: 140 ° C., 20 minutes Film thickness: 25 μm

5. Evaluation [film weight]
The coating weight was determined by measuring the adhesion amount of phosphorus using a fluorescent X-ray analyzer (FXA) and converting from the blending amount in the treatment agent.
[Corrosion resistance]
[SDT]
About the electrodeposition coating plate of SPCC material, GA material, and Al material, the coating surface was cut with the cutter knife diagonally on the coating surface, and the coating plate was immersed in 5% sodium chloride aqueous solution heated at 55 degreeC. This was pulled up after 240 hours, washed with water, dried, and then subjected to a tape peeling test on the cut part to measure the maximum peeling width on both sides.
The evaluation criteria are as follows.
A: Less than 6 mm Δ: 6 mm or more and less than 10 mm ×: 10 mm or more [SST]
About the bare board (before coating) of EG material, GI material, GL material, Al material, or Mg material, the salt spray test prescribed | regulated to JIS-Z2371 was implemented for 120 hours. The white rust resistance was visually measured and evaluated.
The evaluation criteria are as follows.
◎: White rust occurrence rate less than 5% ○: White rust occurrence rate 5% or more and less than 10% △: White rust occurrence rate 10% or more and less than 50% ×: White rust occurrence rate 50% or more Also, SPCC material, GA The salt spray test specified in JIS-Z2371 was carried out for 480 hours on the electrodeposited coated plate made of aluminum and Al, and the general coated plate made of EG, GI, GL, SUS, Al and Mg. . The maximum swollen width on both sides of the X-cut portion was measured and evaluated.
The evaluation criteria are shown below.
◎: No swelling ○: Less than 6 mm △: 6 mm or more and less than 10 mm ×: 10 mm or more [Coating film adhesion]
[Primary adhesion]
SPCC materials, GA materials, EG materials, GI materials, GL materials, SUS materials, Al materials, and Mg materials are placed on the painted surface with a 1 mm square grid so that the painted surface becomes convex. After extruding 5 mm with an Erichsen tester, a tape peeling test was conducted. About the method of putting a grid, the extrusion method of Erichsen, and the method of tape peeling, it implemented according to the method of JIS-K5400.88.2 and JIS-K5400.88.5. Evaluation was performed by the number of coating film peeling.
The evaluation criteria are shown below.
◎: No peeling ○: Number of peeled 1 or more, less than 10 △: Number of peeled 11 or more, less than 50 ×: Number of peeled 51 or more [secondary adhesion]
The electrodeposition coated plate of SPCC material, GA material and Al material was immersed in pure water heated to 40 ° C. This was pulled up after 240 hours, and after drying, the same test as the primary adhesion was performed and evaluated. An EG material, a GI material, a GL material, a SUS material, an Al material, and an Mg material coated plate were immersed in boiling water for 2 hours, and then a test similar to the primary adhesion was performed and evaluated.
The results are shown in Table 2.
As is apparent from the results in Table 2, in the examples using the coating surface treatment agent of the present invention, good coating adhesion and corrosion resistance are obtained.

FIG. 1 is a diagram showing the relationship between the presence / absence of component C and viscosity according to the concept of “gelation / precipitation prevention” according to the present invention. FIG. 2 shows the relationship between voltage and current density in the example.

Claims (9)

  A treatment liquid for anodic electrolysis, comprising at least one selected from the group consisting of zirconium, titanium and vanadium (component A), phosphoric acids (component B), and a gelling / precipitation inhibitor (component C).   The process liquid for anodic electrolysis of Claim 1 whose component C is an organic nitrogen compound and / or an inorganic nitrogen compound.   The process for anodic electrolysis according to claim 1 or 2, wherein the content of component A, component B and component C is 20 to 20000 ppm in terms of metal, 20 to 20000 ppm in terms of P, and 10 to 10,000 ppm in terms of solid content. liquid.   It further comprises at least one component selected from the group consisting of at least one selected from the group consisting of silicon, cerium, lithium, zinc, magnesium, calcium, aluminum and manganese and a group consisting of a water-soluble polymer. The treatment liquid for anodic electrolysis according to any one of 3.   The treatment liquid for anodic electrolysis according to any one of claims 1 to 4, wherein the pH is 2 to 13.   The treatment liquid for anodic electrolysis according to any one of claims 1 to 5, as a temporary rust preventive and / or a coating base material.   Forming a film containing the gelled product and / or the precipitate of component A and component B on the surface of the metal material by performing an anodic electrolysis treatment using the anodic electrolysis treatment solution according to claim 1. The electrolytic processing method characterized by including the process to make. The electrolytic treatment method according to claim 7, wherein the anodic electrolysis is direct current electrolysis having a voltage of 0.2 to 200 V and an anode current density of 0.1 to 100 A / dm ² .   The electrolytic treatment method according to claim 7 or 8, wherein the metal material is an iron-based substrate, a zinc-based substrate, an aluminum-based substrate, and / or a magnesium-based substrate.

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