JP2007138258A - Metal surface treating agent, surface treating method of metal member, and surface-treated metal member - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a coating type surface treatment technology which is free from any ammonium odor, and excellent in corrosion resistance and adhesiveness to a top coating. <P>SOLUTION: The coating type surface treating agent contains at least one kind of metal to be selected from a group consisting of zirconium, titanium and vanadium, and α,β-mono-etylene unsaturated dicarboxylic acids. <P>COPYRIGHT: (C)2007,JPO&INPIT

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 representative 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 of titanium salt, zirconium salt and 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.

Further, 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.

  Furthermore, Patent Documents 5 to 9 disclose coating-type non-chromium metal surface treatment agents containing an aqueous resin and a metal compound. These treatment agents contain an alkali component such as ammonia or amine as a neutralizing agent for an anionic aqueous resin. Further, the other treating agent contains a primary to tertiary amino group or a quaternary ammonium base as a water-soluble functional group of the cationic aqueous resin. Furthermore, the metal compound as the crosslinking agent for the water-based resin is often added to the surface treatment agent as an ammonium complex or an amine complex.

  Here, when a treatment agent of this type is applied to the object to be treated, ammonia and amine volatilize during the drying process, and the free metal reacts with functional groups such as carboxyl groups and hydroxyl groups of the resin. Crosslinking between copolymers. While the treatment agent containing such a metal cross-linked copolymer has excellent properties, a large amount of ammonia volatilizes during application, so the ammonia odor is remarkable and there are many complaints from the application workers. There is. In some cases, metal such as copper may cause stress corrosion cracking due to ammonia or amine.

As for metal compounds such as zirconium compounds, fluorine-containing zirconium compounds are often used as water-soluble Zr sources {eg, zircon hydrofluoric acid (H ₂ ZrF ₆ ), zircon ammonium fluoride ((NH ₄ )). ₂ ZrF ₆ ), potassium zircon fluoride (K ₂ ZrF ₆ ), etc.}. Here, in the field of reactive metal surface treatment agents, although fluorine is often used as a reaction accelerator in order to be effective for etching metal materials, extra fluorine does not remain in the film by washing with water after the reaction treatment. Therefore, there is no problem of remaining fluorine. However, in the field of coating-type non-chromo surface treatment agents, some fluorine in the coating solution is consumed by etching of the metal material during heat drying, but most of the fluorine remains in the film without volatilizing. Therefore, there is a problem that fluorine causes water solubility and adversely affects corrosion resistance and adhesion.

Furthermore, since an inorganic film made of a simple metal compound such as a zirconium compound, a titanium compound, and a vanadium compound does not become a thin and dense film like a chromium film, there is a problem that the barrier property against water, oxygen, and salt is not sufficient. is there. In addition, since the film lacks flexibility due to the hardness and stress of the inorganic film, there is a problem that defects such as cracks are likely to occur.
JP 56-136978 A JP-A-1-246370 JP-A-7-310189 JP-A-11-1312254 JP 2001-081392 A JP 2001-342578 A JP 2002-265821 A JP 2003-201558 A JP 2004-2958

  Accordingly, an object of the present invention is to provide a coating-type surface treatment technique that is free from the problem of ammonia odor and has excellent corrosion resistance and adhesion to a top coating.

  The present inventor has completed the present inventions (1) to (13) as a result of intensive studies to solve the above problems.

  The present invention (1) is a coating type surface treating agent containing at least one metal selected from the group consisting of zirconium, titanium and vanadium, and α, β-monoethylenically unsaturated dicarboxylic acids.

  In the present invention (2), the α, β-monoethylenically unsaturated dicarboxylic acids are obtained from maleic acid, fumaric acid, citraconic acid, itaconic acid, mesaconic acid, their acid anhydrides, their half esters and their salts. The coating type surface treating agent of the invention (1) selected from the group consisting of:

  The present invention (3) is the invention in which at least one metal compound selected from the group consisting of a zirconium compound, a titanium compound and a vanadium compound and an α, β-monoethylenically unsaturated dicarboxylic acid are added ( It is a coating type surface treating agent of 1) or (2).

  The present invention (4) is the coating type surface treatment agent according to the invention (3), wherein the metal compound is a carbonate, silicate, phosphate, organic acid salt, oxide or hydroxide.

  The present invention (5) is the coating type surface treatment agent according to the invention (3) or (4), wherein the metal compound is a compound not containing ammonium, fluorine, acetic acid, nitric acid and sulfuric acid.

  In the invention (6), the content or addition amount of α, β-monoethylenically unsaturated dicarboxylic acids is 1 to 100 in terms of molar ratio with respect to the content or addition amount of the metal. It is a coating type surface treatment agent according to any one of 1) to (5).

  The present invention (7) includes at least one metal component selected from the group consisting of silicon, cerium, lithium, zinc, magnesium, calcium, aluminum and manganese and at least one selected from the group consisting of water-soluble polymers. The coating-type surface treatment agent according to any one of (1) to (6), further comprising a component.

  The present invention (8) is the coating type surface treatment agent according to any one of the inventions (1) to (7), further comprising a component having a carboxyl group-reactive group and / or an unsaturated group-reactive group. .

  The present invention (9) is the coating type surface treatment agent according to any one of the inventions (1) to (8) as a temporary rust inhibitor and / or a coating base material.

  This invention (10) is a surface treatment method including the process of forming a membrane | film | coat by apply | coating and drying any one coating-type surface treating agent of said invention (1)-(9) on the metal material surface. .

  The present invention (11) is the surface treatment method of the invention (10), wherein the metal material is an iron-based, zinc-based, aluminum-based and / or magnesium-based substrate.

  The present invention (12) is a surface-treated metal material having a film formed by the surface treatment method of the invention (10) or (11).

This invention (13) is a surface-treated metal material of the said invention (12) whose film mass of the said surface treatment is 0.01-5 g / m < ² >.

  Here, the meaning of each term in the claims and the present specification will be described. The “coating type” refers to a type in which a liquid surface treatment agent is applied to a metal material and then dried to form a film.

  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 coating type surface treating agent according to the best mode will be described. Here, the surface treatment agent is in the form of an aqueous solution at the time of use, but a concentrated type diluted with water at the time of use and a dry type to which water is added are also included in the concept of the surface treatment agent. Hereinafter, a liquid coating type surface treatment agent (treatment liquid) will be described as an example.

  The surface treatment agent comprises at least one metal selected from the group consisting of zirconium, titanium and vanadium (hereinafter referred to as “component A”) and α, β-monoethylenically unsaturated dicarboxylic acids (hereinafter referred to as “component B”). ")". Here, this surface treating agent contains these components uniformly in a solution state, a sol state, or a dispersed state. For example, the aspect in which the said component exists in the liquid as ion, or exists in the liquid as a colloid can be mentioned. The “ion” means that the corresponding component exists in an ionic state, and there is no limitation on the valence (for example, tetravalent) or the existence form (for example, a metal single ion or a metal-containing complex ion). Hereinafter, each component will be described.

  First, the component A “at least one metal selected from the group consisting of zirconium, titanium, and vanadium” will be described. The metal compound that is a supply source of zirconium, titanium, and / or vanadium is not particularly limited, and examples thereof include carbonates, silicates, phosphates, organic acid salts, oxides, and hydroxides. Examples thereof include compounds not containing ammonium, fluorine, acetic acid, nitric acid and sulfuric acid, and more preferably their poorly water-soluble salts. Here, the reason why it is preferable not to contain components such as ammonium is that, for ammonium, in addition to the fact that the surface treatment agent is a coating type, it is better that there is no water washing step and no extra components, This is because the problem of ammonia odor due to volatilization during drying also occurs. In addition, with respect to fluorine, since the surface treatment agent is a coating type, etching is not necessary, and in addition, there is a problem that fluorine remains as a chelate component in the film. Also, acetic acid causes a problem of acetic acid odor due to volatilization during drying. Further, regarding nitric acid and sulfuric acid, there is a problem that film formation is hindered by the presence of the component. However, as long as the metal compound containing these problem components is not used as the sole metal source, some of these problem components may be contained. In addition, the reason why the poorly water-soluble salt is preferable is that, in general, the salt does not contain the non-preferred component such as fluorine which is a solubilizing component.

  Specific examples are listed below. First, as the zirconium source, water-dispersible zirconium oxide colloid, zirconium hydroxide, zirconium oxycarbonate, basic zirconium carbonate, zirconium carbonate potassium, zirconium silicate, zirconium phosphate, zirconium titanate, Zirconium tungstate, lithium zirconate, aluminum zirconate, magnesium zirconate, strontium zirconate, zirconium maleate, zirconium dimaleate half-zirconium, zirconium diitaconate, zirconium lactate, zirconium oxyoleate, zirconium oxystearate, zirconium ethoxide And zirconium tetra-n-butoxide. Examples of the titanium source include water-dispersible titanium oxide colloid, titanic acid, lithium titanate, zirconium titanate, titanium alkoxide, and the like. Examples of vanadium include metavanadic acid, vanadic acid and salts thereof (for example, sodium and potassium), vanadium oxide such as vanadium pentoxide, vanadium halides such as vanadium pentachloride, vanadium phosphate, vanadium biphosphate, and vanadium acetyl. Organic vanadium compounds such as acetonate and vanadyl acetylacetonate are preferred.

  Next, “α, β-monoethylenically unsaturated dicarboxylic acids” as component B will be described. First, “α, β-monoethylenically unsaturated dicarboxylic acids” have one ethylenic double bond in the molecule and one carboxyl group pendant to each carbon associated with the double bond. It refers to dicarboxylic acids, their anhydrides, their half esters and their salts. Here, examples of the dicarboxylic acid include maleic acid, fumaric acid, citraconic acid (methylmaleic acid), itaconic acid (methylidene succinic acid), and mesaconic acid (methylfumaric acid). In addition, examples of the half ester include esters of alcohol having 1 to 18 carbon atoms. Here, from the viewpoint of water solubility, esters of alcohol having 1 to 10 carbon atoms are preferable and particularly preferable. Are alcohol esters such as methyl, ethyl, and benzyl. Examples of the salt include alkali metal salts such as sodium salt, potassium salt and lithium salt, and alkaline earth metal salts such as magnesium salt and zinc salt. Among these, maleic acid is preferable in that the metal compound can be water-solubilized (or dispersed in water) with a small amount.

  Next, the surface treatment agent according to the best mode is further at least one metal component selected from the group consisting of silicon, cerium, lithium, zinc, magnesium, calcium, aluminum and manganese (hereinafter referred to as “component C”). And at least one component selected from the group consisting of water-soluble polymers (hereinafter referred to as “component D”). By containing these components, corrosion resistance and coating film adhesion can be further improved. Component C may be present in the form of ions, particles such as oxides or fine particles, or a mixture thereof.

  Here, it does not specifically limit as a metal compound used as the supply source of the component C, For example, a water dispersible oxide, a hydroxide, carbonate, a silicate, and a phosphate can be mentioned. 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 them, silica is preferable because it has an effect of increasing the barrier property of the film, and water-dispersible silica is more preferable because it has high dispersibility in the surface treatment liquid. 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 as component D is not particularly limited, and examples thereof include various water-soluble or water-soluble resins. Among these, cellulose derivatives, polyvinyl alcohol, polyethylene glycol, polyethylene oxide, polyglycerin, water-soluble polyphenol resins, water-soluble unsaturated polyester resins, water-soluble epoxy resins, tannins, polymaleic acid, and the like are preferable.

  Here, Component C and Component D are (1) elimination of residual carboxyl group and / or (2) crosslinking by polymerization reaction of unsaturated group with respect to α, β-monoethylenically unsaturated dicarboxylic acid. -It is preferable to have two functions of polymerization. Examples of the component C having the function (1) include an inorganic component containing a hydroxyl group, specifically, a water-dispersible oxide, hydroxide, carbonate, silicate, phosphate, and the like. be able to. Examples of the component D having the function (1) and / or (2) include cellulose derivatives, polyvinyl alcohol, polyethylene glycol, polyethylene oxide, polyglycerin, water-soluble polyphenol resin, tannin, polymaleic acid, and the like. be able to. In addition, although it is suitable for the components C and D to have the said function, when the components C and D do not have the said function, you may add the component which has the said function separately, and a component Even when at least a part of C and D has the above function, a component having the function may be added repeatedly.

  In addition, this surface treating agent can add well-known various additives, such as a wetting agent, a leveling agent, an antifoamer, and a thickener, as needed.

  Next, the content and physical properties of each component in the surface treatment agent according to the best mode will be described. First, the addition amount of the metal compound serving as the supply source of component A is preferably 0.5 to 95 wt% with respect to the total solid content of the surface treatment agent. This is because when the amount added is less than 0.5 wt%, the corrosion resistance and the adhesion after coating tend to be insufficient. When the amount added exceeds 95 wt%, the metal compound in the film becomes excessive and the stability of the treatment liquid decreases. Because there is a tendency to. Here, the lower limit is more preferably 5 wt% or more, and particularly preferably 30 wt% or more. As for the upper limit value, 70 wt% or less is more preferable, and the case of 50 wt% or less is particularly preferable.

  Next, the addition amount of Component B is preferably 5 to 9900 parts by weight with respect to 100 parts by weight of the metal compound (solid content) that is the supply source of Component A. Here, regarding a lower limit, 50 weight part or more is more suitable, and 100 weight part or more is especially suitable. With respect to the upper limit, 5000 parts by weight or less is more preferable, and 2500 parts by weight or less is particularly preferable.

  Next, the addition amount of Component C is preferably 5 to 1900 parts by weight with respect to 100 parts by weight of the metal compound (solid content) serving as the supply source of Component A. Here, regarding a lower limit, 50 weight part or more is more suitable, and 75 weight part or more is especially suitable. The upper limit is more preferably 500 parts by weight or less, and particularly preferably 250 parts by weight or less.

  Next, the addition amount of Component D is preferably 5 to 1900 parts by weight with respect to 100 parts by weight of the metal compound (solid content) serving as the supply source of Component A. Here, regarding a lower limit, 50 weight part or more is more suitable, and 75 weight part or more is especially suitable. With respect to the upper limit value, 500 parts by weight or less is preferable, and 250 parts by weight or less is particularly preferable.

  Here, Component B (α, β-monoethylenically unsaturated dicarboxylic acids) dissolves (or disperses) the metal compound according to Component A when adjusting the treatment agent, and after dissolution (or dispersion), component B Functions as a stabilizer for A. In order to exert the function, the content or addition amount of α, β-monoethylenically unsaturated dicarboxylic acids is 1 to 100 in terms of molar ratio with respect to the content or addition amount of the metal. It is preferred, more preferably 5-50, and most preferably 10 ± 5. In addition, among other acids having a similar structure, there is one that can dissolve the metal compound related to Component A if the concentration is increased, but Component A aggregates when diluted. The α, β-monoethylenically unsaturated dicarboxylic acids according to the present invention are superior to similar acids in that they do not aggregate even when diluted.

  The physical properties of the surface treatment agent are not particularly limited. Although it depends on the α, β-monoethylenically unsaturated dicarboxylic acid used, basically, it is often acidic because pH is not adjusted with ammonium or amine.

  Next, the manufacturing method of this surface treating agent is demonstrated. The manufacturing method of this surface treating agent 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 zirconium maleate, dimaleic acid half ester zirconium, and diitaconate zirconium are added to the solvent, component A and component B are simultaneously provided in the liquid. In this case, the compound corresponds to component A + component B. In this case, the ratio of the addition amount of the metal compound serving as the supply source of component A and the addition amount of component B is the ratio of the metal portion in the compound to the component B portion in the compound. Moreover, regarding each said component, when making it melt | dissolve, you may carry out under normal temperature or under heating (<100 degreeC).

  Next, the usage method (surface treatment method of a metal material) of this surface treating agent is demonstrated. The said method includes the process of apply | coating to the metal material surface, and the process of drying after application | coating. In general, the method includes a degreasing step and a water washing step before the coating step.

  First, the coating process will be described. As a coating method, a conventional method can be applied as it is, for example, roll coating, curtain flow coating, air spray, airless spray, dipping, bar coating, brush coating, and the like.

  Next, the drying process will be described. First, as a drying method, a conventional method can be applied as it is, and examples thereof include heat drying and air drying. Here, the treatment film drying temperature (reaching plate temperature) is preferably 60 to 300 ° C, and more preferably 100 to 250 ° C. There is no particular limitation as long as moisture can be evaporated and dried. However, drying at 100 ° C. to 250 ° C. is particularly preferable from the viewpoints of the rust prevention property of the present invention and the adhesion of the formed surface treatment film to the metal surface, topcoat film or adhesive film.

  The target metal materials are cold-rolled steel sheet, hot-rolled steel sheet, hot-dip galvanized steel sheet, electrogalvanized steel sheet, hot-dip galvanized steel sheet, aluminum-plated steel sheet, aluminum-zinc alloy-plated steel sheet, tin-zinc alloy plating It can be applied to generally known metal materials and plated plates such as steel plates, zinc-nickel alloy plated steel plates, stainless steel plates, aluminum plates, copper plates, titanium plates, magnesium plates and the like. Furthermore, it can cope with mixed processing of plural kinds of materials. These metal materials may be subjected to ordinary treatments such as hot water washing and alkaline degreasing before treatment.

Next, the metal material on which a film is formed by the surface treatment will be described. First, the film mass of the formed film is preferably 0.01 to 5 g / m ² (dry mass). When the coating mass is less than 0.01 g / m ² , the corrosion resistance tends to be insufficient because the coating mass is small. On the other hand, when it exceeds 5 g / m ² , the film forming property deteriorates. Furthermore, the adhesiveness is insufficient or the cost is disadvantageous. A more preferred range, 0.05 g / ^{m 2} or more and 1.5 g / ^{m 2} or less.

  Here, the film formed is presumed to be a hybrid film of zirconium or the like and α, β-monoethylenically unsaturated dicarboxylic acids. Specifically, during drying of the treated membrane, a cross-linking reaction between a carboxyl group of α, β-monoethylenically unsaturated dicarboxylic acids and a metal ion such as zirconium, and α, β- It is presumed that the polymerization reaction of monoethylenically unsaturated dicarboxylic acids occurs simultaneously, forming a denser film, and having excellent corrosion resistance and coating film adhesion. Furthermore, since α, β-monoethylenically unsaturated dicarboxylic acids are likely to volatilize, these easily volatile components volatilize from the film during drying, and the dissolved components do not remain in the film, resulting in further corrosion resistance and adhesion. It is estimated to be excellent.

  Next, the utilization method (use) of the metal material in which the film by this surface treating agent was formed is demonstrated. First, various metal products can be obtained by processing the metal material into a desired shape. Examples of the metal products include anti-fingerprint galvanized steel sheets for home appliances, pre-coated steel sheets for houses for construction, aluminum fin materials for air conditioners, and various metal parts for automobiles. Further, the overcoat film provided on the film is not particularly limited. For example, as the overcoat film, electrodeposition coating, solvent coating, powder coating and special coating, for example, hydrophilic coating layer, lubricating organic coating layer, protective coating Mention may be made, for example, of fungicidal coatings. Further, depending on the level of rust prevention, it is not necessary to provide a top coat (for example, temporary rust prevention).

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)
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 39, Comparative Examples 1 to 24]
Surface treatment agent having the composition shown in Table 1 as an anticorrosive film for temporary rust prevention and / or a base coating film for general coating and pre-coating for SPCC materials, EG materials, GI materials, GA materials, GL materials or Al materials Was applied to a predetermined film thickness by a bar coating method, and dried to PMT 120 ° C. in a drying furnace. In addition, as a base treatment film of a hydrophilic coating agent on an Al material, a surface treatment agent having a composition shown in Table 1 was applied to a predetermined film thickness by a bar coating method, and PMT (maximum reach) was achieved in a drying furnace. (Plate temperature) It dried to 180 degreeC.
[Comparative Examples 25 to 28 (coating chromate treatment)]
Using Al material, EG material, GI material or GL material, using Zinchrome 1300AN (manufactured by Nihon Parkerizing Co., Ltd.) as the coating chromate agent, it is applied by the roll coating method so that the adhesion amount becomes 40 mg / m ^2. Then, it was dried in a hot air drying furnace so that the ultimate plate temperature was 80 ° C.

4). Top coating General coating was performed under the following conditions (SPCC material, EG material, GI material, GL material or Al material).
Paint: Amirac # 1000 (manufactured by Kansai Paint)
Coating method: Bar coating method Baking: 140 ° C., 20 minutes Film thickness: 25 μm
Pre-coating (primer + TOP) was performed under the following conditions (EG material, GI material, GL material, or Al material).
Primer: 7 μm TQ88 (manufactured by NOF Corporation)
Coating method: Bar coating method Baking: PMT 200 ° C. Film thickness: 7 μm
Top: 17μm SRF-05 (Nippon Yushi Co., Ltd.)
Coating method: Bar coating method Baking: PMT 225 ° C. Film thickness: 17 μm
A hydrophilic coating agent was applied under the following conditions (Al material).
Paint: Parlene 5013 (Nippon Parkerizing hydrophilic coating)
Coating method: Roll coater Baking: PMT 200 ° C. Coating amount: 0.8 g / m ²

5. Evaluation [film mass]
The film mass was determined by measuring the amount of metal (Zr, Ti, or V) attached using a fluorescent X-ray analyzer (FXA) and converting from the blended amount in the treatment agent.
[Corrosion resistance]
[SST]
The salt spray test prescribed in JIS-Z2371 was carried out for 240 hours on a bare plate of EG material, GI material, GL material or Al material (surface-treated plate that was not overcoated) and a hydrophilic coated plate of Al material. The white rust resistance of the flat portion was visually measured and evaluated.
The evaluation criteria are as follows.
◎: White rust occurrence rate is less than 5% ○: White rust occurrence rate is 5% or more and less than 10% △: White rust occurrence rate is 10% or more and less than 50% ×: White rust occurrence rate is 50% or more Also, SPCC material, EG The salt spray test prescribed in JIS-Z2371 was carried out for 480 hours on the prepainted plates made of the general coating plate of GI material, GI material, GL material, Al material, EG material, GI material, GL material, and AL material. 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]
After a SPCC material, EG material, GI material, GL material or Al material general coated plate is placed on the painted surface with a 1 mm square grid with a cutter knife and extruded 5 mm with an Erichsen tester so that the painted surface is convex 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 In addition, EG material, GI material, GL material and AL material pre-coated plate Was subjected to a bending test (2T), and was performed at the coating film peeling area after tape peeling.
The evaluation criteria are shown below.
◎: No peeling ○: Peeling area 5% or less □: Peeling area 10% or less △: Peeling area 50% or less ×: Peeling area 80% or more In addition, a small amount of deionized water is allowed to adhere to the surface of the Al coated hydrophilic coating. The appearance of the surface after rubbing strongly 20 times with gauze was observed.
The evaluation criteria are shown below.
◎: The substrate is exposed in less than 1% of the test site. ○: The substrate is exposed in 1% to less than 5% of the test site. △: The substrate is exposed in 5% to less than 50% of the test site. X: 50% or more of the test site. The substrate is exposed [secondary adhesion]
The SPCC material, EG material, GI material, GL material, and Al material general-coated plate were immersed in boiling water for 2 hours, and then the same test as the primary adhesion was performed and evaluated. Moreover, after pre-coating plate of EG material, GI material, GL material, and AL material was immersed in boiling water for 2 hours, it was taken out and evaluated after 24 hours in the same manner as the primary adhesion. The results are shown in Tables 2 and 3. As is clear from the results in Table 2, in the examples using the present coating ground treatment agent, good coating adhesion and corrosion resistance were obtained.

Claims (13)

  A coating type surface treating agent containing at least one metal selected from the group consisting of zirconium, titanium and vanadium, and α, β-monoethylenically unsaturated dicarboxylic acids.   α, β-monoethylenically unsaturated dicarboxylic acids are selected from the group consisting of maleic acid, fumaric acid, citraconic acid, itaconic acid, mesaconic acid, their anhydrides, their half esters and their salts, The coating type surface treating agent according to claim 1.   The coating type surface according to claim 1 or 2, wherein at least one metal compound selected from the group consisting of a zirconium compound, a titanium compound and a vanadium compound and an α, β-monoethylenically unsaturated dicarboxylic acid are added. Processing agent.   The coating type surface treating agent according to claim 3, wherein the metal compound is carbonate, silicate, phosphate, organic acid salt, oxide or hydroxide.   The coating type surface treating agent according to claim 3 or 4, wherein the metal compound is a compound not containing ammonium, fluorine, acetic acid, nitric acid and sulfuric acid.   The content or addition amount of α, β-monoethylenically unsaturated dicarboxylic acids is 1 to 100 in terms of a molar ratio with respect to the content or addition amount of the metal. The coating type surface treating agent as described.   It further comprises at least one metal component selected from the group consisting of silicon, cerium, lithium, zinc, magnesium, calcium, aluminum and manganese and at least one component selected from the group consisting of water-soluble polymers. Item 7. The coating-type surface treatment agent according to any one of Items 1 to 6.   The coating type surface treating agent according to any one of claims 1 to 7, further comprising a component having a carboxyl group-reactive group and / or an unsaturated group-reactive group.   The coating type surface treatment agent according to any one of claims 1 to 8, as a temporary rust preventive and / or a coating base agent.   The surface treatment method including the process of forming a membrane | film | coat by apply | coating and drying the coating type surface treating agent as described in any one of Claims 1-9 on the metal material surface.   The surface treatment method according to claim 10, wherein the metal material is an iron-based, zinc-based, aluminum-based and / or magnesium-based substrate.   A surface-treated metal material having a film formed by the surface treatment method according to claim 10. The surface-treated metal material according to claim 12, wherein a film mass of the surface treatment is 0.01 to 5 g / m ² .