JP5085439B2 - Metal (water) oxide coated metal material - Google Patents

Description

  The present invention relates to a metal surface, and relates to a metal (water) oxide-coated metal material having a coating composed of one or both of an oxide and a hydroxide of a specific metal element.

  Metal materials made of iron, iron-base alloys, zinc, zinc-base alloys, aluminum, aluminum-base alloys, etc., and plating metal materials have been widely subjected to rust prevention treatment with chromate using hexavalent chromate, etc. Furthermore, when fingerprint resistance, lubricity and the like are required, a resin-based film is formed on the chromate film as a base treatment, and various coatings are further applied as necessary.

  In recent years, due to increasing environmental problems, there is a movement to omit the chromate treatment that has been conventionally performed. However, since the chromate-treated layer itself has high corrosion resistance and high paint adhesion to the upper layer film, if this chromate treatment is omitted, a significant decrease in these performances is expected. In order to avoid such a decrease in performance, studies have been made on organic resin-based coatings without base treatment and chemical conversion coatings that replace chromate, but sufficient performance has not been obtained so far. .

  In an example of an organic resin-based film without a base treatment, Patent Document 1 discloses an aqueous resin composition obtained by reacting a composition containing an aqueous polyurethane resin, an aqueous polyolefin resin, a water-dispersible silica, and a silane coupling agent. , A rust-proof coating containing a thiocarbonyl group-containing compound and phosphate ions has been disclosed, but there is a problem that alkali resistance is low due to the inclusion of those having a relatively high acid value. Patent Document 2 discloses an organic composite coated steel sheet having an organic composite film containing a resin in which a specific organic resin is combined on the surface of a zinc-based plated steel sheet or an aluminum-based plated steel sheet, but is insufficiently crosslinked. Therefore, there is a problem that the solvent rubbing test is damaged. Patent Document 3 discloses a galvanized steel sheet having a coating layer formed by applying an aqueous composition containing a metal compound, a water-soluble organic resin and an acid. However, there is a problem that the alkali resistance is poor due to the large amount of carboxyl groups in the water-soluble resin. Patent Document 4 discloses a surface-treated metal plate having an organic coating formed of an epoxy resin and a glycoluril resin, but has a problem of insufficient corrosion resistance because it does not contain a rust preventive. Patent Document 5 includes a surface treatment containing one or both of a water-dispersible resin and a water-soluble resin, a silane coupling agent, phosphoric acid and a hexafluorometal acid on the surface of a zinc-based plated steel sheet or an aluminum-based plated steel sheet. Although a surface-treated steel sheet having a surface-treated film formed by the composition is disclosed, the problem that the alkali resistance is insufficient when the phosphoric acid component is included, the corrosion resistance is insufficient when the hexafluorometal acid is included. There is a problem that there is.

  An example of a chemical conversion coating instead of chromate is a phosphate treatment such as zinc phosphate treatment. However, the phosphate treatment is inferior in corrosion resistance as a primary rust prevention treatment, and is insufficient in corrosion resistance as a coating ground treatment. Patent Document 6 discloses a phosphoric acid / phosphoric acid compound film containing an oxide, and Patent Document 7 discloses a film made of a vanadium compound and phosphoric acid or a phosphoric acid compound. There is a problem that the alkalinity is insufficient. Furthermore, Patent Document 7 discloses a film composed of a vanadium compound and a silicon compound, but has a problem that the corrosion resistance is insufficient.

JP 2001-164182 A JP 2001-199003 JP 2001-214283 A JP2003-49281 Japanese Patent Laid-Open No. 2003-105555 Japanese Patent Laid-Open No. 2004-269921 Japanese Unexamined Patent Publication No. 2006-2171

  In view of the above situation, the present invention is a metal having a coating made of one or both of a metal oxide and a hydroxide on a metal surface, which has bare corrosion resistance and adhesion to an organic resin film that can be used as a chromate film replacement technique. It is an object to provide a metal material having a (water) oxide coating.

As a result of intensive studies, the inventors of the present invention consisted of one or both of 3 to 4 types of oxides and hydroxides selected from Ti, Zr, Hf, V, Nb, Ta, and Si, and at least Ti, Zr, When having a metal (water) oxide coating layer containing one or both of one or both of oxides and hydroxides of Hf, an excellent bare corrosion resistance can be obtained, and an organic resin coating layer formed on the upper layer The present inventors have found that the adhesiveness is excellent, and found that performance equal to or higher than that of the chromate film can be obtained, leading to the present invention. The gist of the present invention is as follows.

(1) A metal material in which a coating of one or both of a metal oxide and a metal hydroxide (metal (water) oxide) is formed by immersion in a liquid phase deposition treatment solution containing metal ions or electrolysis after immersion. Te, said coating, oxides of three metal elements selected from the following a~c group, made from one or both of the hydroxide, oxide of metal element selected at least one of at least a group, hydroxide A metal (hydroxide) -coated metal material comprising one or both of objects.

  a group: Ti, Zr, Hf, b group: V, Nb, Ta, c group: Si

( 2 ) The metal (water) according to ( 1 ), wherein the coating film is composed of one or both of an oxide and a hydroxide of a metal element selected from each of the groups a to c. Oxide coated metal material.

(3) The film (1) or (1), wherein the coating further comprises one or both of an oxide and a hydroxide of at least one additional metal element selected from the groups a to c. 2) The metal (water) oxide-coated metal material described.

(4) The metal (water) oxide-coated metal material according to the above (3), wherein the metal element contained in the film is four types.

(5) the metal in terms of the amount of coating film is characterized in that it is a ^{5 ~200mg / m 2 (1)} ~ (4) metal (hydr) oxide coated metal material according to any one of.

( 6 ) The metal (water) oxide according to any one of (1) to ( 5 ) above, wherein the ratio of the element selected from group a is 25% by mass or more of the metal equivalent of the coating Coated metal material.

( 7 ) The organic resin-based film having a thickness of 0.1 μm to 3.0 μm containing a carboxyl group, a hydroxyl group, and a sulfonic acid group is provided on the upper layer of the film, according to any one of (1) to ( 6 ), Metal (water) oxide coated metal material.

( 8 ) The metal (water) oxide-coated metal material according to any one of (1) to ( 7 ), wherein the metal material is a cold-rolled steel plate or a hot-rolled steel material.

( 9 ) The metal (water) oxide-coated metal material according to any one of (1) to ( 8 ), wherein the metal material is a surface-treated metal material.

( 10 ) The metal (hydroxide) -coated metal material according to ( 9 ), wherein the surface-treated metal material is a galvanized steel material or a zinc alloy-plated steel material.

( 11 ) The metal (hydroxide) -coated metal material according to ( 9 ), wherein the surface-treated metal material is an aluminum-plated steel material or an aluminum alloy-plated steel material.

  According to the present invention, since it does not contain hexavalent chromium, it has a low environmental load, and in the case of forming an organic resin film layer as an upper layer with high corrosion resistance, a metal having a coating layer that is highly adhesive to the organic film layer The material can be provided.

  The present invention is described in detail below.

  The metal (water) oxide-coated metal material of the present invention has a metal (water) oxide coating layer composed of one or both of an oxide and a hydroxide of a specific metal element. As a result of intensive studies by the inventors of the present invention, it was found that even a film not containing hexavalent chromium exhibits characteristics equivalent to or better than a film containing hexavalent chromium, a so-called chromate film. That is, the properties of the chromate film are bare corrosion resistance due to barrier properties, processed part corrosion resistance due to self-repairing ability due to dissolution and precipitation, and excellent adhesion with the upper layer film due to bonding with polar groups in the organic resin layer formed on the upper layer. . As a result of trial and examination on performance obtained by various combinations of oxides and hydroxides of various metals excluding chromium, focusing on these functions (barrier properties, self-repairability, reactivity with polar groups) The inventors have come up with a metal (water) oxide of a metal element that constitutes a film exhibiting performance. More specifically, it is composed of a metal (water) oxide of 2 to 4 metal elements selected from Ti, Zr, Hf, V, Nb, Ta, and Si, and the (water) oxide contains at least Ti and Zr. In addition to having an excellent bare corrosion resistance by having a film containing one or more metal (hydroxide) oxides of Hf, when an organic resin film layer is formed as an upper layer thereof, Found to have high adhesion.

  In addition, Ti, Zr, Hf, V, Nb, Ta, and Si are classified into three groups, a, b, and c, based on their effects, and the metal elements of each group are combined appropriately based on their characteristics. And found that excellent film properties can be obtained.

  First, three elements of Ti, Zr, and Hf are classified into the a group. It has been found that when the (hydric) oxide of group a is contained in the coating, it has the property that the flat plate corrosion resistance is particularly excellent. This is believed to be due to the high barrier properties due to the hydrophobic nature of the coating. Among the group a, it is more preferable to use Zr which is excellent in corrosion resistance as compared with other elements.

  In group b, three elements of V, Nb and Ta are classified. It has been found that when the (hydric) oxide of group b is contained in the coating, it has a characteristic that the processed portion has excellent corrosion resistance. This is presumed to be due to the self-healing ability to cover the film defect part and the corrosion part caused by processing, etc., when the (water) oxide is dissolved in the wet corrosion environment. It is more preferable to use V which is excellent in the corrosion resistance of the processed part as compared with other elements in the group b.

  Si is classified into group c. It has been found that the adhesion with the upper organic resin film layer is particularly high when the c-group (water) oxide is contained in the film. This is presumed to form a strong chemical bond with the organic resin film layer formed thereon.

  Therefore, by combining the a, b, and c groups in a timely manner, it is possible to arbitrarily control the flat plate corrosion resistance, the processed portion corrosion resistance, and the adhesion with the upper film.

  For example, by combining the element Zr selected from the group a and the element Si selected from the group c, it is possible to form a film having excellent corrosion resistance and adhesion with the top coating film, and the elements Zr and b selected from the group a. By combining the element V selected from the group, it is possible to form a film having excellent flat plate corrosion resistance and processed portion corrosion resistance. And, by combining element Zr selected from group a with element V selected from group b, element Si selected from group c, it is possible to obtain performance excellent in flat plate corrosion resistance, processed portion corrosion resistance, and adhesion to the upper film. I can do it.

  Furthermore, it has also been found that even in the combination of the same group, a film composed of two or more elements can provide superior film characteristics as compared with a film composed of one element. For example, a coating composed of two or more elements selected from group a has better processed portion corrosion resistance than a coating composed of one element selected from group a. The performance improvement mechanism by combining elements selected from the same group is not clear, but even the elements of the same group have different conditions and ranges in which their properties are manifested. A film composed of a combination of two or more types is not limited to the characteristics that the group is good at, because the conditions and range of characteristics are expanded and the combined action also works. It is estimated that expression and improvement may be seen.

  Therefore, the element selected from the a group is Zr and Ti, and the element V selected from the b group is combined with the element Si selected from the c group, or the three elements of Ti, Zr, and Hf selected from the a group are combined. It is selected from elements br or c, elements Zr selected from group a and two elements selected from group b and elements in group c, or elements Zr and b selected from group a. By combining the three elements, etc., better film performance is manifested. However, in the case of combinations of 5 elements or more, the performance improvement effect due to the combination of elements is saturated. Therefore, by examining the optimization of the conditions using combinations of 4 elements or less, the required film properties can be obtained efficiently.

The film containing these metal (water) oxides is preferably 5 to 200 mg / m ^{2 in} terms of metal per side. If it is less than 5 mg / m ² , the above characteristics may be insufficient. When it exceeds 200 mg / m ² , the above characteristics are saturated or deteriorated and it is not economical.

  The metal concentration ratio in the film of the group a, that is, the mass ratio of the metal element of the (group) (hydride) oxide constituting the film is preferably 25% or more. More preferably, it is 50% or more. If it is less than 25%, the plate corrosion resistance may be insufficient. This component has a barrier property and is suitable as a basic component constituting the coating film, that is, a matrix of the coating film. Therefore, the upper limit is determined by the corrosion resistance of the processed part by other components and the adhesion performance with the upper film, and only the corrosion resistance of the flat plate. Therefore, there is no particular upper limit on performance because it is 100%.

  Further, the mass ratio of the group b metal elements is preferably 25% or more and 75% or less. If it is less than 25%, the corrosion resistance of the processed part may be insufficient. If it exceeds 75%, the coating may not be maintained in a healthy state in a corrosive environment.

  The mass ratio of the metal element of group c is preferably 25% or more and 75% or less. If it is less than 25%, the adhesion to the upper film may be insufficient. If it exceeds 75%, the corrosion resistance may be insufficient.

  When an organic resin coating is applied to the upper layer, the adhesion with the upper coating is due to adhesion with the organic resin coating that is in direct contact with the coating layer, and therefore the organic resin coating may be either a single layer or a plurality of layers. Moreover, although the film thickness of an organic layer is not restrict | limited, 0.1-3 micrometers is preferable. If the thickness is less than 0.1 μm, the coating may be incomplete and the characteristics are insufficient. If it exceeds 3 μm, the characteristics are saturated and it is not economical.

  The kind of organic resin film is not particularly limited. For example, polyester resin, acrylic resin, epoxy resin, urethane resin, fluorine resin, silicon polyester resin, vinyl chloride resin, polyolefin resin, butyral resin, polycarbonate resin, polyamide resin, polystyrene The resin component such as resin, polyimide resin, phenol resin or their modified resin is crosslinked with butylated melamine, methylated melamine, butylmethyl mixed melamine, urea resin, isocyanate, natural rubber or mixed rubber component of these. Or an electron beam curable type, an ultraviolet curable type, or the like, or those appropriately provided with a functional group. Metal oxide particles such as silica, titania, alumina and zirconia for the purpose of improving corrosion resistance, coloring pigments, dyes, gloss modifiers such as silica, surface smoothing agents, ultraviolet absorbers, hindered amine light stabilizers, viscosity modifiers, An additive such as a curing catalyst, a pigment dispersant, a pigment settling inhibitor, a color separation inhibitor, a rust inhibitor such as a phosphoric acid compound, an antioxidant, and carbon black powder may be included. These may be used alone or in combination. However, it is desirable to select one that takes the global environment into consideration. Also, the method for forming the organic resin coating layer is not particularly limited, and coating, electrodeposition coating, coating, laminating, etc. may be used. In addition, the metal (water) oxide coating of the present invention exhibits good performance even when combined with an organic resin-based coating that conventionally has a chromate film as a base or an organic resin-based coating without a base treatment. And can be used without problems.

  The metal material applicable to the present invention, the metal species of the plated metal material, and the production method are not particularly limited. Further, the shape is not particularly limited, such as a plate, a wire, or a tube. For example, cold rolled steel sheet, hot rolled steel material, stainless steel material, electrogalvanized steel material, electrogalvanized steel material, hot dip galvanized steel material, hot dip galvanized steel material, hot dip aluminum plated steel material, hot dip aluminum alloy plated steel material, electro nickel plated steel material And electrotin plating steel materials.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples.

Metallic materials include electrogalvanized steel sheet (adhesion amount: 20 g / m ² ), hot-dip galvanized steel sheet (adhesion amount: 60 g / m ² ), hot-dip galvanized steel sheet (Al-Si alloy, 6 mass% Si, adhesion amount: 60 g) / m ² ) was used. These were subjected to an ultrasonic degreasing treatment in acetone and then subjected to an experiment. The metal (water) oxide was applied by a liquid phase precipitation method.

  As shown in Tables 1 and 2, the liquid phase precipitation treatment solution is ammonium hexafluorozirconate, zirconyl nitrate, ammonium hexafluorotitanate, vanadyl sulfate, ammonium hexaniobate, potassium fluorinated tantalate, ammonium hexasilicate, oxidation It was prepared by dissolving hafnium (IV) in hydrofluoric acid and adjusting the pH with aqueous ammonia to a predetermined concentration.

  The substrate that had been subjected to the degreasing treatment was immersed in a treatment solution or electrolyzed, and then electrolyzed to form a metal oxide or metal hydroxide film.

For metal oxide and metal hydroxide film formation by electrolysis, the current density was controlled to 50 to 100 mA / cm ² in the treatment liquid, cathode electrolysis was performed at room temperature for 0.1 to 10 seconds, washed with water and dried after film formation. . The film formation of the metal oxide and metal oxide by immersion was immersed for 1 to 10 minutes at room temperature, washed with water and dried after film formation.

  The resulting coating was confirmed for the formation of metal oxides and metal hydroxides and the amount of film formation by X-ray photoelectron spectroscopy and X-ray fluorescence.

  As a comparative example, a coating type chromate treatment was performed. Using a treatment agent in which silica (Snowtex O, manufactured by Nissan Chemical Industries, Ltd.) was added to chromic acid with a reduction rate of 40% so that chromic acid / silica = 1/3 (solid content mass ratio), a bar coater was used. It was applied to a substrate and dried at a plate temperature of 60 ° C.

  For some levels, further organic coating treatment was performed.

  The organic resin film was formed using an aqueous resin. Aqueous epoxy resin (Asahi Denka Kogyo Co., Ltd., Adeka Resin EMO436FS-12), Aqueous phenolic resin (Sumitomo Bakelite Co., Ltd., PR-NPK-261), Aqueous polyester resin (Dainippon Ink Chemical Co., Ltd., Finetech ES-650), water-based polyurethane resin (Asahi Denka Kogyo Co., Ltd., Adekabon titer HUX320), water-based acrylic resin (NSC Japan, Kanebinol KD-5), water-based polyolefin resin (Toho Chemical Industry ( Co., Ltd., HYTEC S-3121), adjusted to a solid content concentration of 20% by mass, applied with a bar coater to a dry film thickness of 1 μm, and dried at a final plate temperature of 150 ° C using a hot air drying oven Then, it was cooled with water. Moreover, about the water-based polyurethane resin, solid content concentration was changed and the dry film thickness was changed to 0.05-4 micrometers. Silica particles (Nissan Chemical Industry Co., Ltd., Snowtex-O) are added to the water-based epoxy resin, and silica particles (Nissan Chemical Industry Co., Ltd., Snowtex-N) are used as the aqueous polyurethane resin. Adjusted so that the solid content concentration is 20% by mass with respect to 20% by mass, and applied with a bar coater to a dry film thickness of 1μm, and dried at a final plate temperature of 150 ° C using a hot air drying oven Then, it was cooled with water.

  Among the obtained specimens, the specimens on which only metal oxides and metal hydroxides were formed were subjected to adhesion amount measurement and naked corrosion resistance (flat plate part, processed part) evaluation. For some levels, the coating composition was also quantified.

  About the test material which performed to the organic coating process, the adhesion amount, the measurement of the organic film thickness, the bare corrosion resistance (a flat plate part, a processing part), and the film adhesion were evaluated.

  Evaluation The following method was used.

(1) Corrosion resistance (flat plate part)
For the bare corrosion resistance of the flat plate portion, the SST (JIS-Z-2371) test was conducted by tape-sealing the edge and back surface of the test plate. The state of white rust generation after 120 hours was observed and evaluated in terms of white rust generation area%. The edge and back surface were tape-sealed, and an SST (JIS-Z-2371) test was conducted. After confirming the occurrence of white rust after 120 hours, a score was given according to the following evaluation criteria, and a score of 3 or higher was accepted.

10: No white rust
9: Less than 1% white rust
8: White rust 1% or more and less than 3%
7: White rust 3% or more and less than 5%
6: White rust 5% or more and less than 7%
5: White rust 7% or more and less than 10%
4: White rust 10% or more and less than 15%
3: White rust 15% or more and less than 20%
2: White rust 20% or more and less than 30%
1: White rust 30% or more (2) Corrosion resistance (processed part)
The corrosion resistance of the processed part was subjected to an SST (JIS-Z-2371) test after the test plate was subjected to 6 mm extrusion using an Erich Centa tester, and then the edge and back surface of the test plate were tape sealed. After confirming the occurrence of processing white rust after 120 hours, scoring was performed according to the following evaluation criteria, and a score of 3 or higher was accepted.

10: No white rust
9: Less than 1% white rust
8: White rust 1% or more and less than 3%
7: White rust 3% or more and less than 5%
6: White rust 5% or more and less than 7%
5: White rust 7% or more and less than 10%
4: White rust 10% or more and less than 15%
3: White rust 15% or more and less than 20%
2: White rust 20% or more and less than 30%
1: 30% or more of white rust (3) Film adhesion The film adhesion is enforced by applying 8mm extrusion to the test plate with an Erich Sensator and then applying cellophane (registered trademark) tape (made by Nichiban) to the extrusion. It peeled. The test plate was immersed in methyl violet staining solution, the state of the coating was observed, and a rating of 10 (no peeling) to 1 (complete peeling) was given according to the remaining rate of the coating. A score of 7 or higher was accepted.

  From the results of Tables 2 to 7 (Experiment Nos. 1 to 67), the specimens having the oxide and hydroxide coating layers according to the present invention show excellent corrosion resistance, and are comparable to the chromate-treated steel sheets of the comparative materials. It can be seen that

  Tables 8 to 11 (Experiment Nos. 68 to 115) show the case where an organic resin film layer is formed on the upper layer of the coating layer, exhibiting high adhesion with the organic coating layer and excellent corrosion resistance, and chromate. It was confirmed that it has the same or better performance than the treatment-based organic coating.

Claims (11)

A metal material in which a coating of one or both of metal oxide and metal hydroxide (metal (water) oxide) is formed by immersing or electrolyzing in a liquid phase deposition treatment solution containing metal ions, coating, oxides of three metal elements selected from the following a~c group, made from one or both of the hydroxide, oxide of metal element selected at least one of at least a group, one of hydroxides A metal (hydroxide) -coated metal material characterized by comprising both or both.
Group a: Ti, Zr, Hf,
b group: V, Nb, Ta,
c group: Si Oxides of metal elements wherein the coating is selected one by one each from each group of a~c group, claim 1, wherein a metal which is characterized by comprising one or both of the hydroxide (hydr) oxide coated metal material. The metal according to claim 1 or 2, wherein the coating further comprises one or both of an oxide and a hydroxide of at least one additional metal element selected from the group a to c. Water) Oxide coated metal material. 4. The metal (water) oxide-coated metal material according to claim 3, wherein the metal element contained in the coating is four types. Metal (hydr) oxide coated metal material according to any one of claims 1 to 4, wherein the metal conversion of the coating film is 5 ~200mg / m ^2. 6. The metal (water) oxide-coated metal material according to any one of claims 1 to 5 , wherein a ratio of an element selected from group a is 25% by mass or more of a metal equivalent amount of the coating film. The metal (water) according to any one of claims 1 to 6 , further comprising an organic resin-based film having a thickness of 0.1 µm to 3.0 µm containing a carboxyl group, a hydroxyl group, and a sulfonic acid group as an upper layer of the coating. ) Oxide coated metal material. Wherein the metal (hydr) oxide coated metal material according to any one of claims 1-7 metal material is cold rolled steel or hot rolled steel. Metal (hydr) oxide coated metal material according to any one of claims 1-8 wherein the metallic material is a surface treated metal material. 10. The metal (water) oxide-coated metal material according to claim 9 , wherein the surface-treated metal material is a galvanized steel material or a zinc alloy plated steel material. 10. The metal (water) oxide-coated metal material according to claim 9 , wherein the surface-treated metal material is an aluminum-plated steel material or an aluminum alloy-plated steel material.