JP2015232155A - Alumite member, manufacturing method of alumite member and treatment agent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an Alumite member having excellent sealing property and corrosion resistance.SOLUTION: An Alumite member has an anodic oxide film and cobalt and/or chromium on a surface of an aluminum base material or an aluminum alloy base material. From a surface of the Alumite member toward the aluminum base material or the aluminum alloy base material, cobalt or chromium is present in whole area of an oxide film or a thickness area having 0.01 μm or more, and abundance ratio of the cobalt is 0.5 mass% to 40 mass% and/or abundance ratio of chromium is 1 mass% to 40 mass% to the a depth of 3 μm from the surface of the Alumite member in a thickness direction.

Description

  The present invention relates to an anodized member, an alumite member manufacturing method, and a treatment agent.

  As one of the surface treatment techniques for aluminum or aluminum alloy, anodization (anodization) treatment has been performed for a long time. Anodizing is a technology that provides an aluminum member with corrosion resistance by forming an oxide film consisting of a porous layer and a barrier layer on the surface of aluminum or an aluminum alloy by anodic electrolysis, and then sealing the holes generated in the porous layer. is there. Moreover, it is also a technique which can give the outstanding color tone and corrosion resistance by immersing in coloring agents, such as dye, after alumite treatment, making a dye soak into the hole of a porous layer, and performing sealing treatment after that. Since many colors are obtained by selecting a dye and the corrosion resistance is also excellent, the alumite treatment has been widely used in the industrial field for a long time.

  Here, with respect to the sealing treatment, the alumite-treated material is immersed in pure water or a nickel acetate aqueous solution. If pure water is used, boiling water is used for 30 minutes or more, and nickel acetate aqueous solution is used for 90 minutes or more for 15 minutes or more. It is a common technique to seal the pores of the porous layer. By performing this sealing treatment, excellent corrosion resistance can be obtained. However, in the case of dyeing, since sealing with boiling water causes dye outflow called crying out, sealing with a nickel acetate aqueous solution is common. However, this sealing treatment needs to be performed for 30 minutes or more with boiling water for pure water, and 15 minutes or more for 90 ° C. or more with an aqueous nickel acetate solution. Industrially, the cost for maintaining this temperature, and sealing The time it takes is a problem. By reducing the temperature and shortening the time, productivity can be improved and costs can be reduced. In addition, when the corrosion resistance of the alumite-treated product subjected to sealing treatment is evaluated by a salt spray test, white rust is generated on the ADC12 material in 24 to 48 hours. Therefore, studies for further improving the corrosion resistance are also performed. Yes.

JP 2004-277866 A Japanese translation of PCT publication No. 2002-532631 JP 2012-036469 A JP 2007-277597 A Japanese National Patent Publication No. 11-509579 Japanese Patent Laid-Open No. 10-088109 JP-A-5-106087 JP 2010-248545 A

Journal of Aluminum Research Society 2013 No. 2 volume 430

  Means for lowering the alumite sealing treatment and improving the corrosion resistance of the alumite have already been studied. However, no technology has been obtained that can improve the corrosion resistance and at the same time reduce the sealing process temperature and time. For example, Patent Document 1 discloses a method of immersing an alumite member and applying a voltage. In this method, it is indispensable to add new electric equipment, and it is not preferable in terms of economy and productivity, rather than a simple process such as conventional dipping and spraying.

  Patent Document 2 contains a fluorinated polymer or copolymer of acrylic acid or methacrylic acid having a fluoroalkyl group, and a solution containing lithium ions and magnesium ions at pH 5.5 to 8.5 at 75 ° C. or higher. A method of processing is disclosed. Although nickel is not contained, the processing temperature is high.

  Patent Document 3 describes a protective film on aluminum or an aluminum alloy. However, although it was tried to divert to alumite, corrosion resistance could not be obtained.

  Patent Document 4 discloses a method of performing a sealing treatment with a solution containing an α-amino acid and a metal, but the treatment temperature is slightly higher than 50 ° C. and the corrosion resistance is not high.

  Patent Document 5 discloses a method using a solution containing lithium ions and fluoride ions, but after the treatment, it is treated as a two-stage treatment into a solution at 80 to 100 ° C. equivalent to the conventional boiling water sealing. Is not preferable in terms of economy and process, and corrosion resistance could not be obtained.

  Patent Documents 6 and 7 disclose compositions for suppressing the adhesion of contaminants, but both require a treatment temperature of 70 ° C. or higher and are not economically preferable.

  Patent Document 8 discloses a method in which dyed alumite is treated with a water-soluble cationic polymer aqueous solution to firmly fix the dye, and then sealed with a sealing treatment solution containing magnesium salt and / or calcium salt. Although disclosed, two-stage treatment is required, and the treatment temperature of the sealing treatment is as high as 80 ° C. or higher, which is not economically preferable.

  Non-Patent Document 1 also describes low-temperature sealing treatment, but it takes time for aging (leaving for stabilization), and low-temperature cracks are generated, resulting in poor corrosion resistance. Moreover, since hot water washing is essential after the sealing treatment, it cannot cope with shortening of the treatment process.

  In view of the above problems, an object of the present invention is to provide an alumite member having excellent sealing properties and corrosion resistance.

  The present inventors diligently studied means for improving the corrosion resistance of alumite, which is the above-mentioned problem of the prior art. As a result, it has been found that a processed product having excellent sealing properties and corrosion resistance can be obtained by providing an aluminum member having an anodized film and cobalt and / or chromium on the surface of an alumite-treated product. At the same time, compared to the conventional nickel acetate sealing treatment, low-temperature and short-time treatment is possible, and it has succeeded in greatly improving workability and cost merit. In addition, by adding zirconium, calcium, zinc, vanadium, nickel, titanium, magnesium, and aluminum in the post-anodite treatment, the treated material will have a calm appearance and no design, without reducing the corrosion resistance. Moreover, it discovered that light resistance was improved.

  The present invention completed on the basis of the above knowledge is, in one aspect, an anodized member in which an anodized film and cobalt and / or chromium are present on the surface of an aluminum base material or an aluminum alloy base material. From the surface to the aluminum substrate or aluminum alloy substrate direction, the cobalt or chromium is present in the whole oxide film or in a thickness region of 0.01 μm or more, and in the thickness direction, between 3 μm from the surface of the anodized member, In the anodized member, the abundance ratio of the cobalt is 0.5 mass% or more and 40 mass% or less, and / or the abundance ratio of the chromium is 1 mass% or more and 40 mass% or less.

  In yet another embodiment, the anodized member of the present invention is dyed after anodized.

  In yet another embodiment of the anodized member of the present invention, the surface of the anodized member includes at least one of a coating, a primer, a paint, and a clear coat containing at least one of the group consisting of silicon, resin, and wax. It has been processed.

  In yet another embodiment, the alumite member of the present invention further contains ions of one or more kinds of metals from the group consisting of zirconium, calcium, zinc, vanadium, nickel, titanium, magnesium, and aluminum.

  Another aspect of the present invention is an alumite member in which cobalt and / or chromium is present on the surface of an aluminum base material or an aluminum alloy base material and has a corrosion resistance of 48 hours or more in a salt spray test.

  In yet another aspect of the present invention, alumite having cobalt and / or chromium present on the surface of an aluminum base material or aluminum alloy base material and not containing nickel and having a corrosion resistance of 48 hours or more in a salt spray test. It is a member.

  In yet another embodiment, the alumite member of the present invention has a corrosion resistance of 72 hours or more in the salt spray test.

  In another aspect of the present invention, the surface of the aluminum base material or aluminum alloy base material is subjected to anodizing pretreatment, anodizing treatment, post-anodizing treatment, and drying treatment in this order. Is the method.

  In yet another aspect of the present invention, the alumite of the present invention wherein the surface of the aluminum base material or aluminum alloy base material is subjected to anodization pretreatment, anodization treatment, post-anodization treatment, hot water washing, and drying treatment in this order. It is a manufacturing method of a member.

  In one embodiment of the method for producing an alumite member of the present invention, the anodizing pretreatment is performed in one or more steps selected from degreasing, etching, desmutting, polishing treatment, and satin treatment.

  In another embodiment of the method for producing an alumite member of the present invention, the post-anodizing treatment is performed under conditions of 5 to 70 ° C., pH 2 to 7, and 1 to 900 seconds.

  In still another embodiment of the method for producing an anodized member of the present invention, the post-anodizing treatment is performed by dipping or spraying.

  In still another embodiment of the method for producing an alumite member of the present invention, a dyeing process is performed between the anodizing process and the post-anodizing process.

  In yet another embodiment of the method for producing an alumite member of the present invention, a coating or primer containing at least one of the group consisting of silicon, resin and wax between the post-anodizing treatment and the drying treatment Apply at least one of painting, clear coating.

  In another aspect of the present invention, there is provided a treating agent used in post-anodizing post-treatment after forming an anodized film on the surface of an aluminum base material or aluminum alloy base material in order to obtain the alumite member of the present invention. , A treatment agent containing cobalt ions and / or chromium ions and fluorine ions.

  In one embodiment, the treatment agent of the present invention further contains ions of one or more kinds of metals from the group consisting of zirconium, calcium, zinc, vanadium, nickel, titanium, magnesium, and aluminum.

  In one embodiment, the treatment agent of the present invention is a treatment agent used in an anodization pretreatment before forming an anodized film on the surface of an aluminum substrate or an aluminum alloy substrate in order to obtain the anodized member of the present invention. Yes, it is a processing agent containing caustic, silica, nitric acid, mineral acid, organic acid, fluorine compound, and surfactant.

  According to the present invention, an alumite-treated member having excellent corrosion resistance and sealing properties can be obtained from aluminum or an aluminum alloy. Furthermore, compared with the conventional nickel acetate sealing treatment, the treatment can be performed at a low temperature and in a short time, and productivity improvement and cost merit can be expected.

2 is a glow discharge luminescent surface analysis result of Comparative Example 1. 4 is a result of glow discharge luminescence surface analysis of Example 1. 6 is a result of glow discharge luminescence surface analysis of Example 2. It is sectional drawing (overall image) of the alumite member of Example 1. FIG. It is sectional drawing (oxygen mapping screen) of the alumite member of Example 1. It is sectional drawing (aluminum mapping screen) of the alumite member of Example 1. FIG. It is sectional drawing (chrome mapping screen) of the alumite member of Example 1. It is sectional drawing (cobalt mapping screen) of the alumite member of Example 1. It is sectional drawing (fluorine mapping screen) of the alumite member of Example 1. FIG.

(Anodized materials)
In the alumite member of the present invention, an anodized film and cobalt and / or chromium are present on the surface of an aluminum base or aluminum alloy base. As for the detailed mechanism for obtaining the high corrosion resistance of the alumite member, from the analysis results, the presence of the anodized film and cobalt and / or chromium on the surface of the substrate in this way allows the film to be sealed at the same time as sealing. An alumite member that is formed and excellent in corrosion resistance and sealing properties is obtained.

  In the anodized member of the present invention, cobalt exists in the entire oxide film or in a thickness region of 0.01 μm or more from the surface of the anodized member toward the aluminum base material or aluminum alloy base material, and 3 μm from the surface of the anodized member in the thickness direction. Between, the abundance ratio of cobalt is 0.5 mass% or more and 40 mass% or less, and / or the abundance ratio of chromium is 1 mass% or more and 40 mass% or less. In the thickness direction, the abundance ratio of cobalt and the abundance ratio of chromium do not need to cover the entire surface of the alumite member between 3 μm from the surface of the alumite member. The region satisfying the abundance ratio may be provided at least in a region that requires excellent sealing properties and corrosion resistance. With such a configuration, the coating itself is stabilized, and excellent corrosion resistance, appearance, and paint adhesion can be obtained. Further, in the thickness direction, the abundance ratio of cobalt is more preferably 1% by mass or more and 11% by mass or less, and more preferably 1% by mass or more and 7% by mass or less, between 3 μm from the surface of the alumite member. . Further, in the thickness direction, the abundance ratio of chromium is more preferably 5% by mass or more and 30% by mass or less, and more preferably 5% by mass or more and 25% by mass or less, between 3 μm from the surface of the anodized member. .

  In another aspect of the alumite member of the present invention, cobalt and / or chromium is present on the surface of the aluminum base material or aluminum alloy base material, and the salt spray test is 48 hours or longer, preferably 72 hours or longer, more preferably. Is an anodized member having corrosion resistance of 120 hours or more. In addition, in another aspect of the anodized member of the present invention, cobalt and / or chromium is present on the surface of the aluminum base material or aluminum alloy base material, nickel is not included, and a salt spray test is performed for 48 hours. The anodized member having a corrosion resistance of 72 hours or longer, more preferably 120 hours or longer, preferably above.

(Treatment metal substrate)
As a to-be-processed metal base material which forms the high corrosion resistance of this invention, it acts effectively with respect to the aluminum alloy member containing an aluminum member, a extending | stretching material, and die-casting. The anodized member of the present invention is produced by performing anodizing pretreatment, anodizing treatment, post-anodizing treatment, and drying treatment in this order on the surface of the aluminum substrate or aluminum alloy substrate.

(Anodic oxidation pretreatment)
First, anodizing pretreatment is performed on the metal substrate to be treated. The treatment agent for the anodization pretreatment preferably contains caustic, silica, nitric acid, mineral acid, organic acid, fluorine compound, and surfactant. With such a configuration, it is possible to remove oil, a release agent and dirt, and a uniform alumite appearance and good corrosion resistance can be obtained in a later step.

(Degreasing pre-anodizing treatment)
By performing degreasing as an anodizing pretreatment, it is possible to improve the treated appearance, corrosion resistance and paint adhesion of the anodized member of the present invention. An acid type or alkaline type degreasing agent can be used for degreasing. Regarding the degreasing time, it is necessary to change the processing conditions depending on the degree of oil adhesion of the member. However, if the degreasing time is short, the degreasing is poor and the final processed product cannot obtain uneven appearance and excellent corrosion resistance.

(Etching of pre-anodizing treatment)
By performing etching as the pre-anodizing treatment, it is possible to improve the treated appearance, dyeability, corrosion resistance and paint adhesion of the anodized member of the present invention. For a member to which a release agent or the like is attached, the release agent can be removed by etching. By performing an etching process using acid or alkali, the release agent can be removed, and the corrosion resistance is improved. If the removal of the release agent or the like is insufficient, the final processed product cannot obtain uneven appearance and excellent corrosion resistance.

(Desmutting of anodizing pretreatment)
When smut is generated on the surface of the processed material, desmutting treatment (for example, treatment by removing it from nitric acid by applying it to nitric acid) is possible. By performing desmutting treatment as anodizing pretreatment, it is possible to improve the treated appearance, dyeability, corrosion resistance and paint adhesion of the anodized member of the present invention. If the desmutting process is insufficient, the final processed product cannot have uneven appearance and excellent corrosion resistance.

(Anodic oxidation pretreatment polishing process)
By performing a polishing treatment as a pretreatment for anodization, it is possible to improve the treatment appearance, dyeability, corrosion resistance and paint adhesion of the anodized member of the present invention. In particular, it is possible to obtain effects such as design properties of the processed material and removal of hot water wrinkles. An acidic type or alkaline type polishing agent can be used, and chemical polishing treatment or electrolytic polishing treatment can be performed.

(Satin finish for anodizing pretreatment)
By performing a satin treatment (a treatment for eliminating luster or the like) as an anodizing pretreatment, it is possible to improve the treatment appearance, dyeability, corrosion resistance and paint adhesion of the anodized member of the present invention. In particular, it is possible to perform a satin treatment in order to obtain effects such as design properties of the processed material and removal of hot water wrinkles. Acidic or alkaline pear finishes can be used, and chemical pear finish or electrolytic pear finish can be performed.

(Aluminum anodizing treatment)
An aluminum anodizing treatment is performed by immersing the metal substrate after the anodizing pretreatment in a treatment bath of an alumite treatment solution. The thickness of the oxide film formed by anodization is preferably 1 to 70 μm, more preferably 5 to 30 μm. If it is 1 μm or less, the corrosion resistance is lowered and the dyeing process becomes difficult, and if it is 70 μm or more, the productivity is lowered, which is not preferable. As long as a film thickness of 1 μm or more can be obtained, the alumite treatment solution, temperature, voltage, and the like can be freely selected. Sulfuric acid, ammonium sulfate, sodium hydrogensulfate, ammonium hydrogensulfate, phosphoric acid, sodium phosphate, boric acid, borax, ammonium carbonate, chromic acid, dichromic acid, sulfamic acid, sulphur, which are treatment liquids used in general anodized and hard anodized baths Acid, tartaric acid, maleic acid, citric acid, ammonium citrate, formic acid, aqueous ammonia, sodium hydroxide, ammonium fluoride, potassium ferricyanide, dimethyl sulfoxide, formamide, hydrogen peroxide, potassium titanate oxalate, sulfosalicylic acid, sulfophthalate A treatment agent containing acid, sulfoisophthalic acid, phenolsulfonic acid and the like and used at −5 to 250 ° C. can be used.

(Dyeing after aluminum anodizing)
A dyeing process can be performed between the anodizing process and the post-anodizing process. At this time, it is possible to obtain good appearance and corrosion resistance by performing post-treatment of the subsequent aluminum anodic oxidation without causing the dye to flow out. By performing the dyeing process, it is possible to improve the processing appearance of the anodized member of the present invention.

(Anodic oxidation post-treatment)
After the aluminum anodizing treatment, post-anodizing treatment is performed. The post-anodizing treatment can be performed by dipping in the treatment liquid or by spraying the treatment liquid. By selecting a treatment method suitable for the treatment plant, it is possible to improve the treatment appearance, corrosion resistance and paint adhesion of the present invention.

(Temperature of anodized post-treatment liquid)
The temperature of the treatment liquid for the post-anodizing treatment is preferably in the range of 5 to 70 ° C, and more preferably in the range of 20 to 50 ° C. A good film can be obtained within the above processing temperature range, and good appearance, sealing properties and corrosion resistance can be obtained. When the treatment temperature is 5 ° C. or lower, it takes time to obtain a film due to a decrease in the reaction rate.

(PH of treatment solution for post-anodizing treatment)
The pH of the treatment liquid for the post-anodizing treatment is preferably in the range of 2 to 7, and more preferably in the range of treatment pH of 3 to 5. When the treatment pH is within the above range, a good film can be obtained, and good appearance, sealing properties and corrosion resistance can be obtained. When the treatment pH is 2 or less, the member is excessively polished, resulting in uneven processing appearance and reduced corrosion resistance. When the treatment pH is 7 or more, the reaction rate is lowered and precipitation tends to occur in the treatment solution, and it is strongly alkaline. Is not preferable. When pH adjustment is necessary, nitric acid and caustic soda can be used. In addition, sulfuric acid, hydrochloric acid, caustic potash, aqueous ammonia and the like can also be used.

(Time of post-anodizing treatment)
The time for the post-anodizing treatment is preferably in the range of 1 to 900 seconds, and more preferably in the range of 2 to 300 seconds. When the treatment time is within the above range, a good film can be obtained, and good appearance, sealing properties and corrosion resistance can be obtained. If the treatment time is 1 second or less, the corrosion resistance is lowered due to insufficient reaction, and if it is 900 seconds or more, the processing is not uniform due to excessive treatment and the productivity is also lowered.

(Anodizing post-treatment agent)
The anodizing post-treatment agent used in the present invention contains cobalt ions and / or chromium ions and fluorine ions.

(Anodizing post-treatment agent-Cobalt ion source)
Cobalt compounds such as cobalt nitrate, cobalt sulfate, cobalt chloride, cobalt phosphate, cobalt acetate, cobalt fluoride, and cobalt hydroxide can be used as an ion source of cobalt ions, which are constituents of the anodizing post-treatment agent. If it is a compound of cobalt, substances other than the above can be used as a source of cobalt. These cobalt compounds may be used alone or in combination of two or more. The cobalt ion concentration of the compound is preferably 0.001 to 50 g / L, and more preferably 0.01 to 20 g / L. A good film can be obtained when the cobalt concentration is within the above range, and good appearance, sealing properties and corrosion resistance can be obtained. When the cobalt concentration is lower than 0.001 g / L, the corrosion resistance and the sealing performance are lowered, and when it exceeds 50 g / L, the cost merit is lowered and precipitation is likely to occur in the treatment liquid.

(Anodizing post-treatment agent-chromium ion source)
The ion source of chromium ion, which is a constituent of the anodizing post-treatment agent, includes trivalent chromium salts such as chromium nitrate, chromium sulfate, chromium chloride, chromium phosphate, chromium acetate, chromium hydroxide, and chromic acid and heavy chromium. A chromium compound such as trivalent chromium obtained by reducing hexavalent chromium such as an acid to trivalent with a reducing agent can be used. If it is a compound of trivalent chromium, substances other than the above can be used as a source of trivalent chromium. These chromium compounds can be used singly or in combination of two or more. The chromium ion concentration of the compound is preferably 0.001 to 50 g / L, and more preferably 0.01 to 20 g / L. When the chromium concentration is within the above range, a good film can be obtained, and good appearance, sealing properties and corrosion resistance can be obtained. When the chromium concentration is lower than 0.001 g / L, the corrosion resistance and the sealing performance are lowered, and when it exceeds 50 g / L, the cost merit is lowered and precipitation is likely to occur in the treatment liquid.

(Anodizing post-treatment agent-Fluorine ion source)
Sources of fluorine ions, which are constituents of the anodizing post-treatment agent, include hydrogen fluoride, ammonium fluoride, acidic ammonium fluoride, potassium fluoride, acidic potassium fluoride, sodium fluoride, acidic sodium fluoride, fluoride. Fluorine compounds such as cobalt fluoride, zircon ammonium fluoride, and borofluoride can be used. If it is a fluorine compound, substances other than those described above can be used as the fluorine supply source. One or two or more of these fluorine compounds can be used. The fluorine ion concentration of the compound is preferably 0.01 to 100 g / L, more preferably 0.1 to 50 g / L. When the fluorine ion concentration is within the above range, a good film is obtained, and good appearance, sealing properties and corrosion resistance are obtained. When the fluorine ion concentration is lower than 0.01 g / L, the corrosion resistance and the sealing performance are lowered, and when it exceeds 100 g / L, the cost merit is lowered and precipitation is likely to occur in the treatment liquid.

(Anodizing post-treatment agent-zirconium source)
Further, the post-anodizing treatment agent may contain a zirconium source. Zirconium compounds such as zirconium oxychloride, zirconium sulfate, zirconium nitrate, zirconium oxide, zircon ammonium fluoride, zircon hydrofluoric acid, and zirconium sol can be used as the zirconium source. If it is a compound of zirconium, substances other than the above can be used as a supply source of zirconium. One or two or more of these zirconium compounds can be used. The zirconium concentration of the compound is preferably 0.001 to 50 g / L, and more preferably 0.01 to 20 g / L. A good film is obtained when the zirconium concentration is within the above range, and good appearance, sealing properties and corrosion resistance are obtained. If the zirconium concentration is lower than 0.001 g / L, it is difficult to obtain design properties and light resistance, and if it exceeds 50 g / L, the cost merit is reduced and precipitation is likely to occur in the treatment liquid.

(Anodizing post-treatment agent-calcium source)
Further, the post-anodizing treatment agent may contain a calcium source. As the calcium source, calcium compounds such as calcium fluoride, calcium sulfate, calcium citrate, calcium lactate, calcium thioglycolate, and calcium tungstate can be used. These calcium compounds can be used alone or in combination of two or more. The calcium concentration of the compound is preferably 0.01 to 10 g / L, and more preferably 0.1 to 1 g / L. A good film can be obtained when the calcium concentration is within the above range, and good appearance, sealing properties and corrosion resistance can be obtained. If the calcium concentration is lower than 0.01 g / L, it is difficult to obtain the effect of improving the design and light resistance, and if it exceeds 10 g / L, the cost merit is reduced and precipitation is likely to occur in the treatment liquid.

(Anodizing post-treatment agent-zinc source)
Further, the post-anodizing treatment agent may contain a zinc source. As the zinc source, zinc compounds such as zinc oxide, zinc nitrate, zinc sulfate, zinc chloride, zinc acetate and zinc carbonate can be used. If it is a compound of zinc, substances other than the above can be used as a source of zinc. These zinc compounds can be used alone or in combination of two or more. The zinc concentration is preferably 0.001 to 50 g / L, and more preferably 0.01 to 30 g / L. When the zinc concentration is within the above range, a good film can be obtained, and good appearance, sealing properties and corrosion resistance can be obtained. When the zinc concentration is lower than 0.001 g / L, it is difficult to obtain the effect of improving the design property and light resistance.

(Anodizing post-treatment agent-vanadium source)
The post-anodizing treatment agent may contain a vanadium source. As the vanadium source, vanadium compounds such as vanadium nitrate, vanadium sulfate, vanadium chloride, vanadic acid, potassium metavanadate, and ammonium metavanadate can be used. If it is a compound of vanadium, substances other than the above can be used as a supply source of vanadium. These vanadium compounds can be used alone or in combination of two or more. The vanadium concentration is preferably 0.001 to 50 g / L, and more preferably 0.01 to 30 g / L. A good film is obtained when the vanadium concentration is within the above range, and good appearance, sealing properties and corrosion resistance are obtained. When the vanadium concentration is lower than 0.001 g / L, it is difficult to obtain an effect of improving the design and light resistance.

(Anodizing post-treatment agent-nickel source)
Further, the post-anodizing treatment agent may contain a nickel source. As the nickel source, nickel compounds such as nickel nitrate, nickel sulfate, nickel chloride, nickel phosphate, nickel sulfamate, nickel acetate and nickel fluoride can be used. If it is a compound of nickel, substances other than the above can be used as a nickel supply source. These nickel compounds can be used alone or in combination of two or more. The nickel concentration is preferably 0.001 to 20 g / L, and more preferably 0.01 to 10 g / L. A good film is obtained when the nickel concentration is within the above range, and good appearance, sealing properties and corrosion resistance are obtained. When the nickel concentration is lower than 0.001 g / L, it is difficult to obtain the effect of improving the design and light resistance, and when it exceeds 20 g / L, the cost merit is reduced and precipitation is likely to occur.

(Anodizing post-treatment agent-titanium source)
Further, the post-anodizing treatment agent may contain a titanium source. As the titanium source, titanium compounds such as titanium chloride, potassium titanium oxalate, ammonium titanium fluoride, potassium titanium fluoride, and titanium sulfate can be used. These titanium compounds can be used alone or in combination of two or more. The titanium concentration is preferably 0.01 to 50 g / L, and more preferably 0.1 to 20 g / L. When the titanium concentration is within the above range, a good film can be obtained, and good appearance, sealing properties and corrosion resistance can be obtained. When the titanium concentration is lower than 0.001 g / L, it is difficult to obtain the effect of improving the design and light resistance, and when it exceeds 50 g / L, the cost merit is reduced and precipitation is likely to occur.

(Anodizing post-treatment agent-magnesium source)
Further, the post-anodizing treatment agent may contain a magnesium source. As the magnesium source, magnesium compounds such as magnesium nitrate, magnesium sulfate, magnesium chloride, magnesium acetate, and magnesium carbonate can be used. If it is a compound of magnesium, substances other than the above can be used as a source of magnesium. These magnesium compounds can be used alone or in combination of two or more. The magnesium concentration is preferably 0.001 to 50 g / L, and more preferably 0.01 to 30 g / L. A good film is obtained when the magnesium concentration is within the above range, and good appearance, sealing properties and corrosion resistance are obtained. When the magnesium concentration is lower than 0.001 g / L, it is difficult to obtain the effect of improving the design and light resistance, and when it exceeds 50 g / L, the cost merit is reduced and precipitation is likely to occur.

(Anodizing post-treatment agent-aluminum source)
Further, the post-anodizing treatment agent may contain an aluminum source. As the aluminum source, aluminum compounds such as aluminum nitrate, aluminum sulfate, aluminum chloride, aluminum acetate, aluminum carbonate, and corydal alumina can be used. A substance other than the above can be used as an aluminum supply source as long as it is an aluminum compound. These aluminum compounds can be used alone or in combination of two or more. The aluminum concentration is preferably 0.001 to 50 g / L, and more preferably 0.01 to 30 g / L. When the aluminum concentration is within the above range, a good film is obtained, and good appearance, sealing properties and corrosion resistance are obtained. If the aluminum concentration is lower than 0.001 g / L, it is difficult to obtain the effect of improving the design and light resistance.

(After anodizing and post-treatment)
It is also possible to perform hot water washing after the post-anodizing treatment. The appearance and corrosion resistance are not affected by the presence or absence of hot water washing, but the washing ability is improved by washing with hot water, and the temperature of the member rises, so that the drying in the subsequent drying process can be easily performed in a short time. it can. Although there is no designation for temperature or time, immersion at 40 to 80 ° C. for 10 seconds to 5 minutes is excellent in mass productivity.

(Coating, primer, painting, clear coating after post-anodizing treatment)
After the post-anodizing treatment, any one or more of coating, primer, painting, and clear coating containing at least one of the group consisting of silicon, resin, and wax may be performed. The coating can mainly impart corrosion resistance. The primer is mainly used as a base for painting and can impart adhesion. The paint is mainly used to control the color tone. The clear coat is mainly used for polishing such as wax. There is no particular limitation on these coatings, primers, paints, clear coats, acrylic resin, olefin resin, alkyd resin, urea resin, epoxy resin, melamine resin, fluororesin, polyethylene, polyvinyl chloride, polystyrene, polypropylene, methacrylic resin, phenol Coatings, primers, paints, and clear coats containing resin, polyester resin, polyurethane, polyamide, polycarbonate, and other resins, silicates, colloidal silica, and the like may be used. These concentrations are preferably from 0.01 to 800 g / L, but the appropriate concentration depends on the type of component. Specific examples of the coating agent include Cosmar Coat (trade name, Kansai Paint Co., Ltd.), Hi Seal 272 (trade name, Nippon Surface Chemistry Co., Ltd.), Stron J Coat (trade name, Nihon Surface Chemical Co., Ltd.) ), Triner TR-170 (trade name, Nippon Surface Chemistry Co., Ltd.), Finigard (trade name, Coventya) and the like. Specific examples of the acrylic resin include GX-235T (trade name, Nippon Surface Chemical Co., Ltd.), hirotite (trade name, Hitachi Chemical Co., Ltd.), alloset (trade name, Nippon Shokubai Co., Ltd.), and the like. Yes, for olefin resin, Frocene (trade name, Sumitomo Seika Co., Ltd.), PES (trade name, Nippon Unicar Co., Ltd.), Chemipearl (trade name, Mitsui Chemicals), Sun Fine (trade name, Asahi Kasei Co., Ltd. and epoxy resins include AL primer (trade name, Isamu Paint Co., Ltd.), Isamu Epolo 500 (trade name, Isamu Paint Co., Ltd.) and the like. Electrodeposition coating can also be performed.

(Drying process)
A drying process is performed after the anodizing post-treatment or after the coating, primer, painting or clear coating.

(Drying temperature)
The drying temperature is not limited as long as the member can be dried, but is preferably in the range of 20 to 200 ° C, and more preferably in the range of 60 to 120 ° C. When the drying temperature is lower than 20 ° C., it takes a long time to reduce the productivity, and when it is 200 ° C. or higher, the cost increases.

(Drying time)
The drying time is not limited as long as the member can be dried, but is preferably in the range of 1 to 20 minutes, more preferably in the range of 5 to 15 minutes. When the drying time is shorter than 1 minute, insufficient drying tends to occur, and when it is 20 minutes or longer, productivity is lowered, which is not preferable.

  The present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to these examples.

  As a metal base material (material) to be processed, A1100 was used as the aluminum base material, and ADC12 material and A5052 material were used as the aluminum alloy base material. The series of experimental steps are degreasing, alkaline etching, desmutting, aluminum anodizing, dyeing treatment as necessary, treatment after aluminum anodizing, coating / primer / painting / clear coat treatment as necessary, and drying. Unless otherwise specified, immersion treatment was performed. All these steps were washed with water. However, it was dried without washing after coating, primer, painting and clear coating. Degreasing was carried out under the conditions of Keiclin 6 (Nippon Surface Chemicals non-ferrous degreasing agent) 50 mL / L, 50 ° C., 5 minutes. Alkaline etching was performed under the conditions of caustic soda 50 g / L, 60 ° C., and 30 seconds. The desmutting treatment was performed under conditions of 67.5% nitric acid 300 mL / L at room temperature for 1 minute. The polishing treatment was performed at Chemilite 53 (Chemical Abrasive manufactured by Nippon Surface Chemical Co., Ltd.) 950 mL / L, 67.5% nitric acid 50 mL / L, 100 ° C., 30 seconds. The satin treatment was performed at Alec 83 (Chemical pear finish manufactured by Nippon Surface Chemical Co., Ltd.) 150 g / L at 65 ° C. for 2 minutes.

Alumite treatment (anodization treatment) was adjusted to a thickness of 10 μm with 98% purified sulfuric acid 150 mL / L, 16 V, 1.3 A / dm ² and eddy current film thickness for each material. The dyeing treatment was performed under the conditions of Jusco Color BL (black dye manufactured by Nippon Surface Chemical Co., Ltd.) 10 g / L, 60 ° C., pH 4.2, 10 minutes. The spray treatment after the aluminum anodization was performed at 1.3 kgf / cm ² . The hot water washing after the treatment after aluminum anodization was performed at 45 ° C. for 1 minute. When performing hot water washing, it processed in the process of the process after aluminum anodizing, water washing, hot water washing, and drying. Stron J coat (silica-based coating agent manufactured by Nippon Surface Chemical Co., Ltd.) was performed at a stock concentration of 40 ° C. for 10 seconds. High seal 272 (acrylic coating agent manufactured by Nippon Surface Chemical Co., Ltd.) was treated at 500 mL / L at room temperature for 10 seconds. GX-235T (acrylic clear coat manufactured by Nippon Surface Chemical Co., Ltd.) was treated at 100 mL / L at room temperature for 10 seconds. Hypon Fine Primer II (modified epoxy resin primer manufactured by Nippon Paint Co., Ltd.) was applied in a stock solution at a room temperature and a bar coater was applied (about 7 μm in No. 3). Fine urethane U100 (urethane paint manufactured by Nippon Paint Co., Ltd.) was applied as a concentrated stock solution and a bar coater was applied at room temperature (about 7 μm for No. 3). The nickel acetate sealing agent in Comparative Examples 1 to 3 was processed by Alseal 87 (Nihon Surface Chemical Co., Ltd.) 6 g / L, 90 ° C., pH 5.9, and 15 minutes. Drying was performed at 80 ° C. for 10 minutes. In Comparative Example 2, (2) Anodizing treatment was not performed, and (1) pretreatment, water washing, (3) post-anodizing treatment, water washing, and drying were carried out in this order. The electrolytic treatment of Comparative Example 14 was performed by -5 V cathodic electrolysis (anode carbon plate). Comparative Example 17 was (3) post-anodizing post-treatment, the first treatment with the composition of No. 40 treatment solution, the water treatment, the second treatment with pure water, and the drying treatment in this order.

  The corrosion resistance test was a salt spray test according to JIS Z 2371. In the coating adhesion test, an epoxy resin is applied to the surface of the test piece, baked and dried, cross-cut in a grid pattern, immersed in boiling water for 30 minutes, cellophane tape is crimped, and peeled off in the vertical direction. evaluated. Regarding the examples subjected to the coating treatment, a cross cut was put in a grid pattern as it was, and after immersion in boiling water for 30 minutes, a cellophane tape was pressure-bonded and peeled in the vertical direction for evaluation. Cobalt and chromium are checked by glow discharge emission surface analysis using a Marcus type high-frequency glow discharge emission analyzer GD-Profiler2 manufactured by HORIBA, Ltd. to confirm whether they are present in the entire oxide film or in a thickness region of 0.01 μm or more. Furthermore, each part of 0 μm, 0.5 μm, 1 μm, 1.5 μm, 2 μm, 2.5 μm, and 3 μm is measured in the depth direction from the surface of the sample to obtain each abundance ratio (mass%), and the average is calculated. did. (3) Regarding Examples 12 to 17 in which coating, primer, coating, and clear coating were performed after the treatment after aluminum anodization, cobalt and chromium were added by glow discharge emission surface analysis before coating, primer, coating, and clear coating. analyzed. The ink test was a test according to JIS H 8683-1.

  Test conditions, drug composition, and evaluation results are shown in the following table. In the table, (1) indicates conditions related to the anodizing pretreatment, (2) indicates conditions related to the aluminum anodizing treatment, and (3) describes conditions related to the postanodizing treatment.

The appearance was evaluated visually on the sample surface.
The salt spray test evaluation (corrosion resistance evaluation) is based on the following criteria.
A: No white rust generation after 1008 hours B: White rust generation after 48 hours C: White rust generation after 24 hours Cross-cut test evaluation in the table for judging coating adhesion is based on the following criteria.
A: No peeling B: Peeling less than 5% C: Peeling less than 10% D: Peeling less than 50% E: Peeling more than 50% An ink test showing sealing properties is based on the following criteria.
A: No ink remaining B: Ink remaining

(Evaluation)
From the experimental results, it was confirmed that excellent appearance, corrosion resistance, paint adhesion, and sealing properties can be obtained by producing an anodized film and an aluminum member containing cobalt and / or chromium. Furthermore, by using the treatment agent after aluminum anodization containing one or more kinds of metal ions out of the group consisting of zirconium, calcium, zinc, vanadium, nickel, titanium, magnesium, and aluminum, the design is further improved. There was no adverse effect on corrosion resistance. On the other hand, it was confirmed from the comparative examples that the corrosion resistance comparable to the examples was not obtained. Even when compared with the nickel acetate sealing treatment product of Comparative Example 1 which is a conventional treatment product, excellent corrosion resistance was obtained at low temperature and short time treatment.

In each of Examples 1-110, it was confirmed that cobalt or chromium was present in the entire oxide film or in a thickness region of 0.01 μm or more.
FIG. 1 shows the results of glow discharge luminescence surface analysis of Comparative Example 1 and FIG. 2 of Example 1 of glow discharge. These are both processed products of ADC12 material. Although the ADC12 material also contains copper and silica, the elements that are not related to the present invention are omitted because the tables are difficult to see. First, Comparative Example 1 is a prior art sealing process using nickel acetate. This sealing treatment is carried out by two types of reaction mechanisms: the hydration sealing reaction (I) accompanied by the volume expansion of the film in the pores of the alumite porous layer and the precipitation reaction (II) that precipitates nickel hydroxide. It is presumed that sealing has been performed. From the results of glow discharge luminescence surface analysis, it can be inferred that a large amount of nickel is deposited at a position shallower than 0.01 μm from the surface layer in this sealing treatment using nickel acetate, and the sealing is performed at a shallow position on the surface layer. .
Al ₂ O ₃ + H ₂ O → Al ₂ O ₃ .H ₂ O (Boehmite) (I)
Ni (CH ₃ COO) ₂ + 2H ₂ O → Ni (OH) ₂ + 2CH ₃ COOH (II)
On the other hand, from the glow discharge luminescence surface analysis result of Example 1 which is the present invention, it can be confirmed that the components cobalt and chromium are very thick up to 4 μm or more.

  FIG. 3 shows the results of glow discharge luminescence surface analysis of Example 2. Comparative Example 1 is a prior art sealing treatment using nickel acetate. Like the ADC12 material of Comparative Example 1, nickel is present only on the surface layer. From the results of glow discharge luminescence surface analysis of Example 2, it can be confirmed that the components cobalt and chromium are very thick up to 4 μm or more. A wrought material such as A1100 is a material that is easy to obtain corrosion resistance, and Example 2 is treated at 40 ° C. for 180 seconds. Considering the corrosion resistance between the treatments at 40 ° C. for 180 seconds in Example 2 and Comparative Example 3, the superiority of the present invention can be proved again.

  Moreover, the FE-SEM-EDX cross-section element mapping photograph of Example 1 is shown in FIGS. From here, it can be confirmed that cobalt and chromium are present even inside the anodized film. From FIG. 9, it is confirmed that fluorine is an element that is not detected in the glow discharge luminescence surface analysis result, but is a substance that is detected in the FE-SEM-EDX cross-section element mapping and exists even inside the alumite film. Although the detailed reaction mechanism of this film is unknown, the thickness of a chemical conversion film such as a general hexavalent chromate or chromium film is generally 0.01 to 0.8 μm, and cobalt exists thicker than 0.01 μm. It is presumed that excellent corrosion resistance can be obtained because a chromium film is obtained in the present invention.

Claims (17)

An anodized member in which an anodized film and cobalt and / or chromium are present on the surface of an aluminum substrate or an aluminum alloy substrate;
From the surface of the anodized member toward the aluminum base material or aluminum alloy base material, the cobalt or chromium is present in the entire oxide film or in a thickness region of 0.01 μm or more,
In the thickness direction, the abundance ratio of cobalt is 0.5 mass% or more and 40 mass% or less and / or the abundance ratio of chromium is 1 mass% or more and 40 mass% or less between 3 μm from the surface of the anodized member. An anodized member.   The anodized member according to claim 1, which has been dyed after anodized.   3. The anodized member according to claim 1, wherein the surface of the anodized member is treated with at least one of a coating, a primer, a paint, and a clear coat containing at least one of the group consisting of silicon, resin, and wax. .   Furthermore, the alumite member as described in any one of Claims 1-3 containing the ion of 1 or more types of metals among the group which consists of zirconium, calcium, zinc, vanadium, nickel, titanium, magnesium, and aluminum.   An alumite member having cobalt and / or chromium on the surface of an aluminum base material or an aluminum alloy base material and having corrosion resistance of 48 hours or more in a salt spray test.   An alumite member having cobalt and / or chromium on the surface of an aluminum base material or an aluminum alloy base material and not containing nickel and having a corrosion resistance of 48 hours or more in a salt spray test.   The anodized member according to claim 5 or 6, which has a corrosion resistance of 72 hours or more in the salt spray test.   The anodized member according to any one of claims 1 to 7, wherein anodizing pretreatment, anodizing treatment, post-anodizing treatment, and drying treatment are performed in this order on the surface of the aluminum substrate or the aluminum alloy substrate. Production method.   The alumite according to any one of claims 1 to 7, wherein an anodizing pretreatment, an anodizing treatment, a post anodizing treatment, hot water washing, and a drying treatment are performed in this order on the surface of the aluminum base material or the aluminum alloy base material. Manufacturing method of member.   The method for producing an alumite member according to claim 8 or 9, wherein the anodizing pretreatment is performed in one or more steps selected from degreasing, etching, desmutting, polishing treatment, and satin treatment.   The manufacturing method of the alumite member as described in any one of Claims 8-10 which performs the said anodic oxidation post-process on 5-70 degreeC, pH 2-7, and the processing conditions of 1 to 900 seconds.   The manufacturing method of the alumite member as described in any one of Claims 8-11 which performs the said anodic oxidation post-process by immersion or spraying.   The manufacturing method of the alumite member as described in any one of Claims 8-12 which performs a dyeing | staining process between the said anodizing process and the said post-anodizing process.   9. The process of any one or more of a coating, a primer, a paint, and a clear coat containing at least one of the group consisting of silicon, resin, and wax is performed between the post-anodizing treatment and the drying process. The manufacturing method of the alumite member as described in any one of -13.   In order to obtain the alumite member as described in any one of Claims 1-7, it is a processing agent used in the post-anodizing post-process after forming an anodized film on the surface of an aluminum base material or an aluminum alloy base material. , A treatment agent containing cobalt ions and / or chromium ions and fluorine ions.   Furthermore, the processing agent of Claim 15 containing the ion of 1 or more types of metals in the group which consists of zirconium, calcium, zinc, vanadium, nickel, titanium, magnesium, and aluminum.   In order to obtain the alumite member as described in any one of Claims 1-7, it is a processing agent used in the anodic oxidation pretreatment before forming an anodic oxide film on the surface of an aluminum base material or an aluminum alloy base material. , A treatment agent containing caustic, silica, nitric acid, mineral acid, organic acid, fluorine compound, and surfactant.