JPH0238680B2 - SANKAHIMAKUOJUSURUARUMINIUMUKEIKINZOKUNOHYOMENSHORIHOHO - Google Patents

Description

[Detailed description of the invention]

(a) Industrial application field The present invention is directed to converting the oxide film of an aluminum-based metal such as aluminum or an alloy containing aluminum into an opaque white to grayish-white film with excellent color resistance and weather resistance. or form a pastel colored film.
The present invention relates to a method for surface treatment of aluminum-based metals having an oxide film. (b) Conventional technology In recent years, with changes in lifestyles and tastes, there has been a demand for coloring aluminum-based metal products used in building materials, nameplates, decorative items, daily necessities, vehicles, etc. In the fields of decorative goods, vehicles, building materials, etc., pastel-colored aluminum-based metal products are in high demand because they give a calm and warm feeling to the viewer. By the way, in order to color an aluminum-based metal product in a pastel tone, it is first necessary to color the aluminum-based metal semi-finished product in a basic opaque white to gray-white color. Conventionally, the following surface treatment method has been proposed as a method for coloring aluminum-based metal semi-finished products in a pastel tone. That is, an aluminum-based metal semi-finished product having an anodized film is treated with calcium salt, magnesium salt,
After being immersed in a solution containing sulfuric acid and at least one of zinc salts and aluminum salts, or electrolyzed in the solution, the product from the salt in the micropores of the treated anodic oxide film reacts with a white to white color. After immersing or electrolyzing in a solution containing one or more substances that form a grayish-white compound, thereby coloring the anodic oxide film white to grayish-white,
It is colored using metal salts or dyeing. (Japanese Patent Application Laid-Open No. 1978-197897). (c) Problems to be Solved by the Invention However, in this method, an aluminum-based metal semi-finished product having an anodized film is colored white to grayish-white through the steps of Even if the product is immersed in the above process and the aqueous solution shown in , the metal salts are not effectively hydrolyzed on the surface or inside of the anodic oxide film, and as a result, the anodic oxide film becomes uniformly opaque white to grayish white. It cannot be colored. In addition, the opaque white to grayish-white film obtained by this method has poor adhesion to the anodic oxide film on aluminum-based metals, so after the anodic oxide film is colored opaque white to grayish-white, it is washed with water. There are problems such as film destruction (film loss), decolorization during sealing, and peeling of the film after sealing during processes such as drying and sealing. A white to grayish-white film has a fatal disadvantage of poor weather resistance and a low degree of whiteness due to a small refractive index of the colored component of the white to grayish-white film. Further, the surface treatment agent used in the above steps cannot uniformly color the anodic oxide film of the aluminum metal, and uneven coloring occurs, making it unsuitable for practical use. (d) Means for Solving the Problems The inventors of the present invention have conducted extensive studies over many years in order to solve the above problems all at once. As a result, when coloring the oxide film part of an aluminum-based metal semi-finished product having an oxide film to an opaque white to grayish white color, the obtained opaque white to grayish white film is uniform, and moreover, the film is destroyed (film loss). ), discoloration during sealing, and peeling of the film after sealing, first of all, enlarge the micropores in the oxide film part of the aluminum-based metal that has an oxide film. to facilitate the penetration of metal salts such as titanium salts, and then pool a fixing agent in the enlarged micropores that binds to metal ions in the metal salts such as titanium salts and fixes them within the micropores; It has been discovered that the metal ions and the fixing agent can be combined in the oxide film to form a white to grayish-white substance uniformly and densely in the oxide film. It has also been found that this white to grayish-white film can be colored into a pastel color with excellent characteristics by dyeing or electrolysis. Therefore, based on this knowledge, the present inventors
After re-examining the surface treatment agents for aluminum-based metals with oxide films that are suitable for use in this coloring, we found that, surprisingly, if a specific fixing agent is used, this coloring can be achieved even in an expanded pH range of 0.5 to 8.5. It was discovered that the oxide film could be colored uniformly and densely, and the present invention was completed. That is, the method for surface treatment of an aluminum-based metal having an oxide film according to the first invention of the present application uses a fixing agent that combines an aluminum-based metal having an oxide film with metal ions of the following metal salts to produce a white to gray-white substance. Step (A) of immersing or electrolyzing the aluminum-based metal in an aqueous solution containing
PH containing at least one metal salt of titanium salt, zinc salt, calcium salt, barium salt, strontium salt, magnesium salt or aluminum salt
Step (B) of immersing or electrolyzing in an aqueous solution of 0.5 to 8.5, the aluminum-based metal obtained in the above step (B),
PH containing at least one metal salt of titanium salt, zinc salt, calcium salt, barium salt, strontium salt, magnesium salt or aluminum salt, and an organic polar solvent and/or chelate compound
The method is characterized by comprising a step (C) of immersion in or electrolysis in an aqueous solution of 0.5 to 8.5. Further, the method for surface treatment of an aluminum-based metal having an oxide film according to the second invention of the present application includes a fixing agent that combines an aluminum-based metal having an oxide film with metal ions of the following metal salts to produce a white to gray-white substance. Step (A) of immersing or electrolyzing the aluminum-based metal in an aqueous solution containing
PH containing at least one metal salt of titanium salt, zinc salt, calcium salt, barium salt, strontium salt, magnesium salt or aluminum salt
Step (B) of immersing or electrolyzing in an aqueous solution of 0.5 to 8.5, the aluminum-based metal obtained in the above step (B),
PH containing at least one metal salt of titanium salt, zinc salt, calcium salt, barium salt, strontium salt, magnesium salt or aluminum salt, and an organic polar solvent and/or chelate compound
Step (C) of immersing or electrolyzing in an aqueous solution of 0.5 to 8.5, the aluminum-based metal obtained in the above step (C),
This method is characterized by comprising a step (D) of immersion in or electrolysis in an aqueous solution containing a fixing agent that combines with the metal ions of the metal salt to produce a white to off-white substance. Furthermore, the method for surface treatment of an aluminum-based metal having an oxide film according to the third invention of the present application includes a fixing agent that combines the aluminum-based metal having an oxide film with metal ions of the following metal salts to produce a white to gray-white substance. Step (A) of immersing or electrolyzing the aluminum-based metal in an aqueous solution containing
PH containing at least one metal salt of titanium salt, zinc salt, calcium salt, barium salt, strontium salt, magnesium salt or aluminum salt
Step (B) of immersing or electrolyzing in an aqueous solution of 0.5 to 8.5, the aluminum-based metal obtained in the above step (B),
PH containing at least one metal salt of titanium salt, zinc salt, calcium salt, barium salt, strontium salt, magnesium salt or aluminum salt, and an organic polar solvent and/or chelate compound
Step (C) of immersing or electrolyzing in an aqueous solution of 0.5 to 8.5, the aluminum-based metal obtained in the above step (C),
A step (D) of coloring by dyeing or electrolysis. Furthermore, the method for surface treatment of an aluminum-based metal having an oxide film according to the fourth invention of the present application includes a fixing agent that combines the aluminum-based metal having an oxide film with metal ions of the following metal salts to produce a white to gray-white substance. Step (A) of immersing or electrolyzing the aluminum-based metal in an aqueous solution containing
PH containing at least one metal salt of titanium salt, zinc salt, calcium salt, barium salt, strontium salt, magnesium salt or aluminum salt
Step (B) of immersing or electrolyzing in an aqueous solution of 0.5 to 8.5, the aluminum-based metal obtained in the above step (B),
PH containing at least one metal salt of titanium salt, zinc salt, calcium salt, barium salt, strontium salt, magnesium salt or aluminum salt, and an organic polar solvent and/or chelate compound
Step (C) of immersing or electrolyzing in an aqueous solution of 0.5 to 8.5, the aluminum-based metal obtained in the above step (C),
A step (D) of immersing the aluminum-based metal obtained in the above step (D) in an aqueous solution containing a fixing agent that combines with the metal ions of the metal salt to form a white to gray-white substance, or electrolyzing the aluminum-based metal in the aqueous solution. ,
It is characterized by comprising a step (E) of coloring by dyeing or electrolysis. The method for surface treatment of an aluminum-based metal having an oxide film according to the fifth invention of the present application includes a fixing agent that binds the aluminum-based metal having an oxide film with metal ions of the following metal salts to produce a white to gray-white substance. Step (A) of immersing or electrolyzing in an aqueous solution, the aluminum metal treated in the above step (A),
PH containing at least one metal salt of titanium salt, zinc salt, calcium salt, barium salt, strontium salt, magnesium salt or aluminum salt
Step (B) of immersing or electrolyzing in an aqueous solution of 0.5 to 8.5, the aluminum-based metal obtained in the above step (B),
PH0.5 to 8.5 containing at least one metal salt of titanium salt, zinc salt, calcium salt, barium salt, strontium salt, magnesium salt, or aluminum salt, an organic polar solvent and/or a chelate compound, and a fixing silicate. (C) immersion in or electrolysis in an aqueous solution. A method for surface treatment of an aluminum-based metal having an oxide film according to the sixth invention of the present application includes a fixing agent that binds the aluminum-based metal having an oxide film with metal ions of the following metal salts to produce a white to gray-white substance. Step (A) of immersing or electrolyzing in an aqueous solution, the aluminum metal treated in the above step (A),
PH containing at least one metal salt of titanium salt, zinc salt, calcium salt, barium salt, strontium salt, magnesium salt or aluminum salt
Step (B) of immersing or electrolyzing in an aqueous solution of 0.5 to 8.5, the aluminum-based metal obtained in the above step (B),
PH0.5 to 8.5 containing at least one metal salt of titanium salt, zinc salt, calcium salt, barium salt, strontium salt, magnesium salt, or aluminum salt, an organic polar solvent and/or a chelate compound, and a fixing silicate. Step (C) of immersing in or electrolyzing the aqueous solution of the aluminum-based metal obtained in the above step (C),
This method is characterized by comprising a step (D) of immersion in or electrolysis in an aqueous solution containing a fixing agent that combines with the metal ions of the metal salt to produce a white to off-white substance. A surface treatment method for an aluminum-based metal having an oxide film according to the seventh invention of the present application includes a fixing agent that binds the aluminum-based metal having an oxide film with metal ions of the following metal salts to produce a white to gray-white substance. Step (A) of immersing or electrolyzing in an aqueous solution, the aluminum metal treated in the above step (A),
PH containing at least one metal salt of titanium salt, zinc salt, calcium salt, barium salt, strontium salt, magnesium salt or aluminum salt
Step (B) of immersing or electrolyzing in an aqueous solution of 0.5 to 8.5, the aluminum-based metal obtained in the above step (B),
PH0.5 to 8.5 containing at least one metal salt of titanium salt, zinc salt, calcium salt, barium salt, strontium salt, magnesium salt, or aluminum salt, an organic polar solvent and/or a chelate compound, and a fixing silicate. Step (C) of immersing in or electrolyzing the aqueous solution of the aluminum-based metal obtained in the above step (C),
It is characterized by comprising a coloring step (D) by dyeing or electrolysis. The method for surface treatment of an aluminum-based metal having an oxide film according to the eighth aspect of the present invention includes a fixing agent that binds the aluminum-based metal having an oxide film with metal ions of the following metal salts to produce a white to gray-white substance. Step (A) of immersing or electrolyzing in an aqueous solution, the aluminum metal treated in the above step (A),
PH containing at least one metal salt of titanium salt, zinc salt, calcium salt, barium salt, strontium salt, magnesium salt or aluminum salt
Step (B) of immersing or electrolyzing in an aqueous solution of 0.5 to 8.5, the aluminum-based metal obtained in the above step (B),
PH0.5 to 8.5 containing at least one metal salt of titanium salt, zinc salt, calcium salt, barium salt, strontium salt, magnesium salt, or aluminum salt, an organic polar solvent and/or a chelate compound, and a fixing silicate. Step (C) of immersing in or electrolyzing the aqueous solution of the aluminum-based metal obtained in the above step (C),
A step (D) of immersing the aluminum-based metal obtained in the above step (D) in an aqueous solution containing a fixing agent that combines with the metal ions of the metal salt to form a white to gray-white substance, or electrolyzing the aluminum-based metal in the aqueous solution. ,
It is characterized by comprising a step (E) of coloring by dyeing or electrolysis. Hereinafter, first, the first invention of the present application will be explained in detail. In the present invention, first, an aluminum-based metal having an oxide film is immersed in an aqueous solution containing a fixing agent that combines with metal ions of the following metal salts to produce a white to grayish white substance, or electrolyzing it in the aqueous solution ( Implement A). The aluminum-based metal having an oxide film used in the present invention refers to an aluminum-based metal in which an oxide film is formed chemically or electrochemically (anodic oxidation) on the surface of aluminum or an alloy containing aluminum. It is preferable to use an anodic oxide film because a pastel-like film with even better characteristics can be obtained. A known anodic oxidation method is employed to form an anodic oxide film on the aluminum-based metal. For example, in inorganic acids such as sulfuric acid, phosphoric acid, and chromic acid, organic acids such as oxalic acid, paraphenolsulfonic acid, sulfosalicylic acid, and malonic acid, or aqueous solutions such as sodium hydroxide and trisodium phosphate, direct current An anodic oxide film is formed by electrolysis using AC, pulse, PR waves, or AC/DC superposition method. The fixing agent used in the present invention is one that combines with metal ions of the following metal salts to produce a white to grayish white substance. The above-mentioned fixing agent enlarges the micropores of the oxide film part of the aluminum-based metal having the above-mentioned oxide film to facilitate the penetration of the following metal salts, and allows the following metal salts to penetrate into the enlarged micropores. , which binds to the metal ions of the intruded metal salt and fixes the product in the micropores, and the white to gray-white product obtained by the combination of the metal ions and the fixing agent This is for uniformly and densely adhering to the oxide film part. Specific examples of the above-mentioned fixing agents include phosphoric acid, sodium phosphate, sodium hydrogen phosphate, potassium phosphate, potassium hydrogen phosphate, boric acid, sodium borate, potassium borate, sodium silicate, potassium silicate, chromium acid potassium, sulfuric acid, sodium sulfate, sodium hydrogen sulfate, potassium sulfate,
Examples include potassium hydrogen sulfate, alkali metal hydroxides, carbonates, and bicarbonates, and these fixing agents may be used alone or in combination of two or more if desired. There are some cases where it is even more effective. The concentration of the above-mentioned fixing agent is 0.1-300g/, preferably 0.5-200g/, particularly preferably 1-300g/
It is desirable to set the amount to 100g/.If the concentration is less than 0.1g/, the concentration will be too thin and the effect as a fixing agent will be insufficient.On the other hand, if it exceeds 300g/, the concentration will be too high and the oxide film of the aluminum metal will be destroyed. When the liquid temperature is lowered (for example, in winter), the fixing agent may precipitate and the concentration may change, which is not preferable because the properties of the film may deteriorate. In the present invention, when an aluminum metal having an oxide film is immersed in an aqueous solution containing the above-mentioned fixing agent and its surface is pretreated, this aqueous solution is charged into a treatment tank, and the concentration is adjusted with water if desired. The temperature is usually room temperature to 75°C, preferably
The temperature may be adjusted to 40 to 70°C, and the aluminum metal may be immersed in this solution for usually 10 seconds to 30 minutes, preferably 1 minute to 20 minutes. Further, in the present invention, the surface of the aluminum metal having an oxide film may be pretreated by immersing it in the above aqueous solution and electrolyzing it in the solution. In this case, the aqueous solution is charged into a treatment tank. ,
The concentration may be adjusted in the same manner as above, and electrolytic treatment may be performed in the aqueous solution by a known method such as a direct current method, an alternating current method, a pulse method, a PR method, or an AC/DC superposition method. In this case, the electrolytic conditions are as follows: liquid temperature is room temperature to 80°C, preferably 20 to 70°C, voltage is 1 to 50V, and current density is 1 to 80°C.
150A/m ² , electrolysis time 10 seconds to 30 minutes, preferably 1
minutes to 20 minutes. In the present invention, the aluminum-based metal treated in the above step (A) has a pH of 0.5 containing at least one metal salt selected from titanium salts, zinc salts, calcium salts, barium salts, strontium salts, magnesium salts, and aluminum salts. - Perform the step (B) of immersion in or electrolysis in the aqueous solution of 8.5. The metal salt used in the present invention is one that combines with the above-mentioned fixing agent to produce a white to grayish-white substance, or produces a white to grayish-white hydrated metal oxide upon hydrolysis, and is soluble in water. Or it is a sparingly soluble metal salt. The above metal salts include titanium salt, zinc salt,
Calcium salt, barium salt, strontium salt,
At least one selected from magnesium salts and aluminum salts is mentioned. The concentration of the above metal salt is 0.01 to 200g/,
Preferably 0.1-150g/, particularly preferably 1-150g/
100g/ is desirable; if it is less than 0.01g/, the concentration will be too thin and a sufficiently dense film may not be obtained; on the other hand, if it exceeds 200g/, the concentration will be too high and the liquid temperature will drop. (e.g. in winter) metal salts precipitate and the concentration changes, resulting in
This is not preferable because it may become difficult to manage the aqueous solution or the properties may deteriorate. The pH of the aqueous solution containing the above metal salt is
It is desirable to adjust the pH to a range of 0.5 to 8.5, especially 1.5 to 6.5; if the pH is less than 0.5, the acidity may become too high and the oxide film on the surface of the aluminum metal may be destroyed; If the pH exceeds 8.5, the oxide film of the aluminum metal may be destroyed, which is not preferable. In the above pH range, it is understood that a few molecules of hydrated metal oxides aggregate to form a colorless and transparent to slightly turbid hydrosol. The above-mentioned PH regulators include inorganic acids such as sulfuric acid and phosphoric acid, organic acids such as acetic acid, citric acid, succinic acid, gluconic acid, glycine, malonic acid, oxalic acid, and formic acid;
alkali metal hydroxides, carbonates or bicarbonates,
Examples include ammonia and alkali metal salts of organic acids. One type of these acids or bases or alkali metal salts of organic acids may be used, or two or more types may be used in combination, and the combination thereof may be particularly effective in some cases. In the present invention, when an aluminum-based metal having an oxide film is immersed in the above aqueous solution and its surface is pretreated, the above aqueous solution is charged into a treatment tank,
If desired, adjust the concentration with water, adjust the temperature of the aqueous solution to usually room temperature to 75°C, preferably 40 to 70°C, and add the above aluminum metal to this solution, usually for 10 seconds to 30 minutes, preferably All you have to do is soak it for 1 minute to 20 minutes. Further, in the present invention, the surface of the aluminum metal having an oxide film may be pretreated by immersing it in the aqueous solution and electrolyzing it in the solution. In this case, the aqueous solution is charged into a treatment tank. ,
The concentration may be adjusted in the same manner as above, and electrolytic treatment may be performed in the aqueous solution by a known method such as a direct current method, an alternating current method, a pulse method, a PR method, or an AC/DC superposition method. In this case, the electrolytic conditions are as follows: liquid temperature is room temperature to 80°C, preferably 20 to 70°C, voltage is 1 to 50V, and current density is 1 to 80°C.
150A/ ^m2 . Electrolysis time 10 seconds to 30 minutes, preferably 1
minutes to 20 minutes. In the present invention, next, the treated aluminum metal obtained in the above step (B) is treated with at least one of titanium salts, zinc salts, calcium salts, barium salts, strontium salts, magnesium salts, or aluminum salts. A step (C) of immersing in or electrolyzing in an aqueous solution of pH 0.5 to 8.5 containing a metal salt and an organic polar solvent and/or a chelate compound is carried out. This step (C) is for chemically or electrolytically forming a dense and uniform white to grayish-white film on the surface of the treated aluminum-based metal obtained in the above step (B). The aqueous solution used in this step (C) is the same as that used in the above step (B).
The aqueous solution used in the process contains at least one organic polar solvent or chelate compound, and other requirements such as the type and concentration of metal salt, PH range, immersion conditions and electrolysis conditions are as described above. This is the same as step (B). The aqueous solution used in step (C) is the aqueous solution in step (B) above containing an organic polar solvent and/or a chelate compound. That is, PH0.5 containing the above metal salt and organic polar solvent.
An aqueous solution containing the above metal salt and chelate compound may be used instead.
An aqueous solution with a pH of 8.5 to 8.5 may be used, or an aqueous solution with a pH of 0.5 to 8.5 containing the metal salt, an organic polar solvent, and a chelate compound may be used instead. The organic polar solvent used in the present invention is not particularly limited as long as it is a water-soluble polar solvent, and specifically includes, for example, lower alcohols such as methanol and ethanol, acetone,
Ketones such as methyl ethyl ketone and diethyl ketone, ethers such as ether and diethyl ether, amines such as methylamine, ethylamine, monoethanolamine, diethanolamine or triethanolamine, glycols such as ethylene glycol, diethylene glycol, propylene glycol, polyethylene glycol, etc. Examples include glycerin, tetrahydrofuran, dimethylformamide, dimethylacetamide, etc., but among these, lower alcohols and amines are preferable because they can prevent the product from being removed from the metal salt during sealing, that is, decolorization. . In addition, the concentration of the organic polar solvent is 0.1~
Preferably, it is 50% by volume. That is, since the aqueous solution used in step (C) contains the organic polar solvent,
By simply immersing an aluminum-based metal with an oxide film, a dense and uniform white to grayish-white film with excellent properties can be formed on the surface.
If the concentration of the organic polar solvent is less than 0.1% by volume, it may become too dilute and sufficient effects may not be obtained.
On the other hand, if it exceeds 50% capacity, the concentration becomes too high and affects the solubility of the metal salt, which is not preferable. In addition, the chelate compound used in the present invention is important for improving the stability of metal ions in the aqueous solution used in step (C), and for reducing the surface area (oxide film) when the aluminum-based metal is immersed or electrolyzed in the aqueous solution. In addition to stabilizing the hydrated metal oxides generated in step 1) and the sol of the product of metal ions and the above-mentioned fixing agent (hereinafter referred to as hydrated metal oxides, etc.), it also stabilizes the oxide film. The above-mentioned hydrated metal oxides etc. can be extremely easily, uniformly and firmly bonded to the oxide film portion of the aluminum-based metal. The above-mentioned hydrated metal oxides refer to metal oxides in which one or more water molecules are coordinated, hydrated metal oxides, metal oxides, or aggregates thereof. Specific representative examples of the above chelate compounds include ethylenediaminetetraacetic acid and its sodium salt, trans-1,2-cyclohexanediaminetetraacetic acid, diethylenetriaminepentaacetic acid, ethylenediaminediacetic acid, 3,6-dioxa-1,8-octane. Polyaminocarboxylic acids such as diaminetetraacetic acid, N-(2-hydroxyethyl)iminodiacetic acid, triethylenetetraminehexaacetic acid, diamines such as ethylenediamine, triethanolamine, triethylenetetramine, etc. containing two or more in one molecule. Amine compounds with amine groups, ethyl acetoacetate, nitrilotriacetic acid, formalin, oxalic acid, maleic acid, tartaric acid, malic acid, citric acid, succinic acid,
Examples include polybasic acids such as gluconic acid or glycine, and soluble metal salts thereof. These include chelate compounds that are insoluble in water, but by adding an organic polar solvent,
In other words, it dissolves in a mixture of water and an organic polar solvent. The concentration of the above chelate compound varies depending on the metal salt used and the type and concentration of the organic polar solvent added if necessary, but is generally 0.1 to 50.
A range of g/g/ is preferable; if it is less than 0.1 g/, the effect will be poor, and if it exceeds 50 g/, the effect will be limited and may affect the solubility of the metal salt, which is not desirable. Next, the second invention of the present application will be explained in detail. The second invention of the present application is an improvement of the first invention, and is obtained by the first invention.
The object of the present invention is to obtain an opaque white to grayish-white colored aluminum-based metal which has better properties than an opaque white to grayish-white colored aluminum-based metal. That is, the second invention of the present application is to immerse an aluminum-based metal having an oxide film in an aqueous solution containing a fixing agent that combines with metal ions of the following metal salts to produce a white to grayish-white substance, or electrolyzes it in the aqueous solution. Step (A): The aluminum metal treated in step (A) above is
PH containing at least one metal salt of titanium salt, zinc salt, calcium salt, barium salt, strontium salt, magnesium salt or aluminum salt
Step (B) of immersing or electrolyzing in an aqueous solution of 0.5 to 8.5, the aluminum-based metal obtained in the above step (B),
PH containing at least one metal salt of titanium salt, zinc salt, calcium salt, barium salt, strontium salt, magnesium salt or aluminum salt, and an organic polar solvent and/or chelate compound
Step (C) of immersing or electrolyzing in an aqueous solution of 0.5 to 8.5, the aluminum-based metal obtained in the above step (C),
This method is characterized by comprising a step (D) of immersion in or electrolysis in an aqueous solution containing a fixing agent that combines with the metal ions of the metal salt to produce a white to off-white substance. The second invention of the present application is to oxidize the opaque white to grayish white products from the metal salts (products of metal ions of the metal salts and the fixing agent and hydrated metal oxides) in the first invention. This is for more uniformly and densely adhering to the oxide film part of the aluminum-based metal having the film. In other words, the second invention of the present application uses an aluminum-based metal having an oxide film in the process of the first invention.
A metal salt such as titanium is pooled in the fine pores of the oxide film of the aluminum-based metal obtained in the same manner as in steps (A) to (C), and the aluminum-based metal is added to the oxide film of the aluminum-based metal. This method is characterized by the addition of a step (D) of immersion in or electrolysis in an aqueous solution containing a fixing agent that combines with the metal ions of the metal salt to produce a white to off-white substance. The second invention of the present application is an improvement of the first invention of the present application, and therefore relates to an aluminum-based metal having an oxide film and a bonding agent used in steps (A) to (C) of the present invention. , metal salt, organic polar solvent, chelate compound, immersion conditions, electrolytic conditions, etc. are the same as in the first invention of the present application. In the present invention, the fixing agent used in step (D) includes phosphoric acid, sodium phosphate, sodium hydrogen phosphate, potassium phosphate, potassium hydrogen phosphate, boric acid, sodium borate, sodium silicate, Examples thereof include potassium silicate, potassium chromate, sulfuric acid, sodium sulfate, sodium hydrogen sulfate, potassium sulfate, potassium hydrogen sulfate, and alkali metal hydroxides, carbonates, and bicarbonates. Also, the concentration of this fixing agent is 0.1 to 300g/
, preferably 0.5 to 200 g/, particularly preferably 1 to 100 g/; if it is less than 0.1 g/, the concentration will be too thin and the effect as a fixing agent will be insufficient; on the other hand, if it exceeds 300 g/, the concentration will be too low. If the temperature becomes too high and the oxide film of the aluminum metal is destroyed, or if the liquid temperature drops (for example, in winter)
The adhesive may precipitate and the concentration may change.
As a result, the properties of the film may deteriorate, which is not preferable. Next, the third invention of the present application will be explained in detail. That is, the step (A) of immersing an aluminum-based metal having an oxide film in an aqueous solution containing a fixing agent that combines with metal ions of the metal salts below to produce a white to grayish-white substance or electrolyzing it in the aqueous solution; A PH containing at least one metal salt of titanium salt, zinc salt, calcium salt, barium salt, strontium salt, magnesium salt, or aluminum salt, using the aluminum-based metal treated in (A)
Step (B) of immersing or electrolyzing in an aqueous solution of 0.5 to 8.5, the aluminum-based metal obtained in the above step (B),
PH containing at least one metal salt of titanium salt, zinc salt, calcium salt, barium salt, strontium salt, magnesium salt or aluminum salt, and an organic polar solvent and/or chelate compound
Step (C) of immersing or electrolyzing in an aqueous solution of 0.5 to 8.5, the aluminum-based metal obtained in the above step (C),
A step (D) of coloring by dyeing or electrolysis. The third invention of the present application is to color the white to grayish-white aluminum metal obtained in the first invention in a pastel color, and the aluminum metal having an oxide film to be white to grayish white. This is a step (D) added to the step of coloring, that is, steps (A) to (C) of the first invention of the present application. In the present invention, an aluminum-based metal having an oxide film is subjected to the same steps (A) to (C) as in the first invention above to form an opaque white to gray-white film on the surface of the aluminum-based metal. Perform (A to C). The conditions for this step (A to C) are the same as in the first invention. A step (D) of coloring the aluminum-based metal having a white to grayish-white film obtained through the above steps (A) to (C) by dyeing or electrolysis is carried out. In the coloring step (D), any coloring method can be adopted, such as coloring by dyeing or coloring by metal salt. Both water-soluble dyes and oil solution dyes can be used as the above-mentioned dyes. Specifically, commercially available acid dyes, basic dyes, and direct dyes that are generally used for coloring white to gray-white coatings on aluminum-based metals are used. Examples include food coloring, mordant dyes, oil solution dyes, etc. Coloring methods using dyes include known coloring methods such as immersion in a dye bath, spraying,
Methods such as tanbo, transfer, screen printing, coil, etc. may be employed. Specific representative examples of the above-mentioned coloring metal salts include various metal salts such as iron, nickel, cobalt, manganese, chromium, cadmium, tin, copper, lead, indium, and vanadium. One type of these metal salts for coloring may be used, or
Two or more types may be used in combination, and there are cases where a combination of two or more types is effective. The concentration of the above-mentioned coloring metal salt varies depending on the type and combination of coloring metal salts used, but is usually 1 to 200g/, preferably 3 to 100g/.
It is appropriately selected from within the range of g/. When coloring the surface of an aluminum-based metal having a white to gray-white film using the above metal salt for coloring, an aqueous solution of the above metal salt for coloring is charged into a treatment tank, and then an organic polar solvent and/or a chelate compound is added. or further water to adjust the concentration, or adjust the pH with a pH adjuster, and adjust the temperature of the aqueous solution to usually room temperature to 95°C, preferably 40 to 90°C.
The above aluminum-based metal is immersed in this solution for usually 10 seconds to 30 minutes, preferably 1 minute to 20 minutes, or electrolyzed to form a dense and uniform film with pastel colors with excellent properties. It is obtained through processing. Further, as the electrolytic coloring method, a known electrolytic coloring method such as an AC electrolytic coloring method, a DC electrolytic coloring method, or other electrolytic coloring methods such as an AC/DC superimposition method can be employed. In this case, the electrolytic conditions are as follows: liquid temperature is room temperature to 95°C, preferably 30 to 80°C, voltage is 1 to 50V, and current density is 1 to 95°C.
150 A/m ² and electrolysis time from 1 minute to 60 minutes. Next, the fourth invention of the present application will be explained in detail. That is, the fourth invention of the present application is to immerse an aluminum-based metal having an oxide film in an aqueous solution containing a fixing agent that combines with metal ions of the following metal salts to produce a white to grayish-white substance, or to electrolyze it in the aqueous solution. step (A), the aluminum-based metal treated in the above step (A),
PH containing at least one metal salt of titanium salt, zinc salt, calcium salt, barium salt, strontium salt, magnesium salt or aluminum salt
Step (B) of immersing or electrolyzing in an aqueous solution of 0.5 to 8.5, the aluminum-based metal obtained in the above step (B),
PH containing at least one metal salt of titanium salt, zinc salt, calcium salt, barium salt, strontium salt, magnesium salt or aluminum salt, and an organic polar solvent and/or chelate compound
step (C) of immersion in or electrolysis in an aqueous solution of 0.5 to 8.5; a fixing agent that combines the aluminum-based metal having an oxide film with the metal ion of the metal salt to produce a white to gray-white substance; Step (D) of immersing or electrolyzing in an aqueous solution, the aluminum-based metal obtained in the above step (D),
It is characterized by comprising a step (E) of coloring by dyeing or electrolysis. A fourth invention of the present application is to color the white to grayish-white aluminum metal obtained in the second invention in a pastel color, the aluminum metal having an oxide film being white to grayish white. A step (E) is further added to the step of coloring, that is, steps (A) to (D) of the second invention of the present application. In the present invention, an aluminum-based metal having an oxide film is subjected to the same steps (A) to (D) as in the second invention to form an opaque white to gray-white film on the surface of the aluminum-based metal ( Perform steps A to D). The conditions for this step (A to D) are the same as in the second invention. A step (E) of coloring the aluminum-based metal having a white to grayish-white film obtained through the above steps (A) to (D) by immersion or electrolysis is carried out. The present invention involves coloring an aluminum-based metal having an oxide film through steps (A) to (D) to make the oxide film more uniform, dense, and opaque white to grayish white, and turning the white to grayish white oxide film into a pastel color. It is colored. In the coloring step of this step (E), coloring can be carried out by the same method as the coloring step of step (D) of the third invention of the present application. Next, the fifth invention of the present application will be explained in detail. That is, the step (A) of immersing an aluminum-based metal having an oxide film in an aqueous solution containing a fixing agent that combines with metal ions of the metal salts below to produce a white to grayish-white substance or electrolyzing it in the aqueous solution; The aluminum metal treated with (A),
PH containing at least one metal salt of titanium salt, zinc salt, calcium salt, barium salt, strontium salt, magnesium salt or aluminum salt
Step (B) of immersion in or electrolysis in an aqueous solution of 0.5 to 8.5; (C) immersion in or electrolysis in an aqueous solution with a pH of 0.5 to 8.5 containing at least one metal salt of an aluminum salt, an organic polar solvent and/or a chelate compound, and a fixing silicate; It is characterized by this. The fifth invention of the present application is an improvement of the first invention of the present application, and in the first invention, the step
A fixing silicate is added to the aqueous solution used in (C), and other conditions are the same as in the first invention of the present application. That is, when a fixing silicate is added to the aqueous solution used in step (C) in the first invention of the present application, the surface part (oxide film part) of the aluminum-based metal having an oxide film becomes a white to gray-white product ( The fixing silicate transfers the product to the surface area during subsequent washing, drying, and sealing. It fixes more reliably and prevents its detachment (bleaching) and film destruction (film loss), thereby further preventing the film from being destroyed during processes such as sealing. The fixing silicate is not particularly limited as long as it can be dissolved or dispersed in a fine powder form in an aqueous solution of water and an organic polar solvent and/or a chelate compound. Soluble alkali silicates such as sodium silicate, potassium silicate or lithium silicate, and aluminum silicate,
Examples include fine particle aqueous dispersions of potassium aluminum silicate, sodium aluminum silicate, and calcium aluminum silicate. In addition, the concentration of the fixing silicate depends on the type and concentration of the organic polar solvent and chelate compound used,
Furthermore, it varies depending on the type of silicate, etc., but usually,
The amount is desirably in the range of 0.1 to 100 g/, preferably 0.5 to 50 g/. Furthermore, the sixth invention of the present application will be explained in detail. That is, the sixth invention of the present application is to immerse an aluminum-based metal having an oxide film in an aqueous solution containing a fixing agent that combines with metal ions of the following metal salts to produce a white to grayish-white substance, or to electrolyze it in the aqueous solution. step (A), the aluminum-based metal treated in the above step (A),
PH containing at least one metal salt of titanium salt, zinc salt, calcium salt, barium salt, strontium salt, magnesium salt or aluminum salt
Step (B) of immersing or electrolyzing in an aqueous solution of 0.5 to 8.5, the aluminum-based metal obtained in the above step (B),
PH0.5 to 8.5 containing at least one metal salt of titanium salt, zinc salt, calcium salt, barium salt, strontium salt, magnesium salt, or aluminum salt, an organic polar solvent and/or a chelate compound, and a fixing silicate. Step (C) of immersing in or electrolyzing the aqueous solution of the aluminum-based metal obtained in the above step (C),
This method is characterized by comprising a step (D) of immersion in or electrolysis in an aqueous solution containing a fixing agent that combines with the metal ions of the metal salt to produce a white to off-white substance. A sixth invention of the present application is an improvement of the second invention, and includes a step in the second invention.
A fixing silicate is added to the aqueous solution used in (C), and other conditions are the same as in the second invention of the present application. That is, when a fixing silicate is added to the aqueous solution used in step (C) in the second invention of the present application,
A white to off-white opaque oxide film with extremely excellent properties is obtained. The type, concentration, etc. of the fixing silicate are the same as in the fifth invention of the present application. Furthermore, the seventh invention of the present application will be explained in detail. That is, the step (A) of immersing an aluminum-based metal having an oxide film in an aqueous solution containing a fixing agent that combines with the metal ion of the metal salt below to produce a white to grayish-white substance or electrolyzing it in the aqueous solution; The aluminum metal treated in (A),
PH containing at least one metal salt of titanium salt, zinc salt, calcium salt, barium salt, strontium salt, magnesium salt or aluminum salt
Step (B) of immersing or electrolyzing in an aqueous solution of 0.5 to 8.5, the aluminum-based metal obtained in the above step (B),
PH0.5 to 8.5 containing at least one metal salt of titanium salt, zinc salt, calcium salt, barium salt, strontium salt, magnesium salt, or aluminum salt, an organic polar solvent and/or a chelate compound, and a fixing silicate. Step (C) of immersing in or electrolyzing the aqueous solution of the aluminum-based metal obtained in the above step (C),
A step (D) of coloring by dyeing or electrolysis. A seventh invention of the present application is an improvement of the third invention, and includes a step in the third invention.
A fixing silicate is added to the aqueous solution used in (C), and other conditions are the same as in the third invention. The fixing silicate used in the seventh invention of the present application is for further preventing detachment (bleaching) and film destruction (film loss) during sealing, etc., and is used in the fifth invention. The same fixing silicates used in the invention can be used. In addition, the concentration of the fixing silicate depends on the type and concentration of the organic polar solvent and chelate compound used,
Although it also varies depending on the type of silicate, it is usually 0.1
The amount is desirably in the range of ~100g/, preferably 0.5-50g/. Furthermore, the eighth scope of the present application will be explained in detail. That is, the eighth invention of the present application is to immerse an aluminum-based metal having an oxide film in an aqueous solution containing a fixing agent that combines with metal ions of the following metal salts to produce a white to grayish white substance, or to electrolyze it in the aqueous solution. step (A), the aluminum-based metal treated in the above step (A),
PH containing at least one metal salt of titanium salt, zinc salt, calcium salt, barium salt, strontium salt, magnesium salt or aluminum salt
Step (B) of immersing or electrolyzing in an aqueous solution of 0.5 to 8.5, the aluminum-based metal obtained in the above step (B),
PH0.5 to 8.5 containing at least one metal salt of titanium salt, zinc salt, calcium salt, barium salt, strontium salt, magnesium salt, or aluminum salt, an organic polar solvent and/or a chelate compound, and a fixing silicate. Step (C) of immersing in or electrolyzing the aqueous solution of the aluminum-based metal obtained in the above step (C),
A step (D) of immersing the aluminum-based metal obtained in the above step (D) in an aqueous solution containing a fixing agent that combines with the metal ion of the metal salt to produce a white to gray-white substance, or electrolyzing the aluminum-based metal in the aqueous solution. ,
It is characterized by comprising a step (E) of coloring by dyeing or electrolysis. The eighth invention of the present application is an improvement of the seventh invention, and in the seventh invention, step (A)
An aluminum-based metal having a transparent white to grayish-white oxide film treated through process (C),
The product is characterized by the addition of a step (D) of immersion in or electrolysis in an aqueous solution containing a fixing agent that combines with the metal ions of the metal salt in the oxide film to produce a white to grayish white substance. It is. The type and concentration of the fixing agent used in the present invention are the same as those in the above invention. The eighth invention of the present application is to treat an aluminum-based metal having an oxide film with a fixing agent before treating it with a metal salt such as titanium, thereby forming a white to gray-white color from the metal salt. The substance is fixed to the oxide film of the aluminum-based metal, and then this white to gray-white product is more securely fixed to the oxide film of the aluminum-based metal, and the opaque white to gray-white oxide product thus obtained is fixed to the oxide film of the aluminum-based metal. The coating is colored more uniformly and minutely by dyeing or electrolysis. For such dyeing or electrolytic coloring, the above-mentioned No. 3
The dyes and coloring metal salts shown in the invention are used,
The density and coloring method can be the same as in the third invention. The colored film obtained by the above method may be sealed by a known method. (e) Effect The surface treatment agent of the present invention has the above structure, and
The fixing agent in the surface treatment agent used in (A) first enlarges the micropores in the oxide film part of the aluminum-based metal that has an oxide film, and thereby allows metal salts such as titanium salts to be used in the subsequent process. Then, the metal salt is allowed to enter into the enlarged micropores, and the metal ions in the infiltrated metal salt and the fixing agent pooled in the micropores are bonded, and the metal ions and A white to grayish-white substance produced by combining with a fixing agent can be uniformly, firmly and densely formed on the oxide film, and as a result, this opaque white to grayish-white film can be formed. It has the effect of preventing destruction of the film (film loss), decolorization during sealing, and peeling of the film after sealing. Furthermore, the present invention provides a method for treating the aluminum-based metal having an oxide film, which has been treated with a fixing agent, in the above step (B), thereby eliminating the white to gray-white products in the subsequent step (C). It facilitates the precipitation of reaction products of metal salts and fixing agents and hydrated metal oxides, and forms a more delicate and uniform film through these two steps (B) and (C). It has an effect. In addition, since the aqueous solution used in the above step (C) contains an organic polar solvent, the degree of freedom of the white to grayish-white product hydrosol is reduced.
When an aluminum-based metal having an oxide film is immersed or electrolyzed, the above-mentioned products are deposited on the oxide film due to a change in pH. In addition, when an organic polar solvent is added to the aqueous solution used in step (C) above, the organic polar solvent may cause water molecules coordinated to the colloidal particles in the hydrosol of the white to gray-white products and the above-mentioned It also has the effect of depriving the water molecules coordinated to the oxide film and continuously producing a hydrosol of fine products on the surface of the aluminum metal. Furthermore, when a chelate compound is used in the aqueous solution used in the above step (C), the chelate compound not only stabilizes the sol of metal ions and products generated due to changes in pH, but also particularly stabilizes the oxide film. It has the effect of bonding the above-mentioned products extremely easily, uniformly, and firmly to the oxide film portion of the aluminum-based metal having the following properties. Among these chelate compounds, when polyaminocarboxylic acids are used in particular, products from metal salts are likely to be fixed within the oxide film of an aluminum-based metal having an oxide film. The reason for this is that in polyaminocarboxylic acids, the -COO ^- bonded to one nitrogen atom is bonded to the product from the metal salt, and the -COO - bonded to the other nitrogen atom.
This is because COO ^- combines with Al ³⁺ that is electrostatically coordinated within the micropores of the aluminum-based metal oxide film, and thus the products from the metal salt are fixed within the micropores of the oxide film. be understood. In particular, when a fixing silicate is added to the aqueous solution used in step (C) above, products generated due to changes in pH etc. are fixed on the oxide film of the aluminum metal, thereby sealing the pores. It is possible to reliably prevent the desorption of products during the process, that is, the decolorization of the aluminum-based metal, and as a result, it is possible to obtain a more excellent white to grayish-white film. In addition, the aluminum-based metal having an oxide film that has been treated with a fixing agent is treated with a metal salt through steps (B) and (C), and then further treated with an aqueous solution containing a fixing agent to form the oxide film. This has the effect of further improving the adhesion between the metal salt and the white to off-white products from the metal salt. The white to grayish-white film obtained by the present invention has the ability to be colored into a uniform and delicate pastel color by known dyeing or electrolytic coloring without the need for special techniques. . (f) Examples Hereinafter, the present invention will be explained in detail based on Examples, but the present invention is not limited thereto. Creation of pure aluminum plate with anodic oxide film The anodic oxide film used in each example and each comparative example described below was prepared by pre-treating a pure aluminum plate with a sulfuric acid concentration of 180g/
, bath temperature 20℃, current density 2A/ ^dm2 , 25
Obtained by direct current electrolysis for one minute. In this case, the thickness of the anodic oxide film was 15 μm. Examples 1 to 11 The above aluminum plate was immersed in an aqueous solution containing the fixing agent shown in Table 1 () at a temperature of 20°C and a voltage of 10 to
Direct current electrolysis was carried out for 10 minutes under the conditions of 20 V and a current density of 1 to 2 A/dm ² (Step A), and the aluminum plate thus obtained was placed in an aqueous solution shown in Table 1 () at a temperature
The aluminum plate obtained in step (B) was immersed at 65°C for 15 minutes in the aqueous solution shown in Table 1 () for 15 minutes at 65°C to obtain an opaque white film. (Step C).

【table】

【table】

【table】

【table】

[Table] Examples 12 to 25 The above aluminum plate was immersed in an aqueous solution containing the adhesive shown in Table 2 () at a temperature of 20°C and a voltage of 10 to
Direct current electrolysis was carried out for 10 minutes under the conditions of 20 V and a current density of 1 to 2 A/dm ² (Step A), and the aluminum plate thus obtained was heated in an aqueous solution at the temperature shown in Table 2 ().
The aluminum plate obtained in step (B) was immersed at 65°C for 15 minutes in the aqueous solution shown in Table 2 () for 15 minutes at 65°C to obtain an opaque white film. (Step C). Examples 26 to 36 The above aluminum plate was immersed in an aqueous solution containing the fixing agent shown in Table 3 () at a temperature of 20°C and a voltage of 10 to
Direct current electrolysis was carried out for 10 minutes under the conditions of 20 V and a current density of 1 to 2 A/ ^dm2 (Step A), and the aluminum plate thus obtained was placed in the aqueous solution shown in Table 3 () at the temperature.
The aluminum plate obtained in step (B) was immersed at 65°C for 15 minutes in the aqueous solution shown in Table 3 () for 15 minutes at 65°C to obtain an opaque white film. (Step C). Examples 37 to 72 After obtaining an opaque white oxide film through each step (A) to step (C) in Examples 1 to 36,
This white oxide film was further immersed in an aqueous solution containing a fixing agent corresponding to each example and electrolyzed under the same conditions. Examples 73-144 The white films obtained in Examples 1-72 were colored by immersing them in the aqueous solutions shown in Table 4 at a temperature of 65° C. for 20 minutes.

【table】

【table】

【table】

【table】

【table】

【table】

【table】

【table】

【table】

【table】

【table】

【table】

【table】

[Table] Examples 145 to 155 The above aluminum plate was immersed in an aqueous solution containing the fixing agent shown in Table 5 () at a temperature of 20°C and a voltage of 10 to
Direct current electrolysis was carried out for 10 minutes under the conditions of 20 V and a current density of 1 to 2 A/ ^dm2 (Step A), and the aluminum plate thus obtained was placed in an aqueous solution shown in Table 5 () at a temperature of
The aluminum plate obtained in step (B) was immersed at 65°C for 15 minutes in the aqueous solution shown in Table 5 () for 15 minutes at 65°C to obtain an opaque white film. (Step C). Examples 156 to 166 After obtaining an opaque white oxide film through each step (A) to step (C) in Examples 145 to 155, this white oxide film was further processed according to each example. Those used were immersed in an aqueous solution containing a fixing agent and electrolyzed under the same conditions. Examples 167-188 The white films obtained in Examples 145-166 were colored by immersing them in the aqueous solutions shown in Table 6 at a temperature of 65° C. for 20 minutes.

【table】

【table】

【table】

【table】

【table】

【table】

【table】

【table】 Table 7 shows the coloring state of each of the above examples.

【table】

【table】

【table】

【table】

【table】

【table】

[Table] appeared, and it was pale white with uneven color.
Comparative Example 1 The above aluminum plate was coated with 30g of calcium acetate/
Electrolyze with an aqueous solution of 0.5g/sulfuric acid (30℃) at AC voltage 20V for 20 minutes, and after washing with water, 30g/sulfuric acid/
An opaque white film was obtained on the surface of the aluminum plate by electrolyzing an aqueous solution (30℃) at an AC voltage of 20V for 20 minutes. Comparative Example 2 The above aluminum plate was treated with aluminum sulfate 50
g/ and 0.5 g/ of sulfuric acid in an aqueous solution (60°C).
After immersing for 20 minutes and washing with water, the aluminum plate was immersed in an aqueous solution containing 20 g of phosphoric acid (40°C) for 20 minutes to obtain an opaque white film on the surface of the aluminum plate. Comparative Example 3 The above aluminum plate was exposed to AC voltage in an aqueous solution (25°C) containing 15 g of zinc sulfate and 0.5 g of sulfuric acid.
After electrolyzing at 20V for 10 minutes and washing with water, add 20g of oxalic acid/
An opaque white film was obtained on the surface of the aluminum plate by electrolyzing an aqueous solution (25℃) at a DC voltage of 15V for 20 minutes. Comparative Example 4 The above aluminum plate was treated with 20g of calcium acetate/
and sulfuric acid 0.5 g/aqueous solution (60℃) for 30 minutes, and after washing with water, sulfuric acid 20 g/aqueous solution (35
℃) for 20 minutes at an AC voltage of 20 V to obtain an opaque white film on the surface of the aluminum plate. Comparative Example 5 The above aluminum plate was treated with sodium selenite 10
Electrolyze with an aqueous solution (30°C) of 15g/g/g of sulfuric acid at an AC voltage of 15V for 5 minutes, color it yellow, and wash with water.
Immerse for 20 minutes in an aqueous solution (60℃) of 30g/g of phosphoric acid (30℃), and after washing with water, apply an AC voltage to an aqueous solution (30℃) of 30g/g of phosphoric acid.
Electrolysis was carried out at 20V for 20 minutes to obtain an opaque cream-colored film on the surface of the aluminum plate. Comparative Example 6 The above aluminum plate was treated with 15g of calcium acetate/
Electrolyzed with sulfuric acid 0.5g/aqueous solution (25℃) at DC voltage 15V for 5 minutes, washed with water, and immersed in 30g/trisodium phosphate solution (40℃) for 20 minutes to form an opaque white film on the surface of the aluminum plate. I got it. Comparative Example 7 The above aluminum plate was treated with magnesium nitrate 30
Electrolyze with an aqueous solution (30℃) of 1 g/g/g of sulfuric acid and 1 g/g of sulfuric acid at an AC voltage of 20 V for 10 minutes, and after washing with water, add sodium carbonate.
An opaque white film was obtained on the surface of the aluminum plate by immersing it in a 30 g/aqueous solution (40°C) for 20 minutes. Comparative Example 8 An aluminum plate was electrolyzed with a coloring solution (25°C) containing 4 g of stannous sulfate and 15 g of sulfuric acid at an AC voltage of 15 V for 5 minutes to give it an olive color, and after washing with water, it was washed with 10 g of calcium acetate and 0.5 g of sulfuric acid. Electrolyze at 20V AC voltage for 5 minutes with an aqueous solution (30℃) of 10g/g of trisodium phosphate (40℃) after washing with water.
An opaque beige film was obtained on the surface of the aluminum plate by immersion in water for 20 minutes. Comparative Examples 9 to 19 Colored films were obtained in the same manner as in Examples 1 to 11, except that the organic polar solvent was removed from the aqueous solution used in step (C). As shown in the color tone results in Table 7, the white film obtained according to the first invention of the present application was uniform and dense, and almost no color unevenness was observed.
In addition, although sealing and other treatments were performed, there was hardly any decolorization, peeling of the film after sealing, or film destruction (film loss). The white film obtained by the second invention of the present application is
It was more uniform and dense, and no color unevenness was observed. In addition, although treatments such as sealing were performed, there was hardly any decolorization, peeling of the film after sealing, or film destruction (film loss). The pastel-colored film obtained according to the third invention of the present application was uniform, dense, and bright. The pastel-colored coating obtained according to the fourth invention of the present application was more uniform and dense, and was superior to the colored coating according to the third invention in terms of vividness. The white film obtained by the fifth invention of the present application is
It is uniform and dense, and the white film is adhered to the aluminum plate by the fixing silicate.
There were almost no problems such as discoloration or film destruction (film loss) during sealing. The white film obtained according to the sixth invention of the present application is
It was uniform, dense, and had a bright white color. Furthermore, the pastel-colored film obtained according to the seventh invention of the present application was more uniform, dense, and vivid, and no peeling or decolorization of the film was observed. Furthermore, the pastel colored film obtained according to the eighth invention of the present application was most excellent in properties such as color clarity, denseness, and adhesion. In each of the above examples, the fixing agent was fixed to the oxide film part by an electrolytic method, but instead of this, a good colored film could also be obtained by a dipping method, and furthermore, a well-known screen printing method using a dye could be used. When the film was colored using a heat transfer method, a thermal transfer method, or a dipping method, and the pores were sealed using a known method, a uniform and dense film with a bright pastel color was obtained. On the other hand, each of the comparative examples had significant color unevenness, and furthermore, decolorization during sealing and peeling of the film due to drying were observed. (g) Effect of the invention The surface treatment method of the present invention fixes a specific adhesive to the oxide film part of an aluminum-based metal having an oxide film, and uses this adhesive to fix a white to gray-white product into an oxide film. Since it is fixed in close contact with the oxide film part, this white to grayish-white film is fixed to the oxide film part, resulting in problems such as discoloration, film breakage, and peeling of the film during subsequent sealing. This has the effect of producing a uniform and dense film with almost no formation. In addition, aluminum-based metals with an oxide film,
If an opaque white to gray-white film is colored and then treated with a fixing agent, an opaque white to gray-white film with even better properties can be obtained, and this film can be made more uniform and dense by dyeing or electrolysis. It has a coloring effect. Furthermore, when a fixing silicate is added to the aqueous solution used in the above step C, the fixing silicate removes the white to gray-white product from the metal salt onto the surface of the aluminum metal (oxidized This has the effect of fixing on the film and preventing its desorption, that is, decolorization, thereby producing a film with even better properties.

Claims (1)

[Scope of Claims] 1. A step of immersing an aluminum-based metal having an oxide film in an aqueous solution containing a fixing agent that combines with metal ions of the metal salts below to produce a white to grayish-white substance, or electrolyzing it in the aqueous solution ( A), the aluminum metal treated in step (A) above,
PH containing at least one metal salt of titanium salt, zinc salt, calcium salt, barium salt, strontium salt, magnesium salt or aluminum salt
Step (B) of immersing or electrolyzing in an aqueous solution of 0.5 to 8.5, the aluminum-based metal obtained in the above step (B),
PH containing at least one metal salt of titanium salt, zinc salt, calcium salt, barium salt, strontium salt, magnesium salt or aluminum salt, and an organic polar solvent and/or chelate compound
1. A method for surface treatment of an aluminum-based metal having an oxide film, comprising: (C) immersion in or electrolysis in an aqueous solution of 0.5 to 8.5. 2 The fixing agent is phosphoric acid, sodium phosphate, sodium hydrogen phosphate, potassium phosphate, potassium hydrogen phosphate, boric acid, sodium borate, potassium borate, sodium silicate, potassium silicate, potassium chromate, sulfuric acid, Sodium sulfate, sodium hydrogen sulfate, potassium sulfate, potassium hydrogen sulfate,
2. The method for surface treating an aluminum metal having an oxide film according to claim 1, wherein the oxide film is an alkali metal hydroxide, carbonate or bicarbonate. 3. The method for surface treatment of an aluminum-based metal having an oxide film according to claim 1 or 2, wherein the concentration of the fixing agent is 0.1 to 300 g/2. 4. The method for surface treatment of an aluminum-based metal having an oxide film according to any one of claims 1 to 3, wherein the concentration of the metal salt is 0.01 to 200 g/3. 5. The method for surface treatment of an aluminum metal having an oxide film according to any one of claims 1 to 4, wherein the concentration of the organic polar solvent is 0.1 to 50% by volume. 6 Chelate compound is polyaminocarboxylic acid,
6. A method for surface treating an aluminum-based metal having an oxide film according to any one of claims 1 to 5, which is a polybasic acid or an amine compound having two or more amine groups in one molecule. 7. The method for surface treatment of an aluminum-based metal having an oxide film according to any one of claims 1 to 6, wherein the concentration of the chelate compound is 0.1 to 50 g/. 8 Step (A) of immersing an aluminum-based metal having an oxide film in an aqueous solution containing a fixing agent that combines with metal ions of the metal salt below to produce a white to grayish-white substance, or electrolyzing it in the aqueous solution, the above step ( The aluminum metal treated with A)
PH containing at least one metal salt of titanium salt, zinc salt, calcium salt, barium salt, strontium salt, magnesium salt or aluminum salt
Step (B) of immersing or electrolyzing in an aqueous solution of 0.5 to 8.5, the aluminum-based metal obtained in the above step (B),
PH containing at least one metal salt of titanium salt, zinc salt, calcium salt, barium salt, strontium salt, magnesium salt or aluminum salt, and an organic polar solvent and/or chelate compound
Step (C) of immersing or electrolyzing in an aqueous solution of 0.5 to 8.5, the aluminum-based metal obtained in the above step (C),
An aluminum-based product having an oxide film, comprising a step (D) of immersion in or electrolysis in an aqueous solution containing a fixing agent that combines with the metal ions of the metal salt to form a white to grayish white substance. Metal surface treatment method. 9 The fixing agent is phosphoric acid, sodium phosphate, sodium hydrogen phosphate, potassium phosphate, potassium hydrogen phosphate, boric acid, sodium borate, potassium borate, sodium silicate, potassium silicate, potassium chromate, sulfuric acid. , sodium sulfate, sodium hydrogen sulfate, potassium sulfate, potassium hydrogen sulfate, alkali metal hydroxide, carbonate, or bicarbonate. Method. 10. The method for surface treatment of an aluminum-based metal having an oxide film according to claim 8 or 9, wherein the concentration of the fixing agent is 0.1 to 300 g/. 11. The method for surface treatment of an aluminum-based metal having an oxide film according to any one of claims 8 to 10, wherein the concentration of the metal salt is 0.01 to 200 g/. 12. The method for surface treatment of an aluminum metal having an oxide film according to any one of claims 8 to 11, wherein the concentration of the organic polar solvent is 0.1 to 50% by volume. 13. Claim 8, wherein the chelate compound is a polyaminocarboxylic acid, a polybasic acid, or an amine compound having two or more amine groups in one molecule.
A method for surface treatment of an aluminum-based metal having an oxide film according to any one of items 1 to 12. 14. The method for surface treatment of an aluminum-based metal having an oxide film according to any one of claims 8 to 13, wherein the concentration of the chelate compound is 0.1 to 50 g/. 15 Aluminum metal with oxide film,
Step (A) of immersing or electrolyzing in an aqueous solution containing a fixing agent that combines with the metal ion of the metal salt below to produce a white to grayish white substance, the aluminum-based metal treated in the above step (A),
PH containing at least one metal salt of titanium salt, zinc salt, calcium salt, barium salt, strontium salt, magnesium salt or aluminum salt
Step (B) of immersing or electrolyzing in an aqueous solution of 0.5 to 8.5, the aluminum-based metal obtained in the above step (B),
PH containing at least one metal salt of titanium salt, zinc salt, calcium salt, barium salt, strontium salt, magnesium salt or aluminum salt, and an organic polar solvent and/or chelate compound
Step (C) of immersing in or electrolyzing in an aqueous solution of 0.5 to 8.5. The aluminum-based metal obtained in the above step (C) is
A method for surface treatment of aluminum-based metals having an oxide film, comprising a step (D) of coloring by dyeing or electrolysis. 16 The fixing agent is phosphoric acid, sodium phosphate, sodium hydrogen phosphate, potassium phosphate, potassium hydrogen phosphate, boric acid, sodium borate, potassium borate, sodium silicate, potassium silicate, potassium chromate, sulfuric acid, The method for surface treatment of aluminum-based metals having an oxide film according to claim 15, which is sodium sulfate, sodium hydrogen sulfate, potassium sulfate, potassium hydrogen sulfate, alkali metal hydroxide, carbonate, or bicarbonate. . 17. The method for surface treatment of an aluminum-based metal having an oxide film according to claim 15 or 16, wherein the concentration of the fixing agent is 0.1 to 300 g/. 18. The method for surface treatment of an aluminum-based metal having an oxide film according to any one of claims 15 to 17, wherein the concentration of the metal salt is 0.01 to 200 g/. 19. The method for surface treatment of an aluminum-based metal having an oxide film according to any one of claims 15 to 18, wherein the concentration of the organic polar solvent is 0.1 to 50% by volume. 20 Claim 1 in which the chelate compound is a polyaminocarboxylic acid, a polybasic acid, or an amine compound having two or more amine groups in one molecule
A method for surface treatment of an aluminum-based metal having an oxide film according to any one of items 5 to 19. 21. The method for surface treatment of an aluminum-based metal having an oxide film according to any one of claims 15 to 20, wherein the concentration of the chelate compound is 0.1 to 50 g/. 22 Aluminum metal with oxide film,
Step (A) of immersing or electrolyzing in an aqueous solution containing a fixing agent that combines with the metal ion of the metal salt below to produce a white to grayish white substance, the aluminum-based metal treated in the above step (A),
PH containing at least one metal salt of titanium salt, zinc salt, calcium salt, barium salt, strontium salt, magnesium salt or aluminum salt
Step (B) of immersing or electrolyzing in an aqueous solution of 0.5 to 8.5, the aluminum-based metal obtained in the above step (B),
PH containing at least one metal salt of titanium salt, zinc salt, calcium salt, barium salt, strontium salt, magnesium salt or aluminum salt, and an organic polar solvent and/or chelate compound
Step (C) of immersing or electrolyzing in an aqueous solution of 0.5 to 8.5, the aluminum-based metal obtained in the above step (C),
A step (D) of immersing or electrolyzing the aluminum metal obtained in the above step (D) in an aqueous solution containing a fixing agent that combines with the metal ion of the metal salt to produce a white to grayish white substance. ,
A method for surface treatment of aluminum-based metals having an oxide film, comprising a step (E) of coloring by dyeing or electrolysis. 23 The fixing agent is phosphoric acid, sodium phosphate, sodium hydrogen phosphate, potassium phosphate, potassium hydrogen phosphate, boric acid, sodium borate, potassium borate, sodium silicate, potassium silicate, potassium chromate, sulfuric acid, The method for surface treatment of aluminum-based metals having an oxide film according to claim 22, which is sodium sulfate, sodium hydrogen sulfate, potassium sulfate, potassium hydrogen sulfate, alkali metal hydroxide, carbonate, or bicarbonate. . 24. The method for surface treatment of an aluminum-based metal having an oxide film according to claim 22 or 23, wherein the concentration of the fixing agent is 0.1 to 300 g/. 25. The method for surface treatment of an aluminum-based metal having an oxide film according to any one of claims 22 to 24, wherein the concentration of the metal salt is 0.01 to 200 g/. 26. The method for surface treatment of an aluminum metal having an oxide film according to any one of claims 22 to 25, wherein the concentration of the organic polar solvent is 0.1 to 50% by volume. 27 Claim 2 in which the chelate compound is a polyaminocarboxylic acid, a polybasic acid, or an amine compound having two or more amine groups in one molecule
A method for surface treatment of an aluminum-based metal having an oxide film according to any one of Items 2 to 26. 28. The method for surface treatment of an aluminum-based metal having an oxide film according to any one of claims 22 to 27, wherein the concentration of the chelate compound is 0.1 to 50 g/. 29 Aluminum metal with oxide film,
Step (A) of immersing or electrolyzing in an aqueous solution containing a fixing agent that combines with the metal ion of the metal salt below to produce a white to grayish white substance, the aluminum-based metal treated in the above step (A),
PH containing at least one metal salt of titanium salt, zinc salt, calcium salt, barium salt, strontium salt, magnesium salt or aluminum salt
Step (B) of immersing or electrolyzing in an aqueous solution of 0.5 to 8.5, the aluminum-based metal obtained in the above step (B),
PH0.5 to 8.5 containing at least one metal salt of titanium salt, zinc salt, calcium salt, barium salt, strontium salt, magnesium salt, or aluminum salt, an organic polar solvent and/or a chelate compound, and a fixing silicate. A method for surface treatment of an aluminum-based metal having an oxide film, comprising: (C) immersing it in an aqueous solution or electrolyzing it in the aqueous solution. 30 The fixing agent is phosphoric acid, sodium phosphate, sodium hydrogen phosphate, potassium phosphate, potassium hydrogen phosphate, boric acid, sodium borate, potassium borate, sodium silicate, potassium silicate, potassium chromate, sulfuric acid, The method for surface treatment of aluminum-based metals having an oxide film according to claim 29, which is sodium sulfate, sodium hydrogen sulfate, potassium sulfate, potassium hydrogen sulfate, alkali metal hydroxide, carbonate, or bicarbonate. . 31. The method for surface treatment of an aluminum-based metal having an oxide film according to claim 29 or 30, wherein the concentration of the fixing agent is 0.1 to 300 g/. 32. The method for surface treatment of an aluminum-based metal having an oxide film according to any one of claims 29 to 31, wherein the concentration of the metal salt is 0.01 to 200 g/. 33. The method for surface treatment of an aluminum-based metal having an oxide film according to any one of claims 29 to 32, wherein the concentration of the organic polar solvent is 0.1 to 50% by volume. 34 Claim 2 in which the chelate compound is a polyaminocarboxylic acid, a polybasic acid, or an amine compound having two or more amine groups in one molecule
A method for surface treatment of an aluminum-based metal having an oxide film according to any one of items 9 to 33. 35. The method for surface treatment of an aluminum-based metal having an oxide film according to any one of claims 29 to 34, wherein the concentration of the chelate compound is 0.1 to 50 g/. 36. The method for surface treatment of an aluminum-based metal having an oxide film according to any one of claims 29 to 35, wherein the fixable silicate is an alkali silicate. 37. The method for surface treatment of an aluminum-based metal having an oxide film according to any one of claims 29 to 36, wherein the concentration of the fixing silicate is 0.1 to 100 g/. 38 Aluminum metal with oxide film,
Step (A) of immersing or electrolyzing in an aqueous solution containing a fixing agent that combines with the metal ion of the metal salt below to produce a white to grayish white substance, the aluminum-based metal treated in the above step (A),
PH containing at least one metal salt of titanium salt, zinc salt, calcium salt, barium salt, strontium salt, magnesium salt or aluminum salt
Step (B) of immersing or electrolyzing in an aqueous solution of 0.5 to 8.5, the aluminum-based metal obtained in the above step (B),
PH0.5 to 8.5 containing at least one metal salt of titanium salt, zinc salt, calcium salt, barium salt, strontium salt, magnesium salt, or aluminum salt, an organic polar solvent and/or a chelate compound, and a fixing silicate. step (C) of immersing or electrolyzing the aqueous solution of the aluminum-based metal obtained in the above step (C),
An aluminum-based product having an oxide film, comprising a step (D) of immersion in or electrolysis in an aqueous solution containing a fixing agent that combines with the metal ions of the metal salt to form a white to grayish white substance. Metal surface treatment method. 39 The fixing agent is phosphoric acid, sodium phosphate, sodium hydrogen phosphate, potassium phosphate, potassium hydrogen phosphate, boric acid, sodium borate, potassium borate, sodium silicate, potassium silicate, potassium chromate, sulfuric acid, The method for surface treatment of aluminum-based metals having an oxide film according to claim 38, which is sodium sulfate, sodium hydrogen sulfate, potassium sulfate, potassium hydrogen sulfate, alkali metal hydroxide, carbonate, or bicarbonate. . 40. The method for surface treatment of an aluminum-based metal having an oxide film according to claim 38 or 39, wherein the concentration of the fixing agent is 0.1 to 300 g/. 41. The method for surface treatment of an aluminum-based metal having an oxide film according to any one of claims 38 to 40, wherein the concentration of the metal salt is 0.01 to 200 g/. 42. The method for surface treatment of an aluminum metal having an oxide film according to any one of claims 38 to 41, wherein the concentration of the organic polar solvent is 0.1 to 50% by volume. 43 Claim 3 in which the chelate compound is a polyaminocarboxylic acid, a polybasic acid, or an amine compound having two or more amine groups in one molecule
A method for surface treatment of an aluminum-based metal having an oxide film according to any one of items 8 to 42. 44. The method for surface treatment of an aluminum-based metal having an oxide film according to any one of claims 38 to 43, wherein the concentration of the chelate compound is 0.1 to 50 g/. 45. The method for surface treatment of an aluminum-based metal having an oxide film according to any one of claims 38 to 44, wherein the fixable silicate is an alkali silicate. 46. The method for surface treatment of an aluminum-based metal having an oxide film according to any one of claims 38 to 45, wherein the fixing silicate has a concentration of 0.1 to 100 g/. 47 Aluminum metal with oxide film,
Step (A) of immersing or electrolyzing in an aqueous solution containing a fixing agent that combines with the metal ion of the metal salt below to produce a white to grayish white substance, the aluminum-based metal treated in the above step (A),
PH containing at least one metal salt of titanium salt, zinc salt, calcium salt, barium salt, strontium salt, magnesium salt or aluminum salt
Step (B) of immersing or electrolyzing in an aqueous solution of 0.5 to 8.5, the aluminum-based metal obtained in the above step (B),
PH0.5 to 8.5 containing at least one metal salt of titanium salt, zinc salt, calcium salt, barium salt, strontium salt, magnesium salt, or aluminum salt, an organic polar solvent and/or a chelate compound, and a fixing silicate. Step (C) of immersing in or electrolyzing the aqueous solution of the aluminum-based metal obtained in the above step (C),
A method for surface treatment of aluminum-based metals having an oxide film, comprising a step (D) of coloring by dyeing or electrolysis. 48 The fixing agent is phosphoric acid, sodium phosphate, sodium hydrogen phosphate, potassium phosphate, potassium hydrogen phosphate, boric acid, sodium borate, potassium borate, sodium silicate, potassium silicate, potassium chromate, sulfuric acid, The method for surface treatment of aluminum-based metals having an oxide film according to claim 47, which is sodium sulfate, sodium hydrogen sulfate, potassium sulfate, potassium hydrogen sulfate, alkali metal hydroxide, carbonate, or bicarbonate. . 49. The method for surface treatment of an aluminum-based metal having an oxide film according to claim 47 or 48, wherein the concentration of the fixing agent is 0.1 to 300 g/. 50. The method for surface treatment of an aluminum-based metal having an oxide film according to any one of claims 47 to 49, wherein the concentration of the metal salt is 0.01 to 200 g/. 51. The method for surface treatment of an aluminum-based metal having an oxide film according to any one of claims 47 to 50, wherein the concentration of the organic polar solvent is 0.1 to 50% by volume. 52 Claim 4 in which the chelate compound is a polyaminocarboxylic acid, a polybasic acid, or an amine compound having two or more amine groups in one molecule
A method for surface treatment of an aluminum-based metal having an oxide film according to any one of items 7 to 51. 53. The method for surface treatment of an aluminum-based metal having an oxide film according to any one of claims 47 to 52, wherein the concentration of the chelate compound is 0.1 to 50 g/. 54. The method for surface treatment of an aluminum-based metal having an oxide film according to any one of claims 47 to 53, wherein the fixable silicate is an alkali silicate. 55. The method for surface treatment of an aluminum-based metal having an oxide film according to any one of claims 47 to 54, wherein the concentration of the fixing silicate is 0.1 to 100 g/. 56 Aluminum metal with oxide film,
Step (A) of immersing or electrolyzing in an aqueous solution containing a fixing agent that combines with the metal ion of the metal salt below to produce a white to grayish white substance, the aluminum-based metal treated in the above step (A),
PH containing at least one metal salt of titanium salt, zinc salt, calcium salt, barium salt, strontium salt, magnesium salt or aluminum salt
Step (B) of immersing in or electrolyzing an aqueous solution of 0.5 to 8.5. The aluminum-based metal obtained in the above step (B) is
PH0.5 to 8.5 containing at least one metal salt of titanium salt, zinc salt, calcium salt, barium salt, strontium salt, magnesium salt, or aluminum salt, an organic polar solvent and/or a chelate compound, and a fixing silicate. Step (C) of immersing in or electrolyzing the aqueous solution of the aluminum-based metal obtained in the above step (C),
A step (D) of immersing the aluminum-based metal obtained in the above step (D) in an aqueous solution containing a fixing agent that combines with the metal ions of the metal salt to form a white to gray-white substance, or electrolyzing the aluminum-based metal in the aqueous solution. ,
A method for surface treatment of aluminum-based metals having an oxide film, comprising a step (E) of coloring by dyeing or electrolysis. 57 The fixing agent is phosphoric acid, sodium phosphate, sodium hydrogen phosphate, potassium phosphate, potassium hydrogen phosphate, boric acid, sodium borate, potassium borate, sodium silicate, potassium silicate, potassium chromate, sulfuric acid, The method for surface treatment of aluminum-based metals having an oxide film according to claim 56, which is sodium sulfate, sodium hydrogen sulfate, potassium sulfate, potassium hydrogen sulfate, alkali metal hydroxide, carbonate, or bicarbonate. . 58. The method for surface treatment of an aluminum-based metal having an oxide film according to claim 56 or 57, wherein the concentration of the fixing agent is 0.1 to 300 g/. 59. The method for surface treatment of an aluminum-based metal having an oxide film according to any one of claims 56 to 58, wherein the concentration of the metal salt is 0.01 to 200 g/. 60. The method for surface treatment of an aluminum metal having an oxide film according to any one of claims 56 to 59, wherein the concentration of the organic polar solvent is 0.1 to 50% by volume. 61 Claim 5 in which the chelate compound is a polyaminocarboxylic acid, a polybasic acid, or an amine compound having two or more amine groups in one molecule
A method for surface treatment of an aluminum-based metal having an oxide film according to any one of items 6 to 60. 62. The method for surface treatment of an aluminum-based metal having an oxide film according to any one of claims 56 to 61, wherein the concentration of the chelate compound is 0.1 to 50 g/. 63. The method for surface treatment of an aluminum-based metal having an oxide film according to any one of claims 56 to 62, wherein the fixing silicate is an alkali silicate. 64. The method for surface treatment of an aluminum-based metal having an oxide film according to any one of claims 56 to 63, wherein the concentration of the fixing silicate is 0.1 to 100 g/.